Crystal structures of ten phosphane chalcogenide complexes of gold(III) chloride and bromide

Upmann, D.; Bockfeld, D.; Jones, P.G.; Târcoveanu, E.

doi:10.1107/S2056989024002032

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 80| Part 4| April 2024| Pages 355-369

https://doi.org/10.1107/S2056989024002032

Open

access

Crystal structures of ten phosphane chalcogenide complexes of gold(III) chloride and bromide

Daniel Upmann,^a Dirk Bockfeld,^a Peter G. Jones ^a ^* and Eliza Târcoveanu ^a

^aInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-braunschweig.de

Edited by C. Schulzke, Universität Greifswald, Germany (Received 5 February 2024; accepted 1 March 2024; online 12 March 2024)

Phosphane chalcogenides and their metal complexes, Part 7. Part 6: Upmann et al. (2024).

The structures of ten phosphane chalcogenide complexes of gold(III) halides, with general formula R¹_3–nR²_nPEAuX₃ (R¹ = t-butyl; R² = i-propyl; n = 0 to 3; E = S or Se; X = Cl or Br) are presented. The eight possible chlorido derivatives are: 9a, n = 3, E = S; 10a, n = 2, E = S; 11a, n = 1, E = S; 12a, n = 0, E = S; 13a, n = 3, E = Se; 14a, n = 2, E = Se; 15a, n = 1, E = Se; and 16a, n = 0, E = Se, and the corresponding bromido derivatives are 9b–16b in the same order. Structures were obtained for 9a, 10a (and a second polymorph 10aa), 11a (and its deuterochloroform monosolvate 11aa), 12a (as its dichloromethane monosolvate), 14a, 15a (as its deuterochloroform monosolvate 15aa, in which the solvent molecule is disordered over two positions), 9b, 11b, 13b and 15b. The structures of 11a, 15a, 11b and 15b form an isotypic set, and those of compounds 10aa and 14a form an isotypic pair. All structures have Z′ = 1. The gold(III) centres show square-planar coordination geometry and the chalcogenide atoms show approximately tetrahedral angles (except for the very wide angle in 12a, probably associated with the bulky t-butyl groups). The bond lengths at the gold atoms are lengthened with respect to the known gold(I) derivatives, and demonstrate a considerable trans influence of S and Se donor atoms on a trans Au—Cl bond. Each compound with an isopropyl group shows a short intramolecular contact of the type C—H_methine⋯X_cis; these may be regarded as intramolecular ‘weak’ hydrogen bonds, and they determine the orientation of the AuX₃ groups. The molecular packing is analysed in terms of various short contacts such as weak hydrogen bonds C—H⋯X and contacts between the heavier atoms, such as X⋯X (9a, 10aa, 11aa, 15aa and 9b), S⋯S (10aa, 11a and 12a) and S⋯Cl (10a). The packing of the polymorphs 10a and 10aa is thus quite different. The solvent molecules take part in C—H⋯Cl hydrogen bonds; for 15aa, a disordered solvent region at z ≃ 0 is observed. Structure 13b involves unusual inversion-symmetric dimers with Se⋯Au and Se⋯Br contacts, further connected by Br⋯Br contacts.

Keywords: crystal structure; gold(III) halides; phosphane chalcogenides; secondary interactions.

CCDC references: 2156390; 2156786; 2156787; 2156789; 2156790; 2156867; 2156868; 2156869; 2156870; 2338821; 2338822; 2338823; 2338824

1. Chemical context

In Part 6 of this series (Upmann et al., 2024 ), we presented the structures of sixteen halogenido-gold(I) complexes of various trialkylphosphane chalcogenides. Appropriate background material, together with a summary of our previous results, can be found in that publication and is not repeated here.

In this paper, we report the structures of ten trialkylphosphane chalcogenide complexes of gold(III) trihalides, with general formula (^tBu_3–nⁱPr_nP=E)AuX₃, of which there are sixteen possible permutations of n, the chalcogenide E (restricted to S or Se) and X (for X = Cl or Br; triiodido complexes are generally not accessible). The eight theoretically obtainable trichlorido derivatives are: 9a, n = 3, E = S; 10a, n = 2, E = S; 11a, n = 1, E = S; 12a, n = 0, E = S; 13a, n = 3, E = Se; 14a, n = 2, E = Se; 15a, n = 1, E = Se; and 16a, n = 0, E = Se, and the corresponding tribromido derivatives are 9b–16b in the same order. These are generally obtained from the gold(I) precursors (numbered analogously as 1a–8a and 1b–8b in our previous publication; Upmann et al., 2024) using one mole equivalent of elemental bromine or PhICl₂ [commonly known as iodobenzene dichloride; systematic name dichloro(phenyl)-λ³-iodane] as oxidizing agents. However, ^tBu₃P = SeAuCl, 8a, was found to be unstable, thus ruling out the preparation of 16a; 13a also proved to be unstable; and the attempted syntheses of 10b, 12b, 14b and 16b led to different products, to be described in future publications. This left ten successfully synthesized compounds, leading to thirteen structures; 10a was obtained as two polymorphs (the second termed 10aa), whereas structures of 11a and 15a were determined both solvent-free and as the deuterochloroform monosolvates 11aa and 15aa. Compound 12a was obtained as a dichloromethane monosolvate. The structures of 10a, 11a, 14a and 15aa were briefly presented in a preliminary communication (Upmann & Jones, 2013 ), but have been re-refined using a much more recent version of SHELXL (2019 rather than 1997; Sheldrick, 2015 ) and are discussed in more detail here. Details of the composition of each compound studied are given in Table 1.

Table 1
Compositions of the R¹R²R³PEAuX₃ structures presented in this paper (see Scheme)

Compound	R¹	R²	R³	E	X	Comments
9a	ⁱPr	ⁱPr	ⁱPr	S	Cl
10a	ⁱPr	ⁱPr	^tBu	S	Cl
10aa	ⁱPr	ⁱPr	^tBu	S	Cl	Second polymorph of 10a
11a	ⁱPr	^tBu	^tBu	S	Cl
11aa	ⁱPr	^tBu	^tBu	S	Cl	CDCl₃ solvate of 11a
12a	^tBu	^tBu	^tBu	S	Cl	CH₂Cl₂ solvate
14a	ⁱPr	ⁱPr	^tBu	Se	Cl
15a	ⁱPr	^tBu	^tBu	Se	Cl
15aa	ⁱPr	^tBu	^tBu	Se	Cl	CDCl₃ solvate of 15a
9b	ⁱPr	ⁱPr	ⁱPr	S	Br
11b	ⁱPr	^tBu	^tBu	S	Br
13b	ⁱPr	ⁱPr	ⁱPr	Se	Br
15b	ⁱPr	^tBu	^tBu	Se	Br

We had earlier synthesized all four permutations (E = S or Se, X = Cl or Br) of Ph₃PEAuX₃ (Taouss et al., 2015 ), but were unable to determine any of the structures because of extensive ‘streaking’ of the diffraction images.

2. Structural commentary

General comments: All compounds crystallize with one formula unit in the asymmetric unit. The molecular structures are shown in Figs. 1–13 ; selected molecular dimensions are given in Tables 2–14 . The trans (to E) halogen atoms are numbered as X1 throughout. All comparisons to the analogous series of gold(I) compounds refer to our previous paper (Upmann et al., 2024). As expected, all compounds show square planar coordination geometry (angle ranges ca 87–95 and 172–179°) at the gold(III) centres; the largest mean deviation from the plane containing the gold atom and all donor atoms is 0.078 Å for 11b. The approximately tetrahedral angles (except for 12a) at the chalcogenide atoms would also be expected (discussed below in more detail).

Table 2
Selected geometric parameters (Å, °) for 9a

Au1—Cl3	2.2818 (5)	S1—P1	2.0574 (7)
Au1—Cl2	2.2846 (5)	P1—C2	1.829 (2)
Au1—Cl1	2.3064 (5)	P1—C3	1.8317 (19)
Au1—S1	2.3250 (5)	P1—C1	1.8387 (19)

Cl3—Au1—Cl2	175.341 (18)	C2—P1—C3	108.01 (9)
Cl3—Au1—Cl1	90.151 (18)	C2—P1—C1	115.39 (9)
Cl2—Au1—Cl1	88.999 (19)	C3—P1—C1	106.80 (9)
Cl3—Au1—S1	92.249 (18)	C2—P1—S1	111.92 (7)
Cl2—Au1—S1	88.545 (18)	C3—P1—S1	113.32 (7)
Cl1—Au1—S1	177.472 (17)	C1—P1—S1	101.34 (7)
P1—S1—Au1	106.70 (2)

Cl3—Au1—S1—P1	−72.41 (3)	Au1—S1—P1—C3	−51.87 (8)
Cl2—Au1—S1—P1	112.19 (3)	Au1—S1—P1—C1	−165.92 (7)
Au1—S1—P1—C2	70.57 (7)

Table 3
Selected geometric parameters (Å, °) for 10a

Au1—Cl3	2.2818 (6)	S1—P1	2.0538 (9)
Au1—Cl2	2.2837 (6)	P1—C2	1.843 (3)
Au1—Cl1	2.2989 (7)	P1—C3	1.845 (2)
Au1—S1	2.3294 (7)	P1—C1	1.875 (3)

Cl3—Au1—Cl2	177.46 (2)	C2—P1—C3	109.58 (12)
Cl3—Au1—Cl1	88.54 (2)	C2—P1—C1	109.67 (13)
Cl2—Au1—Cl1	89.23 (3)	C3—P1—C1	109.94 (12)
Cl3—Au1—S1	94.93 (2)	C2—P1—S1	102.70 (10)
Cl2—Au1—S1	87.39 (2)	C3—P1—S1	111.45 (9)
Cl1—Au1—S1	174.30 (2)	C1—P1—S1	113.25 (9)
P1—S1—Au1	111.29 (3)

Cl3—Au1—S1—P1	56.17 (4)	Au1—S1—P1—C3	−77.45 (10)
Cl2—Au1—S1—P1	−122.80 (4)	Au1—S1—P1—C1	47.12 (11)
Au1—S1—P1—C2	165.31 (9)

Table 4
Selected geometric parameters (Å, °) for 10aa

Au1—Cl3	2.2815 (8)	S1—P1	2.0592 (11)
Au1—Cl2	2.2851 (8)	P1—C3	1.836 (3)
Au1—Cl1	2.3116 (8)	P1—C2	1.839 (3)
Au1—S1	2.3281 (8)	P1—C1	1.871 (3)

Cl3—Au1—Cl2	176.43 (3)	C3—P1—C2	110.36 (15)
Cl3—Au1—Cl1	90.10 (3)	C3—P1—C1	108.88 (16)
Cl2—Au1—Cl1	89.18 (3)	C2—P1—C1	111.39 (14)
Cl3—Au1—S1	93.11 (3)	C3—P1—S1	111.66 (12)
Cl2—Au1—S1	87.51 (3)	C2—P1—S1	101.38 (11)
Cl1—Au1—S1	176.43 (3)	C1—P1—S1	113.03 (11)
P1—S1—Au1	111.18 (4)

Cl3—Au1—S1—P1	61.27 (5)	Au1—S1—P1—C2	168.88 (11)
Cl2—Au1—S1—P1	−122.25 (5)	Au1—S1—P1—C1	49.55 (12)
Au1—S1—P1—C3	−73.62 (13)

Table 5
Selected geometric parameters (Å, °) for 11a

Au1—Cl2	2.2881 (5)	S1—P1	2.0665 (6)
Au1—Cl3	2.2889 (5)	P1—C3	1.8442 (19)
Au1—Cl1	2.3080 (5)	P1—C2	1.8741 (18)
Au1—S1	2.3346 (5)	P1—C1	1.8765 (18)

Cl2—Au1—Cl3	175.769 (17)	C3—P1—C2	112.66 (9)
Cl2—Au1—Cl1	89.44 (2)	C3—P1—C1	108.88 (9)
Cl3—Au1—Cl1	89.35 (2)	C2—P1—C1	113.61 (8)
Cl2—Au1—S1	87.963 (19)	C3—P1—S1	109.17 (7)
Cl3—Au1—S1	93.175 (19)	C2—P1—S1	101.48 (6)
Cl1—Au1—S1	177.237 (19)	C1—P1—S1	110.81 (6)
P1—S1—Au1	111.35 (2)

Cl2—Au1—S1—P1	−117.55 (3)	Au1—S1—P1—C2	169.16 (6)
Cl3—Au1—S1—P1	66.53 (3)	Au1—S1—P1—C1	48.21 (7)
Au1—S1—P1—C3	−71.70 (7)

Table 6
Selected geometric parameters (Å, °) for 11aa

Au1—Cl3	2.2871 (5)	S1—P1	2.0622 (6)
Au1—Cl2	2.2903 (5)	P1—C3	1.8465 (19)
Au1—Cl1	2.3060 (4)	P1—C1	1.8737 (18)
Au1—S1	2.3312 (4)	P1—C2	1.8778 (18)

Cl3—Au1—Cl2	177.050 (16)	C3—P1—C1	108.94 (8)
Cl3—Au1—Cl1	88.505 (17)	C3—P1—C2	112.62 (8)
Cl2—Au1—Cl1	89.783 (17)	C1—P1—C2	114.39 (8)
Cl3—Au1—S1	92.936 (17)	C3—P1—S1	108.73 (6)
Cl2—Au1—S1	88.609 (16)	C1—P1—S1	110.75 (6)
Cl1—Au1—S1	175.816 (16)	C2—P1—S1	101.09 (6)
P1—S1—Au1	111.96 (2)

Cl3—Au1—S1—P1	69.79 (3)	Au1—S1—P1—C1	52.74 (7)
Cl2—Au1—S1—P1	−112.73 (3)	Au1—S1—P1—C2	174.37 (6)
Au1—S1—P1—C3	−66.93 (7)

Table 7
Selected geometric parameters (Å, °) for 12a

Au1—Cl3	2.2860 (5)	P1—C3	1.888 (2)
Au1—Cl2	2.2894 (6)	P1—C2	1.8906 (19)
Au1—Cl1	2.3013 (5)	P1—C1	1.906 (2)
Au1—S1	2.3323 (5)	P1—S1	2.0658 (6)

Cl3—Au1—Cl2	176.996 (18)	C3—P1—C1	111.29 (9)
Cl3—Au1—Cl1	88.53 (2)	C2—P1—C1	111.38 (9)
Cl2—Au1—Cl1	89.55 (2)	C3—P1—S1	110.17 (6)
Cl3—Au1—S1	93.402 (18)	C2—P1—S1	111.66 (6)
Cl2—Au1—S1	88.30 (2)	C1—P1—S1	99.33 (6)
Cl1—Au1—S1	174.441 (19)	P1—S1—Au1	117.50 (3)
C3—P1—C2	112.33 (9)

C3—P1—S1—Au1	−78.75 (7)	Cl3—Au1—S1—P1	82.19 (3)
C2—P1—S1—Au1	46.80 (8)	Cl2—Au1—S1—P1	−100.28 (3)
C1—P1—S1—Au1	164.36 (6)

Table 8
Selected geometric parameters (Å, °) for 14a

Au1—Cl3	2.2803 (19)	Se1—P1	2.211 (2)
Au1—Cl2	2.283 (2)	P1—C3	1.832 (8)
Au1—Cl1	2.326 (2)	P1—C2	1.845 (8)
Au1—Se1	2.4393 (8)	P1—C1	1.864 (8)

Cl3—Au1—Cl2	176.18 (8)	C3—P1—C2	110.8 (4)
Cl3—Au1—Cl1	90.53 (7)	C3—P1—C1	108.9 (4)
Cl2—Au1—Cl1	89.72 (8)	C2—P1—C1	111.3 (4)
Cl3—Au1—Se1	92.70 (5)	C3—P1—Se1	111.7 (3)
Cl2—Au1—Se1	86.98 (6)	C2—P1—Se1	101.0 (3)
Cl1—Au1—Se1	176.59 (6)	C1—P1—Se1	113.0 (3)
P1—Se1—Au1	108.25 (6)

Cl3—Au1—Se1—P1	58.66 (8)	Au1—Se1—P1—C2	169.6 (3)
Cl2—Au1—Se1—P1	−125.16 (8)	Au1—Se1—P1—C1	50.7 (3)
Au1—Se1—P1—C3	−72.6 (3)

Table 9
Selected geometric parameters (Å, °) for 15a

Au1—Cl2	2.2871 (5)	Se1—P1	2.2240 (5)
Au1—Cl3	2.2889 (5)	P1—C3	1.8435 (18)
Au1—Cl1	2.3207 (5)	P1—C2	1.8762 (18)
Au1—Se1	2.4460 (2)	P1—C1	1.8802 (17)

Cl2—Au1—Cl3	176.794 (17)	C3—P1—C2	112.81 (8)
Cl2—Au1—Cl1	89.966 (18)	C3—P1—C1	108.96 (8)
Cl3—Au1—Cl1	89.946 (18)	C2—P1—C1	114.08 (8)
Cl2—Au1—Se1	87.383 (14)	C3—P1—Se1	109.45 (6)
Cl3—Au1—Se1	92.617 (13)	C2—P1—Se1	101.19 (6)
Cl1—Au1—Se1	176.951 (14)	C1—P1—Se1	110.07 (5)
P1—Se1—Au1	108.487 (14)

Cl2—Au1—Se1—P1	−118.493 (18)	Au1—Se1—P1—C2	170.76 (6)
Cl3—Au1—Se1—P1	64.717 (19)	Au1—Se1—P1—C1	49.76 (6)
Au1—Se1—P1—C3	−69.97 (6)

Table 10
Selected geometric parameters (Å, °) for 15aa

Au1—Cl3	2.2825 (7)	Se1—P1	2.2232 (6)
Au1—Cl2	2.2889 (6)	P1—C3	1.844 (3)
Au1—Cl1	2.3172 (6)	P1—C2	1.874 (2)
Au1—Se1	2.4476 (3)	P1—C1	1.878 (2)

Cl3—Au1—Cl2	177.64 (2)	C3—P1—C2	112.97 (12)
Cl3—Au1—Cl1	89.67 (2)	C3—P1—C1	108.44 (11)
Cl2—Au1—Cl1	89.66 (2)	C2—P1—C1	114.23 (11)
Cl3—Au1—Se1	92.332 (18)	C3—P1—Se1	108.64 (9)
Cl2—Au1—Se1	88.238 (18)	C2—P1—Se1	101.78 (8)
Cl1—Au1—Se1	176.855 (18)	C1—P1—Se1	110.54 (8)
P1—Se1—Au1	107.617 (18)

Cl3—Au1—Se1—P1	68.16 (3)	Au1—Se1—P1—C2	170.69 (8)
Cl2—Au1—Se1—P1	−114.14 (3)	Au1—Se1—P1—C1	48.97 (9)
Au1—Se1—P1—C3	−69.90 (9)

Table 11
Selected geometric parameters (Å, °) for 9b

Au1—S1	2.3413 (7)	P1—C2	1.828 (3)
Au1—Br3	2.4233 (3)	P1—C3	1.830 (3)
Au1—Br2	2.4333 (3)	P1—C1	1.832 (3)
Au1—Br1	2.4341 (3)	P1—S1	2.0523 (10)

S1—Au1—Br3	92.317 (19)	C2—P1—C1	114.26 (14)
S1—Au1—Br2	88.43 (2)	C3—P1—C1	106.86 (14)
Br3—Au1—Br2	175.188 (12)	C2—P1—S1	111.90 (10)
S1—Au1—Br1	177.35 (2)	C3—P1—S1	113.79 (11)
Br3—Au1—Br1	89.771 (11)	C1—P1—S1	102.26 (11)
Br2—Au1—Br1	89.350 (11)	P1—S1—Au1	107.77 (4)
C2—P1—C3	107.76 (14)

C2—P1—S1—Au1	72.07 (10)	Br3—Au1—S1—P1	−74.36 (4)
C3—P1—S1—Au1	−50.38 (12)	Br2—Au1—S1—P1	110.40 (4)
C1—P1—S1—Au1	−165.21 (10)

Table 12
Selected geometric parameters (Å, °) for 11b

Au1—S1	2.3477 (6)	P1—C3	1.847 (2)
Au1—Br3	2.4310 (3)	P1—C2	1.872 (2)
Au1—Br2	2.4330 (3)	P1—C1	1.877 (2)
Au1—Br1	2.4399 (4)	P1—S1	2.0640 (8)

S1—Au1—Br3	93.532 (19)	C3—P1—C1	108.53 (11)
S1—Au1—Br2	87.959 (19)	C2—P1—C1	113.56 (10)
Br3—Au1—Br2	172.720 (9)	C3—P1—S1	109.09 (8)
S1—Au1—Br1	177.293 (16)	C2—P1—S1	101.70 (7)
Br3—Au1—Br1	89.099 (14)	C1—P1—S1	111.23 (7)
Br2—Au1—Br1	89.510 (14)	P1—S1—Au1	111.56 (3)
C3—P1—C2	112.57 (10)

C3—P1—S1—Au1	−70.82 (8)	Br3—Au1—S1—P1	70.22 (3)
C2—P1—S1—Au1	170.07 (8)	Br2—Au1—S1—P1	−116.91 (3)
C1—P1—S1—Au1	48.86 (9)

Table 13
Selected geometric parameters (Å, °) for 13b

Au1—Br2	2.4241 (4)	P1—C2	1.831 (4)
Au1—Br3	2.4321 (4)	P1—C1	1.835 (4)
Au1—Se1	2.4535 (4)	P1—C3	1.835 (4)
Au1—Br1	2.4597 (5)	P1—Se1	2.2085 (11)

Br2—Au1—Br3	178.373 (15)	C2—P1—C3	107.15 (18)
Br2—Au1—Se1	87.616 (16)	C1—P1—C3	107.53 (19)
Br3—Au1—Se1	91.709 (14)	C2—P1—Se1	112.81 (14)
Br2—Au1—Br1	90.566 (17)	C1—P1—Se1	101.08 (14)
Br3—Au1—Br1	90.031 (16)	C3—P1—Se1	112.75 (13)
Se1—Au1—Br1	176.522 (15)	P1—Se1—Au1	107.24 (3)
C2—P1—C1	115.50 (19)

C2—P1—Se1—Au1	67.97 (14)	Br2—Au1—Se1—P1	114.96 (3)
C1—P1—Se1—Au1	−168.10 (13)	Br3—Au1—Se1—P1	−66.53 (3)
C3—P1—Se1—Au1	−53.58 (15)

Table 14
Selected geometric parameters (Å, °) for 15b

Au1—Br2	2.4302 (3)	P1—C3	1.847 (2)
Au1—Br3	2.4320 (3)	P1—C2	1.875 (3)
Au1—Br1	2.4549 (3)	P1—C1	1.883 (3)
Au1—Se1	2.4606 (3)	P1—Se1	2.2247 (7)

Br2—Au1—Br3	174.078 (10)	C3—P1—C1	108.84 (11)
Br2—Au1—Br1	90.066 (11)	C2—P1—C1	114.02 (11)
Br3—Au1—Br1	89.729 (12)	C3—P1—Se1	109.35 (9)
Br2—Au1—Se1	87.317 (11)	C2—P1—Se1	101.46 (8)
Br3—Au1—Se1	92.892 (11)	C1—P1—Se1	110.34 (8)
Br1—Au1—Se1	177.377 (9)	P1—Se1—Au1	108.81 (2)
C3—P1—C2	112.60 (11)

C3—P1—Se1—Au1	−69.41 (9)	Br2—Au1—Se1—P1	−117.58 (2)
C2—P1—Se1—Au1	171.47 (8)	Br3—Au1—Se1—P1	68.34 (2)
C1—P1—Se1—Au1	50.27 (9)

Figure 1
The structure of compound 9a in the crystal. Ellipsoids represent 50% probability levels. The dashed line represents an intramolecular hydrogen bond (see text).

Figure 2
The structure of compound 10a (the first polymorph) in the crystal. Ellipsoids represent 50% probability levels.

Figure 3
Structure 10aa (the second polymorph of 10a) in the crystal. Ellipsoids represent 50% probability levels.

Figure 4
The structure of compound 11a (the solvent-free form) in the crystal. Ellipsoids represent 50% probability levels.

Figure 5
Structure 11aa (the CDCl₃ solvate of 11a) in the crystal. Ellipsoids represent 50% probability levels. The dashed lines represent ‘weak’ hydrogen bonds.

Figure 6
The structure of compound 12a in the crystal. Ellipsoids represent 50% probability levels. The dashed line represents a ‘weak’ hydrogen bond.

Figure 7
The structure of compound 14a in the crystal. Ellipsoids represent 30% probability levels.

Figure 8
The structure of compound 15a (the solvent-free form) in the crystal. Ellipsoids represent 50% probability levels.

Figure 9
The structure of 15aa (the CDCl₃ solvate of 15a) in the crystal. Ellipsoids represent 50% probability levels. Only one position of the disordered solvent is shown. The dashed line indicates a weak D⋯Cl hydrogen bond.

Figure 10
The structure of compound 9b in the crystal. Ellipsoids represent 50% probability levels.

Figure 11
The structure of compound 11b in the crystal. Ellipsoids represent 50% probability levels.

Figure 12
The structure of compound 13b in the crystal. Ellipsoids represent 50% probability levels.

Figure 13
The structure of compound 15b in the crystal. Ellipsoids represent 50% probability levels.

Isotypy: In an extensive series of closely analogous structures, several would be expected to be isotypic. Indeed, the four compounds 11a, 15a, 11b and 15b form an isotypic set, and compounds 10aa and 14a form an isotypic pair.

Bond lengths and angles (1). P—E—Au—X₃ groups: The P—S and P—Se bond lengths lie in the ranges 2.0523–2.0665 (av. 2.0602) and 2.2085–2.2247 (av. 2.2183) Å, respectively, significantly longer than in the gold(I) derivatives (av. 2.0368 and 2.1938 Å, respectively); this further lengthening with respect to the ‘standard’ bond lengths of ca 1.95 and 2.11 Å, respectively, in the free ligands implies a slightly higher contribution of the ‘resonance’ form with a P—E single bond to the overall bonding. The bond lengths at the gold atoms are in general considerably lengthened with respect to the gold(I) derivatives; the average bond lengths (Å), with the corresponding Au^I values in square brackets, are Au—S 2.3337 [2.2760], Au—Se 2.4494 [2.3845], Au—Cl trans to E 2.3107 [2.2840], cis to E 2.2855, Au—Br trans to E 2.4471 [2.3979], cis to E 2.4336.

The considerable trans influence of S and Se donor atoms on a trans Au—Cl bond is striking. Thus the six Au—Cl bonds trans to S have an average length of 2.3054 Å, with twelve shorter cis bond lengths, average 2.2857 Å; three Au—Cl bond lengths trans to Se have an average length of 2.3213 Å, with six shorter cis bond lengths, average 2.2851 Å. However, few other clear trends can be recognized; the Au—S and Au—Se bonds are slightly longer trans to Br (av. 2.3445 and 2.4571 Å) than trans to Cl (av. 2.3301 and 2.4443 Å), but the differences and the sample sizes are both small. This would be consistent with similar trans influences for S, Se and Br.

The angles P—S—Au lie in the range 106.70–111.96 (av. 110.29°), with P—Se—Au = 107.24–108.49 (av. 108.08°). The angles are appreciably wider than for the Au^I derivatives (av. 106.17 and 103.86°). Here we have, however, excluded the extreme outlier 12a, with a P—S—Au angle of 117.50 (3)°, which we tentatively attribute to steric effects; 12a is the only ^tBu₃P=E derivative reported in this paper (see also Section 4).

Bond lengths and angles (2). Phosphane chalcogenide ligands: For the Au^I derivatives involving both types of alkyl groups, the carbon atom antiperiplanar to Au across the Au—E—P—C sequence generally belongs to an i-propyl group (the exceptions are the ^tBu₂ⁱPrP=E derivatives 3a and 3b). For the Au^III derivatives, however, all six structures involving such ligands have an antiperiplanar t-butyl group. Because of the bulky alkyl substituents at phosphorus, most C—P—C bond angles are greater than the ideal tetrahedral value. As compensation for this, the E—P—C angles to the carbon atom antiperiplanar to E are narrower, with values in the range 99.3–102.7°. The steric crowding is also reflected in several short intramolecular contacts involving the hydrogen atoms. These are listed for convenience in the tables of hydrogen bonds. In particular, contacts of the type C—H⋯X_cis, invariably involving a methine hydrogen (except for the ^tBu₃P=S derivative 12a, which has no methine hydrogens), are short enough to be regarded as intramolecular ‘weak’ hydrogen bonds; we suggest that the formation of these hydrogen bonds overrides the tendency for the i-propyl group to adopt the antiperiplanar position. The halogen atoms are numbered such that X3 is the intramolecular hydrogen-bond acceptor. This hydrogen bond is drawn explicitly only for compound 9a (Fig. 1), although the C—H group pointing towards X3 can easily be recognized for several other compounds. Another effect associated with these hydrogen bonds is the consistent positioning of the AuX₃ group, with X—Au—E—P torsion angles of ca 65° for the hydrogen-bonded X atom and ca 115° (with the opposite sign) for the other cis X; again, the ^tBu₃P=S derivative 12a behaves differently, with X—Au—E—P torsion angles of 82.19 (3) and −100.28 (3)°. The C—H⋯Au contacts (the latter with H⋯Au as short as 2.68 Å) all involve methyl groups and could be regarded as an inevitable consequence of the crowding effects rather than any significant interaction. This applies a fortiori to the short C—H⋯E contacts, which have very narrow angles at the hydrogen atom.

For the compounds with two structure determinations, least-squares fits were performed (for non-hydrogen atoms) using the program XP (Bruker, 1998 ). The r.m.s. deviations were 0.20 Å for 10a/10aa (0.10 Å if methyl carbon atoms were omitted; Fig. 14), 0.13 Å for 11a/11aa and 0.05 Å for 15a/15aa (the latter were fitted with one structure inverted).

Figure 14
A least-squares fit of structures 10a/10aa (the latter with dashed bonds). The fitted atoms (which exclude the methyl carbons) are labelled. The r.m.s. deviation is 0.10 Å for all fitted atoms (max. 0.23 Å for Cl3).

Molecular volumes: For the gold(I) species, the change in molecular volume (cell volume/Z) on changing the elements E or X (for the same phosphine) was calculated for six pairs S/Se and for six pairs Cl/Br. The values thus obtained were generally consistent with the atomic volumes calculated by Hofmann (2002 ), namely S 25.5, Se 30.3, Cl 25.8 and Br 32.7 Å³. For the gold(III) series, fewer pairs are available, but the results are less convincing. The two polymorphs 10a/10aa already differ by 4.4 Å³, which is comparable to the difference in volume between S and Se according to the density rule postulated by Kitaigorodskii (1961 ). More ‘rational’ (denser) crystal packing should correspond to a more stable polymorph, so that 10aa (D_x = 2.073 Mg m⁻³) should be more stable than 10a (D_x = 2.051 Mg m⁻³). For three pairs Cl/Br, the volume increases range from 13 to 20 Å³, but for four pairs S/Se, the differences range from 1.5 to 7 Å³ and for the pair 9b/13b the difference has the wrong sign (the sulfur-containing 9b has a slightly larger volume, by 1 Å³). Clearly such a simple additive model for the molecular volumes does not apply well here.

3. Supramolecular features

For general aspects of packing and types of secondary interaction, as applied to these compounds, a series of general articles are quoted in our previous paper (Upmann et al., 2024). Hydrogen bonds are given in Tables 15–27 ; these include intramolecular contacts (see above) and several borderline cases. The corresponding symmetry operators, not given explicitly in the following discussion, may also be found in those Tables. In all packing diagrams presented here, hydrogen atoms not involved in hydrogen bonding are omitted for clarity, and the atom labels indicate the asymmetric unit. It is worth repeating the caveat that X-ray methods reveal short intermolecular contacts, but not the corresponding energies, so that descriptions of molecular packing in terms of particular secondary contacts must to some extent be subjective. Similarly, there is no clear objective judgement, on the basis of contact lengths and angles, as to which contacts should be regarded as more important or less important for the packing. Finally, the exposed nature of the one-coordinate halogen atoms, combined with the large number of hydrogen atoms, means that some short H⋯X contacts are inevitable. Nevertheless, it is possible to obtain informative packing diagrams.

Table 15
Hydrogen-bond geometry (Å, °) for 9a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32C⋯Au1	0.98	2.69	3.485 (2)	138
C2—H2⋯Cl3	1.00	2.68	3.437 (2)	133
C12—H12B⋯S1	0.98	2.73	3.310 (2)	118
C1—H1⋯Cl2ⁱ	1.00	2.82	3.506 (2)	126
C11—H11C⋯Cl2ⁱ	0.98	2.91	3.582 (2)	127
C22—H22A⋯Cl1ⁱⁱ	0.98	2.86	3.803 (2)	161
C2—H2⋯Cl3ⁱⁱ	1.00	2.86	3.688 (2)	141
C32—H32A⋯Cl2ⁱⁱⁱ	0.98	2.87	3.847 (2)	180
C3—H3⋯Cl2^iv	1.00	2.95	3.881 (2)	155
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Table 16
Hydrogen-bond geometry (Å, °) for 10a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32B⋯Cl3	0.98	2.75	3.452 (3)	130
C3—H3⋯Cl3	1.00	2.89	3.476 (3)	118
C13—H13A⋯Cl3	0.98	2.85	3.729 (3)	150
C13—H13B⋯Cl2ⁱ	0.98	2.77	3.704 (3)	160
C31—H31A⋯Cl1ⁱⁱ	0.98	2.87	3.372 (3)	113
C13—H13C⋯Cl2ⁱⁱⁱ	0.98	2.91	3.878 (3)	170
C32—H32A⋯Cl3^iv	0.98	2.91	3.800 (3)	152
Symmetry codes: (i) ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) ; (iv) .

Table 17
Hydrogen-bond geometry (Å, °) for 10aa

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl3	1.00	2.70	3.427 (3)	130
C3—H3⋯Cl2ⁱ	1.00	2.95	3.665 (3)	129
C21—H21C⋯Cl2ⁱⁱ	0.98	2.99	3.706 (4)	131
C22—H22A⋯Cl2ⁱⁱ	0.98	2.94	3.675 (4)	133
C13—H13C⋯Cl3ⁱⁱⁱ	0.98	2.99	3.832 (4)	145
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 18
Hydrogen-bond geometry (Å, °) for 11a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯Au1	0.98	2.71	3.6142 (19)	154
C12—H12C⋯S1	0.98	2.86	3.391 (2)	115
C3—H3⋯Cl3	1.00	2.62	3.451 (2)	140
C12—H12C⋯Cl2	0.98	2.81	3.788 (2)	174
C13—H13C⋯Cl2ⁱ	0.98	2.91	3.851 (2)	161
Symmetry code: (i) .

Table 19
Hydrogen-bond geometry (Å, °) for 11aa

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯Au1	0.98	2.68	3.6027 (19)	156
C21—H21A⋯S1	0.98	2.63	3.1082 (19)	110
C12—H12C⋯S1	0.98	2.86	3.411 (2)	116
C3—H3⋯Cl3	1.00	2.65	3.4471 (18)	137
C12—H12C⋯Cl2	0.98	2.78	3.755 (2)	171
C99—D99⋯Cl1	1.00	2.74	3.537 (2)	137
C99—D99⋯Cl2	1.00	2.69	3.489 (2)	137
C12—H12A⋯Cl1ⁱ	0.98	2.91	3.596 (2)	128
Symmetry code: (i) .

Table 20
Hydrogen-bond geometry (Å, °) for 12a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23A⋯Au1	0.98	2.69	3.438 (2)	134
C13—H13B⋯S1	0.98	2.61	3.131 (2)	114
C32—H32A⋯S1	0.98	2.83	3.323 (2)	112
C23—H23A⋯Cl2	0.98	2.82	3.778 (2)	168
C32—H32A⋯Cl3	0.98	2.88	3.759 (2)	150
C33—H33B⋯Cl3	0.98	2.73	3.623 (2)	152
C99—H99A⋯Cl2	0.99	2.84	3.749 (3)	153
C99—H99B⋯Cl3ⁱ	0.99	2.96	3.903 (3)	160
C22—H22A⋯Cl3ⁱ	0.98	2.82	3.791 (2)	171
Symmetry code: (i) .

Table 21
Hydrogen-bond geometry (Å, °) for 14a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl3	1.00	2.74	3.445 (9)	128
C3—H3⋯Cl2ⁱ	1.00	2.99	3.714 (8)	130
C21—H21C⋯Cl2ⁱⁱ	0.98	2.98	3.730 (10)	135
C22—H22A⋯Cl2ⁱⁱ	0.98	2.94	3.646 (11)	130
C13—H13C⋯Cl3ⁱⁱⁱ	0.98	2.98	3.860 (10)	151
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 22
Hydrogen-bond geometry (Å, °) for 15a

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯Au1	0.98	2.76	3.6818 (18)	158
C21—H21C⋯Se1	0.98	2.68	3.1887 (19)	113
C12—H12C⋯Se1	0.98	2.92	3.4566 (18)	116
C3—H3⋯Cl3	1.00	2.65	3.4842 (19)	141
C12—H12C⋯Cl2	0.98	2.94	3.9145 (19)	174
C13—H13C⋯Cl2ⁱ	0.98	2.93	3.8489 (19)	157
Symmetry code: (i) .

Table 23
Hydrogen-bond geometry (Å, °) for 15aa

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C99—D99⋯Cl2	1.00	2.76	3.580 (7)	139
C13—H13A⋯Au1	0.98	2.69	3.618 (3)	158
C21—H21C⋯Se1	0.98	2.70	3.208 (3)	112
C3—H3⋯Cl3	1.00	2.65	3.497 (3)	142
C13—H13C⋯Cl2ⁱ	0.98	2.92	3.866 (3)	163
Symmetry code: (i) .

Table 24
Hydrogen-bond geometry (Å, °) for 9b

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32C⋯Au1	0.98	2.76	3.473 (3)	131
C12—H12B⋯S1	0.98	2.68	3.261 (3)	118
C2—H2⋯Br3	1.00	2.71	3.560 (3)	143
C22—H22B⋯Au1ⁱ	0.98	2.98	3.551 (3)	119
C21—H21C⋯Br1ⁱⁱ	0.98	3.02	3.829 (3)	141
C3—H3⋯Br2ⁱ	1.00	2.91	3.796 (3)	148
C32—H32A⋯Br2ⁱⁱⁱ	0.98	3.06	3.900 (3)	145
C11—H11C⋯Br2^iv	0.98	2.91	3.661 (3)	134
Symmetry codes: (i) ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (iv) .

Table 25
Hydrogen-bond geometry (Å, °) for 11b

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯Au1	0.98	2.69	3.607 (2)	156
C21—H21A⋯S1	0.98	2.63	3.109 (2)	110
C12—H12A⋯S1	0.98	2.89	3.417 (2)	114
C3—H3⋯Br3	1.00	2.71	3.546 (2)	141
C12—H12A⋯Br2	0.98	2.89	3.863 (2)	174
C13—H13A⋯Br2ⁱ	0.98	3.00	3.931 (2)	159
Symmetry code: (i) .

Table 26
Hydrogen-bond geometry (Å, °) for 13b

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32C⋯Au1	0.98	2.77	3.578 (5)	140
C12—H12B⋯Se1	0.98	2.90	3.479 (5)	119
C2—H2⋯Br3	1.00	2.71	3.497 (4)	136
C11—H11C⋯Br3ⁱ	0.98	2.78	3.752 (5)	171
C32—H32A⋯Br2ⁱⁱ	0.98	2.99	3.933 (4)	163
Symmetry codes: (i) ; (ii) .

Table 27
Hydrogen-bond geometry (Å, °) for 15b

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯Au1	0.98	2.74	3.679 (3)	160
C21—H21A⋯Se1	0.98	2.69	3.197 (3)	113
C12—H12A⋯Se1	0.98	2.96	3.484 (3)	115
C3—H3⋯Br3	1.00	2.75	3.585 (3)	142
C12—H12A⋯Br2	0.98	3.01	3.980 (3)	173
C13—H13A⋯Br2ⁱ	0.98	3.02	3.929 (3)	156
Symmetry code: (i) .

For compound 9a, five H⋯Cl contacts (from H1, H2, H3, H22A and H11C) combine to form a layer structure parallel to (011) (Fig. 15). A short Cl3⋯Cl3 contact of 3.625 (1) Å, operator 1 − x, −y, 1 − z, is also observed. We have previously noted the tendency of tetrahalogenidoaurate(III) anions to display short X⋯X contacts (Döring & Jones, 2016 ), and these are also observed in some neutral trihalogenidogold(III) complexes such as tribromido(piperidine)gold(III) (Döring & Jones, 2023 ).

Figure 15
Packing diagram of 9a, showing the formation of a layer structure parallel to (011) in the region y ≃ 0.25, z ≃ 0.25. Dashed lines indicate H⋯Cl contacts (thin) or Cl⋯Cl contacts (thick).

Compound 10a also forms a layer structure, parallel to the ac plane, involving three H⋯Cl contacts (from H13B, H13C and H32A) and one S⋯Cl contact [S1⋯Cl3(1 − x, 1 − y, 1 − z) = 3.6746 (9) Å] (Fig. 16). The second polymorph 10aa has a completely different packing; there are no H⋯Cl contacts < 2.94 Å, but instead the molecules associate to form dimers (Fig. 17) with a short S1⋯S1 contact of 3.622 (2) Å (operator 1 − x, −y, 1 − z). The corresponding S1⋯Au1 distance is 4.0282 (8) Å, and there is a borderline H22C⋯Au1 contact of 3.18 Å. Dimers are linked to form a chain parallel to the a axis by the contact Cl2⋯Cl3 3.5885 (11) Å (operator −1 + x, y, z; Fig. 18). The packing of 11a is similar to that of 10a, again involving inversion-symmetric dimers [S1⋯S1 = 3.4257 (9), S1⋯Au1 = 4.0467 (5), H21C⋯Au1 = 3.03 Å, operator 1 − x, 1 − y, −z], but with these being linked by the contact H13⋯Cl2 to form chains parallel to the c axis (Fig. 19). Compound 14a (isotypic to 10aa) has contact distances Se1⋯Se1′ = 3.615 (2) and Cl2⋯Cl3′ = 3.511 (3) Å. Compounds 11b, 15a and 15b (isotypic to 11a) have distances Se1⋯Se1′ = 3.3447 (4), S1⋯S1′ = 3.4513 (11) and Se1⋯Se1′ = 3.3734 (5) Å, respectively. The primes indicate the operators given above for the parent structures.

Figure 16
Packing diagram of 10a viewed parallel to the b axis in the region y ≃ 0.5. Dashed lines indicate H⋯Cl contacts (thin) or S⋯Cl contacts (thick).

Figure 17
The inversion-symmetric dimer of 10aa. The short S1⋯S1 contact is shown by the thick dashed line. Thin dashed lines indicate the borderline contacts S1⋯Au1 and H22C⋯Au1.

Figure 18
Structure 10aa: Association of dimers to form chains parallel to the a axis. The two chains lie in the regions y ≃ 0.5, z ≃ 0 and y ≃ 0, z ≃ 0.5. Thick dashed lines indicate Cl⋯Cl and S⋯S contacts; the latter are viewed almost end-on. Hydrogen atoms are omitted.

Figure 19
Compound 11a: Association of dimers to form chains parallel to the c axis. The view direction is perpendicular to the ab plane. Dashed lines indicate H⋯Cl and S⋯S contacts (thick) or borderline S⋯Au and H⋯Au contacts (thin).

For compound 11aa, which is the deuterochloroform solvate of 11a, the solvent molecule is well-ordered, and its deuterium atom is involved in a three-centre hydrogen bond to Cl1 and Cl2. The residues are further linked by the short contact Cl3⋯Cl6 = 3.6706 (7) Å (operator x, −1 + y, z), forming chains parallel to the b axis (Fig. 20). There are no H⋯Cl contacts < 2.91 Å.

Figure 20
Compound 11aa: Association of residues to form chains parallel to the b axis. The view direction is perpendicular to the ab plane. Dashed lines indicate hydrogen bonds or Cl⋯Cl contacts.

Compound 12a, which is a dichloromethane solvate, has a three-dimensional packing in which the most striking feature is the formation of dimers via the contact S1⋯S1(1 − x, 1 − y, 1 − z) = 3.4357 (10) Å. The packing involves layers parallel to (011); these include the solvent contacts H99A⋯Cl2 (also shown in Fig. 6) = 2.84, H99B⋯Cl3 = 2.96 and Cl5⋯Cl5(2 − x, 2 − y, −z) = 3.3990 (14) Å (Fig. 21). The alkyl groups of one layer project into the gaps of neighbouring layers. The contacts H22A⋯Cl3 are not shown in Fig. 21.

Figure 21
Compound 12a: The layer structure parallel to (011), viewed perpendicular to this plane in the region x ≃ 1. Dashed lines indicate S⋯S and Cl⋯Cl contacts (thick) or H⋯Cl contacts (thin).

Compound 15aa, the deuterochloroform solvate of 15a, has few short contacts between the molecules of the gold complex itself; the contact Cl1⋯Cl1(−x, 2 − y, 1 − z) = 3.5208 (13) Å links the molecules into simple dimers. Instead it is the disordered solvent, occupying the region at z ≃ 0, that lies between and thus connects the molecules of the gold complex. Fig. 22 shows this pattern for the major disorder component, with D99⋯Cl2 = 2.76, Au1⋯Cl5 = 3.547 (2) and Cl2⋯Cl5 = 3.603 (2) Å (both −x, 2 − y, −z) and Cl6⋯Cl6 = 3.546 (6) Å (−x, 1 − y, −z). The minor component, somewhat displaced from its major counterpart [C99⋯C99′ = 0.59 (1) Å, angle between C—D vectors = 9°], makes a similar series of contacts, which we do not discuss explicitly.

Figure 22
Compound 15aa: The disordered solvent, only the major component of which is shown here, lies between the molecules of the gold complex, forming a variety of short contacts Au⋯Cl, H⋯Cl and Cl⋯Cl (dashed lines). The view direction is perpendicular to the ab plane in the region x ≃ 0.

Compound 9b has a short Br1⋯Br3(−x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) contact of 3.7110 (4) Å. This combines with four H⋯Br contacts and one H⋯Au contact to form a layer structure parallel to (10 $[\overline{2}]$ ) (Fig. 23).

Figure 23
Compound 9b: The layer structure parallel to (10 $[\overline{2}]$ ), formed by Br⋯Br contacts (thick dashed lines) and five weak hydrogen bonds (thin dashed lines).

The packing of compound 13b involves the formation of striking inversion-symmetric dimers, with short contacts Au1⋯Se1′ = 3.7472 (5) and Se1⋯Br3′ = 3.4874 (6) Å, via the operator 1 − x, 1 − y, −z (Fig. 24). The corresponding Au1⋯Au1′ and Au1⋯Br2′ distances of 4.1897 (3) and 4.0038 (5) Å are probably too long to represent any significant interaction. The dimer formation is reminiscent of the stacking of AuX₃ moieties, as observed for example for the infinite stacks in four polymorphs of trichlorido(tetrahydrothiophene)gold(III) (Upmann & Jones, 2017 ), but with the important difference that the Se atom of 13b is also involved. The dimers are linked by a short Br2⋯Br3 contact of 3.5478 Å (operator 1 + x, y, z), forming a chain parallel to the a axis (Fig. 25).

Figure 24
Compound 13b: Dimer formation via short Se⋯Au and Se⋯Br contacts (thick dashed lines)

Figure 25
Compound 13b: Linkage of dimers parallel to the a axis via a short Br⋯Br interaction. The view direction is parallel to the b axis.

4. Database survey

The searches employed the routine ConQuest (Bruno et al., 2002 ), part of Version 2022.3.0 of the Cambridge Structural Database (Groom et al., 2016 ).

A search for all structures containing the moiety R₃P=S—TM (coordination numbers of 4 for P and 2 for S, bond orders unspecified, TM = any transition metal), excluding any structure in which the P=S or S—TM bonds were involved in rings, gave 83 hits. The 108 bond angles at sulfur ranged from 95.6–127.9°, so that this angle is clearly highly variable. The largest value of 127.88 (2)° was observed for the only structure involving ^tBu₃P=S, namely [(^tBu₃PS)Fe(CO)₂Cp][PF₆] (RIDJUK; Kuckmann et al., 2007 ), cf. structure 12a above. Similarly, 39 hits for R₃P=Se—TM were registered, with 58 angles at selenium in the range 92.1–113.3°. One of the smallest angles, 92.91 (12)°, was observed for (9-phenanthryl)Ph₂PSeAuCl (as its benzene solvate); the analogous sulfur derivative (solvent-free) had a P—S—Au angle of 100.85 (6)° (DUGSAB & DUGFOC; Breshears et al., 2015 ).

Searches for other compounds of the type (R₃P=E)AuX₃ gave only our own structures, i.e. all four permutations (E = S or Se, X = Cl or Br) of (PCP)ⁱPr₂EAuX₃ (PCP = [2.2]paracyclophanyl; Upmann et al., 2019 ).

5. Synthesis and crystallization

For several of the compounds, the syntheses can be found in the PhD thesis of D. Upmann (Upmann, 2015 ). The following do not appear there:

Compound 9a. 125 mg (0.3 mmol) of ⁱPr₃PSAuCl were dissolved in 5 mL of dichloromethane, and a solution of iodobenzene dichloride (82 mg, 0.3 mmol) in 5 mL of dichloromethane was added. The red solution was stirred for 30 min. The solvent was removed under vacuum. The product, a red solid, was precipitated with n-pentane and dried under vacuum. The yield was not recorded. ³¹P-NMR (200 MHz, CDCl₃, 300 K): δ (ppm) 78.64 (s). Elemental analysis (%): calculated: C 21.81, H 4.27, S 6.47; found: C 22.06, H 4.07, S 6.26. Single crystals were obtained by liquid diffusion of n-pentane into a solution of 9a in dichloromethane. Similar attempts to synthesize the selenium analogue (which would have been compound 13a) were unsuccessful; the product was always an intractable gum that decomposed.

Compound 9b. 187.4 mg (0.399 mmol) of ⁱPr₃PSAuBr were dissolved in 3 mL of dichloromethane, and 4.16 mL of a 0.096 M solution of bromine in dichloromethane were added. The product, a red solid, was precipitated with n-pentane and dried under vacuum. Yield: 132.6 mg (0.211 mmol, 53%). ³¹P-NMR (81 MHz, CDCl₃, 300 K): δ (ppm) 77.17 (s). Elemental analysis (%): calculated: C 17.19, H 3.37, S 5.10; found: C 17.42, H 3.40, S 5.31. Single crystals were obtained by liquid diffusion of n-pentane into a solution of 9b in dichloromethane.

Compound 11b. 336 mg (0.675 mmol) of ⁱPr₂^tBuPSAuBr were dissolved in 3 mL of dichloromethane, and 6.7 mL of a 0.1 M solution of bromine in dichloromethane were added. The solution was overlayered with n-pentane and stored in a refrigerator (278 K) overnight. Crystals suitable for structure determination formed. After removal of the solvent under vacuum, the product was recrystallized from a mixture of dichloromethane and n-pentane as a dark-red solid. Yield: 341 mg (0.685 mmol, quantitative). ³¹P-NMR (81 MHz, CDCl₃, 300 K): δ (ppm) 85.18 (s). Elemental analysis (%): calculated: C 20.11, H 3.84, S 4.88; found: C 20.98, H 4.01, S 4.97.

Compound 12a was synthesized by the same general method as the other chloro derivatives (e.g. 9a, see above), but the details have unfortunately been lost.

Compound 13b. 194.7 mg (0.377 mmol) of ⁱPr₃PSeAuBr were dissolved in 3 mL of dichloromethane, and 3.93 mL of a 0.096 M solution of bromine in dichloromethane were added. The product, a red solid, was precipitated with n-pentane and dried under vacuum. Yield: 141.2 mg (0.209 mmol, 55%). ³¹P-NMR (81 MHz, CDCl₃, 300 K): δ (ppm) 74.46 (s, ¹J_P–Se = 520 Hz). Single crystals were obtained by liquid diffusion of n-pentane into a solution of 13b in dichloromethane. Elemental analysis (%): calculated: C 15.99, H 3.13; found: C 16.22, H 3.18.

Compound 15b. 303 mg (0.557 mmol) of ⁱPr^tBu₂PSeAuBr were dissolved in 3 mL of dichloromethane, and 5.6 mL of a 0.1 M solution of bromine in dichloromethane were added. The solution was overlayered with n-pentane and stored in a refrigerator (278 K) overnight. After removal of the solvent under vacuum, the product was recrystallized twice from a mixture of dichloromethane and n-pentane as a dark red solid, from which a crystal was selected for measurement. The yield was only ca 20%, and neither the elemental analyses nor the ³¹P-NMR results were satisfactory (despite the successful structure determination). We suspect partial decomposition of the product.

The conditions under which the polymorph 10aa arose were unfortunately not recorded. Crystals of the deuterochloroform solvates 11aa and 15aa were obtained fortuitously by evaporation from the corresponding NMR solutions.

6. Refinement

Details of the measurements and refinements are given in Table 28. Structures were refined anisotropically on F². Methine and methylene hydrogens were included at calculated positions and refined using a riding model with C—H = 1.00 or 0.99 Å respectively and U_iso(H) = 1.2 × U_eq(C). Methyl groups were refined, using the command AFIX 137, as idealized rigid groups allowed to rotate but not tip, with C—H = 0.98 Å, H—C—H = 109.5° and U_iso(H) = 1.5 × U_eq(C). The use of this command determines the initial hydrogen positions (before refinement) by analysis of maxima in the residual electron density at suitable C—H distances, and these peaks may not be entirely reliable in the presence of a very heavy atom (although in general the refinement seemed to proceed satisfactorily), so that any postulated hydrogen bonds involving methyl hydrogen atoms should be interpreted with caution.

Table 28
Experimental details

	9a	10a	10aa	11a	11aa
Crystal data
Chemical formula	[AuCl₃(C₉H₂₁PS)]	[AuCl₃(C₁₀H₂₃PS)]	[AuCl₃(C₁₀H₂₃PS)]	[AuCl₃(C₁₁H₂₅PS)]	[AuCl₃(C₁₁H₂₅PS)]·CDCl₃
M_r	495.60	509.63	509.63	523.66	644.03
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100	100	100	101
a, b, c (Å)	8.0262 (3), 9.0839 (3), 10.7162 (3)	8.4533 (2), 17.0563 (4), 11.4826 (3)	7.9363 (3), 14.4096 (4), 14.2851 (4)	8.6034 (4), 9.7779 (4), 11.4231 (4)	9.6382 (4), 10.2787 (3), 11.8483 (5)
α, β, γ (°)	86.185 (2), 85.730 (3), 84.468 (3)	90, 94.525 (2), 90	90, 91.774 (3), 90	78.876 (3), 71.456 (4), 72.702 (4)	75.115 (3), 68.875 (4), 89.728 (3)
V (Å³)	774.13 (4)	1650.43 (7)	1632.85 (9)	864.69 (7)	1053.13 (8)
Z	2	4	4	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	10.23	9.60	9.70	9.16	7.91
Crystal size (mm)	0.22 × 0.05 × 0.01	0.3 × 0.2 × 0.02	0.3 × 0.2 × 0.2	0.15 × 0.15 × 0.08	0.15 × 0.06 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )
T_min, T_max	0.421, 1.000	0.192, 1.000	0.159, 0.247	0.577, 1.000	0.454, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	56439, 4632, 4428	40041, 4863, 4483	42542, 4881, 4296	68815, 5155, 4939	76947, 6247, 5976
R_int	0.037	0.040	0.046	0.038	0.038
(sin θ/λ)_max (Å⁻¹)	0.720	0.722	0.721	0.721	0.723

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.033, 1.05	0.021, 0.046, 1.07	0.025, 0.045, 1.12	0.016, 0.036, 1.08	0.016, 0.033, 1.05
No. of reflections	4632	4863	4881	5155	6247
No. of parameters	142	152	152	163	199
No. of restraints	0	0	0	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.96	2.15, −1.41	2.52, −1.50	1.64, −0.93	1.02, −0.95
Extinction method	None	None	None	F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4 (SHELXL2019/3; Sheldrick, 2015)	F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4 (SHELXL2019/3; Sheldrick, 2015)
Extinction coefficient	–	–	–	0.00097 (14)	0.00133 (9)

	12a	14a	15a	15aa	9b
Crystal data
Chemical formula	[AuCl₃(C₁₂H₂₇PS)]·CH₂Cl₂	[AuCl₃(C₁₀H₂₃PSe)]	[AuCl₃(C₁₁H₂₅PSe)]	[AuCl₃(C₁₁H₂₅PSe)]·CDCl₃	[AuBr₃(C₁₀H₂₃PS)]
M_r	622.61	556.53	570.55	690.93	628.98
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c
Temperature (K)	100	100	100	100	100
a, b, c (Å)	8.4202 (3), 11.2194 (4), 11.8355 (4)	7.92516 (18), 14.5559 (4), 14.3635 (4)	8.5878 (4), 9.8435 (4), 11.5022 (5)	8.5343 (2), 9.7185 (3), 14.0759 (4)	9.1341 (2), 7.9039 (2), 22.6420 (4)
α, β, γ (°)	98.398 (3), 101.174 (3), 95.991 (3)	90, 91.264 (2), 90	78.391 (3), 71.168 (4), 73.463 (4)	74.398 (2), 78.121 (2), 73.257 (2)	90, 94.519 (2), 90
V (Å³)	1074.95 (7)	1656.54 (7)	875.78 (7)	1066.31 (5)	1629.56 (6)
Z	2	4	2	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	7.63	11.64	11.01	9.42	16.58
Crystal size (mm)	0.15 × 0.1 × 0.1	0.15 × 0.15 × 0.1	0.18 × 0.15 × 0.12	0.4 × 0.25 × 0.08	0.15 × 0.1 × 0.1

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )
T_min, T_max	0.783, 1.000	0.483, 1.000	0.700, 1.000	0.151, 1.000	0.486, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	157605, 6558, 6124	196706, 4112, 3878	54532, 5231, 4984	76069, 6287, 6060	64266, 4964, 4633
R_int	0.054	0.084	0.032	0.040	0.037
(sin θ/λ)_max (Å⁻¹)	0.727	0.667	0.722	0.721	0.722

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.037, 1.05	0.043, 0.093, 1.32	0.014, 0.030, 1.10	0.021, 0.048, 1.10	0.022, 0.038, 1.23
No. of reflections	6558	4112	5231	6287	4964
No. of parameters	199	152	163	235	143
No. of restraints	0	0	0	39	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.76, −1.01	3.81, −2.41	0.84, −0.73	1.88, −1.30	1.58, −0.95
Extinction method	None	None	F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4 (SHELXL2019/3; Sheldrick, 2015)	None	F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4 (SHELXL2019/3; Sheldrick, 2015)
Extinction coefficient	–	–	0.00113 (8)	–	0.00043 (2)

	11b	13b	15b
Crystal data
Chemical formula	[AuBr₃(C₁₁H₂₅PS)]	[AuBr₃(C₉H₂₁PSe)]	[AuBr₃(C₁₁H₂₅PSe)]
M_r	657.04	675.88	703.93
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100	100
a, b, c (Å)	8.6067 (8), 10.1161 (12), 11.5123 (12)	8.3928 (2), 10.1417 (4), 10.7567 (4)	8.6000 (5), 10.2045 (7), 11.5987 (7)
α, β, γ (°)	77.873 (10), 70.257 (10), 71.867 (10)	94.419 (3), 105.612 (3), 110.113 (3)	77.475 (6), 69.764 (6), 72.601 (6)
V (Å³)	890.37 (18)	813.33 (5)	904.02 (11)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	15.18	18.72	16.85
Crystal size (mm)	0.2 × 0.2 × 0.2	0.2 × 0.1 × 0.01	0.2 × 0.06 × 0.04

Data collection
Diffractometer	Oxford Diffaction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos	Oxford Diffraction Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ )
T_min, T_max	0.447, 1.000	0.200, 1.000	0.376, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	65025, 5297, 5057	44535, 4825, 4278	25566, 5282, 4719
R_int	0.038	0.059	0.033
(sin θ/λ)_max (Å⁻¹)	0.721	0.724	0.721

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.036, 1.14	0.028, 0.074, 1.05	0.020, 0.036, 1.05
No. of reflections	5297	4825	5282
No. of parameters	163	142	163
No. of restraints	0	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −1.43	1.43, −1.49	1.04, −0.80
Extinction method	F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4 (SHELXL2019/3; Sheldrick, 2015)	None	F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4 (SHELXL2019/3; Sheldrick, 2015)
Extinction coefficient	0.00557 (11)	–	0.00115 (6)
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2019/3 (Sheldrick, 2015) and XP (Bruker, 1998).

Special features: The deuterochloroform molecule of 15aa is disordered over two positions with occupation factors 0.525 (4) and 0.475 (4). Appropriate restraints were employed to improve refinement stability, but the dimensions of disordered groups should always be interpreted with caution. The data for 14a were significantly affected by the presence of a small (and at first undetected) satellite crystal, rotated by ca 5° from the main crystal. Attempts to treat the structure using procedures developed for non-merohedral twins did not lead to any improvement, and no better crystals were found. The U values are significantly higher than for the other structures, and the ellipsoid plot (Fig. 7) is drawn at 30% rather than 50% levels.

Supporting information

CCDC references: 2156390; 2156786; 2156787; 2156789; 2156790; 2156867; 2156868; 2156869; 2156870; 2338821; 2338822; 2338823; 2338824

Crystal structure: contains datablocks 9a, 10a, 10aa, 11a, 11aa, 12a, 14a, 15a, 15aa, 9b, 11b, 13b, 15b, global. DOI: https://doi.org/10.1107/S2056989024002032/yz2051sup1.cif

Structure factors: contains datablock 9a. DOI: https://doi.org/10.1107/S2056989024002032/yz20519asup2.hkl

Structure factors: contains datablock 10a. DOI: https://doi.org/10.1107/S2056989024002032/yz205110asup3.hkl

Structure factors: contains datablock 10aa. DOI: https://doi.org/10.1107/S2056989024002032/yz205110aasup4.hkl

Structure factors: contains datablock 11a. DOI: https://doi.org/10.1107/S2056989024002032/yz205111asup5.hkl

Structure factors: contains datablock 11aa. DOI: https://doi.org/10.1107/S2056989024002032/yz205111aasup6.hkl

Structure factors: contains datablock 12a. DOI: https://doi.org/10.1107/S2056989024002032/yz205112asup7.hkl

Structure factors: contains datablock 14a. DOI: https://doi.org/10.1107/S2056989024002032/yz205114asup8.hkl

Structure factors: contains datablock 15a. DOI: https://doi.org/10.1107/S2056989024002032/yz205115asup9.hkl

Structure factors: contains datablock 15aa. DOI: https://doi.org/10.1107/S2056989024002032/yz205115aasup10.hkl

Structure factors: contains datablock 9b. DOI: https://doi.org/10.1107/S2056989024002032/yz20519bsup11.hkl

Structure factors: contains datablock 11b. DOI: https://doi.org/10.1107/S2056989024002032/yz205111bsup12.hkl

Structure factors: contains datablock 13b. DOI: https://doi.org/10.1107/S2056989024002032/yz205113bsup13.hkl

Structure factors: contains datablock 15b. DOI: https://doi.org/10.1107/S2056989024002032/yz205115bsup14.hkl

checkCIF report

Computing details top

Trichlorido(tripropan-2-ylphosphane sulfide-κS)gold(III) (9a) top

Crystal data top

[AuCl₃(C₉H₂₁PS)]	Z = 2
M_r = 495.60	F(000) = 472
Triclinic, P1	D_x = 2.126 Mg m⁻³
a = 8.0262 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0839 (3) Å	Cell parameters from 25652 reflections
c = 10.7162 (3) Å	θ = 2.3–30.7°
α = 86.185 (2)°	µ = 10.23 mm⁻¹
β = 85.730 (3)°	T = 100 K
γ = 84.468 (3)°	Plate, dichroic orange / yellow
V = 774.13 (4) Å³	0.22 × 0.05 × 0.01 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	4632 independent reflections
Radiation source: Enhance (Mo) X-ray source	4428 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.037
ω scans	θ_max = 30.8°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −11→11
T_min = 0.421, T_max = 1.000	k = −12→12
56439 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.015	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.033	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0167P)² + 0.4566P] where P = (F_o² + 2F_c²)/3
4632 reflections	(Δ/σ)_max = 0.002
142 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −0.96 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.74127 (2)	0.15601 (2)	0.24499 (2)	0.01058 (3)
Cl1	0.90254 (7)	−0.06826 (5)	0.24307 (5)	0.02024 (10)
Cl3	0.67060 (6)	0.11336 (6)	0.45357 (5)	0.01749 (9)
Cl2	0.83231 (6)	0.20433 (6)	0.04060 (4)	0.01903 (10)
S1	0.58505 (6)	0.38531 (5)	0.23869 (5)	0.01309 (9)
P1	0.33654 (6)	0.34414 (5)	0.25253 (4)	0.01036 (9)
C1	0.2343 (2)	0.5273 (2)	0.20553 (19)	0.0136 (4)
H1	0.278877	0.550333	0.117475	0.016*
C2	0.2705 (2)	0.2697 (2)	0.40925 (18)	0.0136 (4)
H2	0.342680	0.174844	0.423351	0.016*
C3	0.2864 (3)	0.2158 (2)	0.13891 (19)	0.0152 (4)
H3	0.161322	0.217320	0.143959	0.018*
C11	0.0440 (3)	0.5277 (2)	0.2004 (2)	0.0235 (5)
H11A	−0.008072	0.516636	0.285805	0.035*
H11B	0.019245	0.445182	0.152445	0.035*
H11C	−0.001015	0.621446	0.159793	0.035*
C12	0.2796 (3)	0.6527 (2)	0.2818 (2)	0.0257 (5)
H12A	0.238861	0.748320	0.241944	0.039*
H12B	0.401672	0.647672	0.285129	0.039*
H12C	0.227092	0.642306	0.367069	0.039*
C21	0.3038 (3)	0.3672 (2)	0.5135 (2)	0.0214 (4)
H21A	0.225900	0.457144	0.510729	0.032*
H21B	0.419396	0.394310	0.501883	0.032*
H21C	0.287352	0.312734	0.594864	0.032*
C22	0.0893 (3)	0.2277 (3)	0.4200 (2)	0.0211 (4)
H22A	0.066095	0.175991	0.501716	0.032*
H22B	0.073806	0.162680	0.353195	0.032*
H22C	0.012040	0.317689	0.411899	0.032*
C31	0.3395 (3)	0.2667 (3)	0.0039 (2)	0.0232 (5)
H31A	0.462041	0.264402	−0.006264	0.035*
H31B	0.289704	0.367907	−0.014347	0.035*
H31C	0.300690	0.200277	−0.053941	0.035*
C32	0.3543 (3)	0.0551 (2)	0.1703 (2)	0.0203 (4)
H32A	0.306801	−0.010584	0.116174	0.030*
H32B	0.322688	0.027578	0.258217	0.030*
H32C	0.476851	0.045590	0.156468	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.00962 (4)	0.01142 (4)	0.01073 (4)	−0.00084 (2)	−0.00111 (2)	−0.00061 (2)
Cl1	0.0213 (2)	0.0167 (2)	0.0215 (2)	0.00572 (18)	−0.00174 (19)	−0.00262 (19)
Cl3	0.0157 (2)	0.0213 (2)	0.0138 (2)	0.00148 (17)	0.00099 (17)	0.00419 (18)
Cl2	0.0198 (2)	0.0250 (2)	0.0116 (2)	−0.00060 (19)	0.00136 (17)	−0.00064 (18)
S1	0.0115 (2)	0.0108 (2)	0.0169 (2)	−0.00201 (16)	−0.00067 (17)	0.00050 (17)
P1	0.0103 (2)	0.0095 (2)	0.0114 (2)	−0.00047 (16)	−0.00153 (17)	−0.00085 (17)
C1	0.0149 (9)	0.0102 (8)	0.0152 (9)	0.0012 (7)	−0.0019 (7)	0.0012 (7)
C2	0.0120 (9)	0.0155 (9)	0.0131 (9)	−0.0022 (7)	−0.0006 (7)	0.0012 (7)
C3	0.0135 (9)	0.0157 (9)	0.0172 (9)	−0.0004 (7)	−0.0033 (7)	−0.0061 (7)
C11	0.0144 (10)	0.0197 (10)	0.0344 (13)	0.0032 (8)	−0.0019 (9)	0.0055 (9)
C12	0.0358 (13)	0.0118 (9)	0.0303 (12)	0.0047 (9)	−0.0124 (10)	−0.0050 (8)
C21	0.0293 (12)	0.0221 (10)	0.0131 (9)	−0.0061 (9)	0.0016 (8)	−0.0023 (8)
C22	0.0141 (9)	0.0290 (11)	0.0200 (10)	−0.0058 (8)	−0.0013 (8)	0.0062 (9)
C31	0.0294 (12)	0.0268 (11)	0.0147 (10)	−0.0027 (9)	−0.0048 (9)	−0.0057 (8)
C32	0.0228 (10)	0.0131 (9)	0.0264 (11)	−0.0026 (8)	−0.0044 (9)	−0.0070 (8)

Geometric parameters (Å, º) top

Au1—Cl3	2.2818 (5)	C11—H11B	0.9800
Au1—Cl2	2.2846 (5)	C11—H11C	0.9800
Au1—Cl1	2.3064 (5)	C12—H12A	0.9800
Au1—S1	2.3250 (5)	C12—H12B	0.9800
S1—P1	2.0574 (7)	C12—H12C	0.9800
P1—C2	1.829 (2)	C21—H21A	0.9800
P1—C3	1.8317 (19)	C21—H21B	0.9800
P1—C1	1.8387 (19)	C21—H21C	0.9800
C1—C12	1.531 (3)	C22—H22A	0.9800
C1—C11	1.532 (3)	C22—H22B	0.9800
C1—H1	1.0000	C22—H22C	0.9800
C2—C21	1.525 (3)	C31—H31A	0.9800
C2—C22	1.534 (3)	C31—H31B	0.9800
C2—H2	1.0000	C31—H31C	0.9800
C3—C31	1.531 (3)	C32—H32A	0.9800
C3—C32	1.533 (3)	C32—H32B	0.9800
C3—H3	1.0000	C32—H32C	0.9800
C11—H11A	0.9800

Cl3—Au1—Cl2	175.341 (18)	C1—C11—H11C	109.5
Cl3—Au1—Cl1	90.151 (18)	H11A—C11—H11C	109.5
Cl2—Au1—Cl1	88.999 (19)	H11B—C11—H11C	109.5
Cl3—Au1—S1	92.249 (18)	C1—C12—H12A	109.5
Cl2—Au1—S1	88.545 (18)	C1—C12—H12B	109.5
Cl1—Au1—S1	177.472 (17)	H12A—C12—H12B	109.5
P1—S1—Au1	106.70 (2)	C1—C12—H12C	109.5
C2—P1—C3	108.01 (9)	H12A—C12—H12C	109.5
C2—P1—C1	115.39 (9)	H12B—C12—H12C	109.5
C3—P1—C1	106.80 (9)	C2—C21—H21A	109.5
C2—P1—S1	111.92 (7)	C2—C21—H21B	109.5
C3—P1—S1	113.32 (7)	H21A—C21—H21B	109.5
C1—P1—S1	101.34 (7)	C2—C21—H21C	109.5
C12—C1—C11	111.53 (18)	H21A—C21—H21C	109.5
C12—C1—P1	113.93 (14)	H21B—C21—H21C	109.5
C11—C1—P1	112.89 (14)	C2—C22—H22A	109.5
C12—C1—H1	105.9	C2—C22—H22B	109.5
C11—C1—H1	105.9	H22A—C22—H22B	109.5
P1—C1—H1	105.9	C2—C22—H22C	109.5
C21—C2—C22	111.88 (17)	H22A—C22—H22C	109.5
C21—C2—P1	113.49 (14)	H22B—C22—H22C	109.5
C22—C2—P1	113.14 (14)	C3—C31—H31A	109.5
C21—C2—H2	105.8	C3—C31—H31B	109.5
C22—C2—H2	105.8	H31A—C31—H31B	109.5
P1—C2—H2	105.8	C3—C31—H31C	109.5
C31—C3—C32	111.51 (17)	H31A—C31—H31C	109.5
C31—C3—P1	112.32 (14)	H31B—C31—H31C	109.5
C32—C3—P1	113.08 (14)	C3—C32—H32A	109.5
C31—C3—H3	106.5	C3—C32—H32B	109.5
C32—C3—H3	106.5	H32A—C32—H32B	109.5
P1—C3—H3	106.5	C3—C32—H32C	109.5
C1—C11—H11A	109.5	H32A—C32—H32C	109.5
C1—C11—H11B	109.5	H32B—C32—H32C	109.5
H11A—C11—H11B	109.5

Cl3—Au1—S1—P1	−72.41 (3)	C1—P1—C2—C21	−60.06 (17)
Cl2—Au1—S1—P1	112.19 (3)	S1—P1—C2—C21	55.13 (16)
Au1—S1—P1—C2	70.57 (7)	C3—P1—C2—C22	−50.58 (17)
Au1—S1—P1—C3	−51.87 (8)	C1—P1—C2—C22	68.81 (17)
Au1—S1—P1—C1	−165.92 (7)	S1—P1—C2—C22	−176.00 (13)
C2—P1—C1—C12	66.59 (18)	C2—P1—C3—C31	−179.04 (14)
C3—P1—C1—C12	−173.36 (16)	C1—P1—C3—C31	56.26 (17)
S1—P1—C1—C12	−54.51 (16)	S1—P1—C3—C31	−54.47 (16)
C2—P1—C1—C11	−61.96 (17)	C2—P1—C3—C32	−51.75 (17)
C3—P1—C1—C11	58.09 (17)	C1—P1—C3—C32	−176.45 (15)
S1—P1—C1—C11	176.93 (14)	S1—P1—C3—C32	72.83 (16)
C3—P1—C2—C21	−179.45 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32C···Au1	0.98	2.69	3.485 (2)	138
C2—H2···Cl3	1.00	2.68	3.437 (2)	133
C12—H12B···S1	0.98	2.73	3.310 (2)	118
C1—H1···Cl2ⁱ	1.00	2.82	3.506 (2)	126
C11—H11C···Cl2ⁱ	0.98	2.91	3.582 (2)	127
C22—H22A···Cl1ⁱⁱ	0.98	2.86	3.803 (2)	161
C2—H2···Cl3ⁱⁱ	1.00	2.86	3.688 (2)	141
C32—H32A···Cl2ⁱⁱⁱ	0.98	2.87	3.847 (2)	180
C3—H3···Cl2^iv	1.00	2.95	3.881 (2)	155

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z; (iv) x−1, y, z.

(tert-Butyldipropan-2-ylphosphane sulfide-κS)trichloridogold(III) (10a) top

Crystal data top

[AuCl₃(C₁₀H₂₃PS)]	F(000) = 976
M_r = 509.63	D_x = 2.051 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.4533 (2) Å	Cell parameters from 16512 reflections
b = 17.0563 (4) Å	θ = 2.1–30.8°
c = 11.4826 (3) Å	µ = 9.60 mm⁻¹
β = 94.525 (2)°	T = 100 K
V = 1650.43 (7) Å³	Plate, dichroic red / orange
Z = 4	0.3 × 0.2 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	4863 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4483 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.040
ω scan	θ_max = 30.9°, θ_min = 2.4°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→11
T_min = 0.192, T_max = 1.000	k = −24→23
40041 measured reflections	l = −15→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.046	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0188P)² + 1.7957P] where P = (F_o² + 2F_c²)/3
4863 reflections	(Δ/σ)_max = 0.004
152 parameters	Δρ_max = 2.15 e Å⁻³
0 restraints	Δρ_min = −1.41 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.53732 (2)	0.45811 (2)	0.69892 (2)	0.01252 (3)
Cl1	0.60148 (8)	0.33007 (4)	0.74376 (6)	0.02142 (13)
Cl2	0.78118 (7)	0.49571 (4)	0.77945 (6)	0.01953 (13)
Cl3	0.29411 (8)	0.41592 (4)	0.62396 (6)	0.01961 (13)
S1	0.49553 (7)	0.58842 (4)	0.64406 (6)	0.01545 (12)
P1	0.29578 (8)	0.63290 (4)	0.71079 (5)	0.01203 (12)
C1	0.2845 (3)	0.61053 (17)	0.8698 (2)	0.0175 (5)
C2	0.3186 (3)	0.73939 (16)	0.6906 (2)	0.0181 (5)
H2	0.225743	0.765191	0.723585	0.022*
C3	0.1136 (3)	0.59893 (16)	0.6267 (2)	0.0136 (5)
H3	0.086801	0.546807	0.659853	0.016*
C11	0.1916 (4)	0.6760 (2)	0.9271 (3)	0.0302 (7)
H11A	0.087035	0.681955	0.884754	0.045*
H11B	0.250247	0.725398	0.924447	0.045*
H11C	0.178412	0.662105	1.008626	0.045*
C12	0.4522 (3)	0.60526 (18)	0.9316 (2)	0.0210 (6)
H12A	0.444865	0.599219	1.015825	0.032*
H12B	0.511144	0.653237	0.916622	0.032*
H12C	0.507673	0.559959	0.901581	0.032*
C13	0.2002 (4)	0.53228 (19)	0.8846 (3)	0.0255 (7)
H13A	0.251077	0.491559	0.840353	0.038*
H13B	0.088482	0.537125	0.855490	0.038*
H13C	0.206934	0.517989	0.967533	0.038*
C21	0.4686 (4)	0.77242 (18)	0.7570 (3)	0.0269 (7)
H21A	0.562457	0.747474	0.728384	0.040*
H21B	0.465404	0.761735	0.840654	0.040*
H21C	0.473607	0.829162	0.744403	0.040*
C22	0.3144 (4)	0.76266 (18)	0.5614 (3)	0.0255 (6)
H22A	0.327366	0.819562	0.555111	0.038*
H22B	0.212447	0.747082	0.521601	0.038*
H22C	0.400784	0.736199	0.524910	0.038*
C31	−0.0295 (3)	0.65284 (17)	0.6416 (2)	0.0181 (5)
H31A	−0.008746	0.704791	0.609683	0.027*
H31B	−0.046308	0.657606	0.724769	0.027*
H31C	−0.124461	0.630425	0.599796	0.027*
C32	0.1375 (3)	0.58531 (16)	0.4971 (2)	0.0165 (5)
H32A	0.038294	0.566233	0.456976	0.025*
H32B	0.221306	0.546296	0.490133	0.025*
H32C	0.168064	0.634707	0.461534	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01036 (5)	0.01403 (6)	0.01301 (5)	−0.00005 (4)	−0.00001 (3)	−0.00017 (3)
Cl1	0.0212 (3)	0.0170 (3)	0.0257 (3)	0.0027 (3)	−0.0009 (2)	0.0029 (3)
Cl2	0.0117 (3)	0.0263 (4)	0.0201 (3)	−0.0019 (3)	−0.0024 (2)	0.0002 (3)
Cl3	0.0141 (3)	0.0168 (3)	0.0270 (3)	−0.0017 (2)	−0.0045 (2)	−0.0010 (3)
S1	0.0124 (3)	0.0152 (3)	0.0192 (3)	−0.0010 (2)	0.0032 (2)	0.0019 (2)
P1	0.0111 (3)	0.0123 (3)	0.0124 (3)	−0.0007 (2)	−0.0011 (2)	−0.0005 (2)
C1	0.0145 (12)	0.0266 (15)	0.0110 (11)	0.0018 (11)	−0.0019 (9)	0.0000 (10)
C2	0.0157 (12)	0.0137 (13)	0.0244 (13)	−0.0018 (10)	−0.0016 (10)	−0.0023 (10)
C3	0.0120 (11)	0.0154 (12)	0.0128 (11)	−0.0020 (10)	−0.0023 (9)	−0.0008 (9)
C11	0.0291 (16)	0.045 (2)	0.0170 (13)	0.0155 (15)	0.0014 (11)	−0.0051 (13)
C12	0.0196 (13)	0.0261 (15)	0.0165 (12)	0.0013 (12)	−0.0041 (10)	−0.0012 (11)
C13	0.0257 (15)	0.0347 (18)	0.0157 (13)	−0.0060 (13)	−0.0006 (11)	0.0074 (12)
C21	0.0222 (15)	0.0180 (14)	0.0392 (17)	−0.0055 (12)	−0.0059 (12)	−0.0050 (13)
C22	0.0287 (16)	0.0194 (15)	0.0284 (15)	−0.0054 (13)	0.0026 (12)	0.0058 (12)
C31	0.0119 (12)	0.0204 (14)	0.0214 (13)	0.0011 (11)	−0.0020 (9)	−0.0029 (10)
C32	0.0185 (13)	0.0181 (13)	0.0124 (11)	−0.0003 (11)	−0.0026 (9)	−0.0005 (10)

Geometric parameters (Å, º) top

Au1—Cl3	2.2818 (6)	C11—H11C	0.9800
Au1—Cl2	2.2837 (6)	C12—H12A	0.9800
Au1—Cl1	2.2989 (7)	C12—H12B	0.9800
Au1—S1	2.3294 (7)	C12—H12C	0.9800
S1—P1	2.0538 (9)	C13—H13A	0.9800
P1—C2	1.843 (3)	C13—H13B	0.9800
P1—C3	1.845 (2)	C13—H13C	0.9800
P1—C1	1.875 (3)	C21—H21A	0.9800
C1—C13	1.529 (4)	C21—H21B	0.9800
C1—C12	1.537 (4)	C21—H21C	0.9800
C1—C11	1.542 (4)	C22—H22A	0.9800
C2—C21	1.534 (4)	C22—H22B	0.9800
C2—C22	1.534 (4)	C22—H22C	0.9800
C2—H2	1.0000	C31—H31A	0.9800
C3—C32	1.535 (3)	C31—H31B	0.9800
C3—C31	1.540 (4)	C31—H31C	0.9800
C3—H3	1.0000	C32—H32A	0.9800
C11—H11A	0.9800	C32—H32B	0.9800
C11—H11B	0.9800	C32—H32C	0.9800

Cl3—Au1—Cl2	177.46 (2)	C1—C12—H12A	109.5
Cl3—Au1—Cl1	88.54 (2)	C1—C12—H12B	109.5
Cl2—Au1—Cl1	89.23 (3)	H12A—C12—H12B	109.5
Cl3—Au1—S1	94.93 (2)	C1—C12—H12C	109.5
Cl2—Au1—S1	87.39 (2)	H12A—C12—H12C	109.5
Cl1—Au1—S1	174.30 (2)	H12B—C12—H12C	109.5
P1—S1—Au1	111.29 (3)	C1—C13—H13A	109.5
C2—P1—C3	109.58 (12)	C1—C13—H13B	109.5
C2—P1—C1	109.67 (13)	H13A—C13—H13B	109.5
C3—P1—C1	109.94 (12)	C1—C13—H13C	109.5
C2—P1—S1	102.70 (10)	H13A—C13—H13C	109.5
C3—P1—S1	111.45 (9)	H13B—C13—H13C	109.5
C1—P1—S1	113.25 (9)	C2—C21—H21A	109.5
C13—C1—C12	108.6 (2)	C2—C21—H21B	109.5
C13—C1—C11	109.1 (3)	H21A—C21—H21B	109.5
C12—C1—C11	109.1 (2)	C2—C21—H21C	109.5
C13—C1—P1	110.25 (18)	H21A—C21—H21C	109.5
C12—C1—P1	110.19 (19)	H21B—C21—H21C	109.5
C11—C1—P1	109.59 (19)	C2—C22—H22A	109.5
C21—C2—C22	109.9 (2)	C2—C22—H22B	109.5
C21—C2—P1	113.0 (2)	H22A—C22—H22B	109.5
C22—C2—P1	112.4 (2)	C2—C22—H22C	109.5
C21—C2—H2	107.0	H22A—C22—H22C	109.5
C22—C2—H2	107.0	H22B—C22—H22C	109.5
P1—C2—H2	107.0	C3—C31—H31A	109.5
C32—C3—C31	111.2 (2)	C3—C31—H31B	109.5
C32—C3—P1	112.74 (18)	H31A—C31—H31B	109.5
C31—C3—P1	112.65 (18)	C3—C31—H31C	109.5
C32—C3—H3	106.6	H31A—C31—H31C	109.5
C31—C3—H3	106.6	H31B—C31—H31C	109.5
P1—C3—H3	106.6	C3—C32—H32A	109.5
C1—C11—H11A	109.5	C3—C32—H32B	109.5
C1—C11—H11B	109.5	H32A—C32—H32B	109.5
H11A—C11—H11B	109.5	C3—C32—H32C	109.5
C1—C11—H11C	109.5	H32A—C32—H32C	109.5
H11A—C11—H11C	109.5	H32B—C32—H32C	109.5
H11B—C11—H11C	109.5

Cl3—Au1—S1—P1	56.17 (4)	S1—P1—C1—C11	150.83 (18)
Cl2—Au1—S1—P1	−122.80 (4)	C3—P1—C2—C21	−179.5 (2)
Au1—S1—P1—C2	165.31 (9)	C1—P1—C2—C21	59.7 (2)
Au1—S1—P1—C3	−77.45 (10)	S1—P1—C2—C21	−60.9 (2)
Au1—S1—P1—C1	47.12 (11)	C3—P1—C2—C22	−54.4 (2)
C2—P1—C1—C13	156.8 (2)	C1—P1—C2—C22	−175.1 (2)
C3—P1—C1—C13	36.3 (2)	S1—P1—C2—C22	64.2 (2)
S1—P1—C1—C13	−89.1 (2)	C2—P1—C3—C32	81.7 (2)
C2—P1—C1—C12	−83.3 (2)	C1—P1—C3—C32	−157.68 (19)
C3—P1—C1—C12	156.11 (19)	S1—P1—C3—C32	−31.3 (2)
S1—P1—C1—C12	30.7 (2)	C2—P1—C3—C31	−45.2 (2)
C2—P1—C1—C11	36.8 (2)	C1—P1—C3—C31	75.4 (2)
C3—P1—C1—C11	−83.8 (2)	S1—P1—C3—C31	−158.18 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32B···Cl3	0.98	2.75	3.452 (3)	130
C3—H3···Cl3	1.00	2.89	3.476 (3)	118
C13—H13A···Cl3	0.98	2.85	3.729 (3)	150
C13—H13B···Cl2ⁱ	0.98	2.77	3.704 (3)	160
C31—H31A···Cl1ⁱⁱ	0.98	2.87	3.372 (3)	113
C13—H13C···Cl2ⁱⁱⁱ	0.98	2.91	3.878 (3)	170
C32—H32A···Cl3^iv	0.98	2.91	3.800 (3)	152

Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+1, −z+1.

(tert-Butyldipropan-2-ylphosphane sulfide-κS)trichloridogold(III) (10aa) top

Crystal data top

[AuCl₃(C₁₀H₂₃PS)]	F(000) = 976
M_r = 509.63	D_x = 2.073 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.9363 (3) Å	Cell parameters from 14677 reflections
b = 14.4096 (4) Å	θ = 2.8–30.4°
c = 14.2851 (4) Å	µ = 9.70 mm⁻¹
β = 91.774 (3)°	T = 100 K
V = 1632.85 (9) Å³	Block, red
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	4881 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4296 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.046
ω scan	θ_max = 30.8°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −11→11
T_min = 0.159, T_max = 0.247	k = −20→19
42542 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.045	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0115P)² + 2.5557P] where P = (F_o² + 2F_c²)/3
4881 reflections	(Δ/σ)_max = 0.001
152 parameters	Δρ_max = 2.52 e Å⁻³
0 restraints	Δρ_min = −1.50 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.47137 (2)	0.07045 (2)	0.32157 (2)	0.01326 (4)
Cl1	0.43370 (11)	0.01606 (6)	0.17013 (5)	0.02278 (17)
Cl2	0.18806 (10)	0.09762 (6)	0.32608 (6)	0.02314 (17)
Cl3	0.75081 (10)	0.03377 (6)	0.31862 (6)	0.02016 (16)
S1	0.49165 (10)	0.12326 (5)	0.47552 (5)	0.01625 (16)
P1	0.65482 (10)	0.23397 (5)	0.48821 (5)	0.01177 (15)
C1	0.6113 (4)	0.3267 (2)	0.3991 (2)	0.0177 (7)
C2	0.6125 (4)	0.2749 (2)	0.6072 (2)	0.0164 (6)
H2	0.701534	0.321315	0.624880	0.020*
C3	0.8755 (4)	0.1971 (2)	0.4808 (2)	0.0217 (7)
H3	0.889522	0.177394	0.414348	0.026*
C11	0.6778 (4)	0.4205 (2)	0.4368 (2)	0.0226 (7)
H11A	0.664136	0.467885	0.387920	0.034*
H11B	0.797448	0.414501	0.454791	0.034*
H11C	0.614084	0.438648	0.491501	0.034*
C12	0.4234 (5)	0.3349 (3)	0.3759 (3)	0.0324 (9)
H12A	0.363374	0.349423	0.433018	0.049*
H12B	0.381545	0.276083	0.349810	0.049*
H12C	0.404201	0.384591	0.329903	0.049*
C13	0.7034 (6)	0.3016 (2)	0.3089 (2)	0.0331 (9)
H13A	0.669156	0.239351	0.288111	0.050*
H13B	0.825429	0.302658	0.321490	0.050*
H13C	0.673948	0.346738	0.259745	0.050*
C21	0.4421 (5)	0.3221 (2)	0.6167 (2)	0.0247 (8)
H21A	0.351900	0.277980	0.600347	0.037*
H21B	0.434612	0.375598	0.574483	0.037*
H21C	0.430237	0.342953	0.681460	0.037*
C22	0.6245 (5)	0.1950 (3)	0.6794 (2)	0.0278 (8)
H22A	0.612684	0.220219	0.742566	0.042*
H22B	0.734042	0.164198	0.675259	0.042*
H22C	0.534206	0.150064	0.666093	0.042*
C31	1.0042 (5)	0.2758 (3)	0.4984 (4)	0.0467 (13)
H31A	0.987941	0.302640	0.560531	0.070*
H31B	0.987610	0.323988	0.450586	0.070*
H31C	1.118712	0.250844	0.495347	0.070*
C32	0.9210 (5)	0.1124 (3)	0.5405 (3)	0.0389 (11)
H32A	1.025232	0.084618	0.518326	0.058*
H32B	0.829555	0.066760	0.535428	0.058*
H32C	0.937441	0.131286	0.606022	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01406 (6)	0.01090 (6)	0.01491 (6)	−0.00074 (5)	0.00199 (4)	−0.00097 (4)
Cl1	0.0267 (4)	0.0249 (4)	0.0166 (4)	0.0004 (3)	−0.0017 (3)	−0.0040 (3)
Cl2	0.0141 (4)	0.0280 (4)	0.0274 (4)	0.0012 (3)	0.0008 (3)	−0.0010 (3)
Cl3	0.0158 (4)	0.0216 (4)	0.0232 (4)	0.0025 (3)	0.0025 (3)	−0.0077 (3)
S1	0.0198 (4)	0.0138 (4)	0.0154 (4)	−0.0050 (3)	0.0055 (3)	−0.0016 (3)
P1	0.0117 (4)	0.0104 (4)	0.0132 (4)	0.0005 (3)	0.0017 (3)	−0.0007 (3)
C1	0.0267 (17)	0.0126 (15)	0.0141 (15)	0.0007 (13)	0.0026 (13)	0.0024 (12)
C2	0.0171 (15)	0.0186 (16)	0.0136 (14)	0.0001 (12)	0.0031 (12)	−0.0049 (12)
C3	0.0162 (16)	0.0229 (18)	0.0261 (18)	0.0047 (13)	0.0000 (13)	−0.0079 (14)
C11	0.0268 (18)	0.0126 (16)	0.0287 (18)	−0.0035 (13)	0.0069 (14)	0.0010 (13)
C12	0.036 (2)	0.0202 (19)	0.040 (2)	0.0030 (16)	−0.0183 (18)	0.0052 (16)
C13	0.064 (3)	0.0171 (18)	0.0192 (17)	0.0021 (18)	0.0139 (18)	0.0036 (14)
C21	0.0299 (19)	0.0241 (18)	0.0205 (17)	0.0074 (15)	0.0094 (15)	0.0023 (14)
C22	0.036 (2)	0.033 (2)	0.0152 (16)	0.0104 (17)	0.0005 (15)	0.0009 (15)
C31	0.0168 (19)	0.046 (3)	0.077 (3)	−0.0011 (18)	−0.001 (2)	−0.037 (2)
C32	0.032 (2)	0.054 (3)	0.031 (2)	0.029 (2)	0.0032 (17)	0.0061 (19)

Geometric parameters (Å, º) top

Au1—Cl3	2.2815 (8)	C11—H11C	0.9800
Au1—Cl2	2.2851 (8)	C12—H12A	0.9800
Au1—Cl1	2.3116 (8)	C12—H12B	0.9800
Au1—S1	2.3281 (8)	C12—H12C	0.9800
S1—P1	2.0592 (11)	C13—H13A	0.9800
P1—C3	1.836 (3)	C13—H13B	0.9800
P1—C2	1.839 (3)	C13—H13C	0.9800
P1—C1	1.871 (3)	C21—H21A	0.9800
C1—C12	1.522 (5)	C21—H21B	0.9800
C1—C11	1.541 (4)	C21—H21C	0.9800
C1—C13	1.544 (4)	C22—H22A	0.9800
C2—C21	1.524 (4)	C22—H22B	0.9800
C2—C22	1.546 (5)	C22—H22C	0.9800
C2—H2	1.0000	C31—H31A	0.9800
C3—C32	1.527 (5)	C31—H31B	0.9800
C3—C31	1.542 (5)	C31—H31C	0.9800
C3—H3	1.0000	C32—H32A	0.9800
C11—H11A	0.9800	C32—H32B	0.9800
C11—H11B	0.9800	C32—H32C	0.9800

Cl3—Au1—Cl2	176.43 (3)	C1—C12—H12A	109.5
Cl3—Au1—Cl1	90.10 (3)	C1—C12—H12B	109.5
Cl2—Au1—Cl1	89.18 (3)	H12A—C12—H12B	109.5
Cl3—Au1—S1	93.11 (3)	C1—C12—H12C	109.5
Cl2—Au1—S1	87.51 (3)	H12A—C12—H12C	109.5
Cl1—Au1—S1	176.43 (3)	H12B—C12—H12C	109.5
P1—S1—Au1	111.18 (4)	C1—C13—H13A	109.5
C3—P1—C2	110.36 (15)	C1—C13—H13B	109.5
C3—P1—C1	108.88 (16)	H13A—C13—H13B	109.5
C2—P1—C1	111.39 (14)	C1—C13—H13C	109.5
C3—P1—S1	111.66 (12)	H13A—C13—H13C	109.5
C2—P1—S1	101.38 (11)	H13B—C13—H13C	109.5
C1—P1—S1	113.03 (11)	C2—C21—H21A	109.5
C12—C1—C11	109.3 (3)	C2—C21—H21B	109.5
C12—C1—C13	108.8 (3)	H21A—C21—H21B	109.5
C11—C1—C13	109.3 (3)	C2—C21—H21C	109.5
C12—C1—P1	111.3 (2)	H21A—C21—H21C	109.5
C11—C1—P1	109.5 (2)	H21B—C21—H21C	109.5
C13—C1—P1	108.6 (2)	C2—C22—H22A	109.5
C21—C2—C22	108.0 (3)	C2—C22—H22B	109.5
C21—C2—P1	114.4 (2)	H22A—C22—H22B	109.5
C22—C2—P1	111.6 (2)	C2—C22—H22C	109.5
C21—C2—H2	107.5	H22A—C22—H22C	109.5
C22—C2—H2	107.5	H22B—C22—H22C	109.5
P1—C2—H2	107.5	C3—C31—H31A	109.5
C32—C3—C31	110.7 (3)	C3—C31—H31B	109.5
C32—C3—P1	114.1 (3)	H31A—C31—H31B	109.5
C31—C3—P1	113.9 (2)	C3—C31—H31C	109.5
C32—C3—H3	105.8	H31A—C31—H31C	109.5
C31—C3—H3	105.8	H31B—C31—H31C	109.5
P1—C3—H3	105.8	C3—C32—H32A	109.5
C1—C11—H11A	109.5	C3—C32—H32B	109.5
C1—C11—H11B	109.5	H32A—C32—H32B	109.5
H11A—C11—H11B	109.5	C3—C32—H32C	109.5
C1—C11—H11C	109.5	H32A—C32—H32C	109.5
H11A—C11—H11C	109.5	H32B—C32—H32C	109.5
H11B—C11—H11C	109.5

Cl3—Au1—S1—P1	61.27 (5)	S1—P1—C1—C13	−85.6 (3)
Cl2—Au1—S1—P1	−122.25 (5)	C3—P1—C2—C21	170.2 (2)
Au1—S1—P1—C3	−73.62 (13)	C1—P1—C2—C21	49.1 (3)
Au1—S1—P1—C2	168.88 (11)	S1—P1—C2—C21	−71.3 (2)
Au1—S1—P1—C1	49.55 (12)	C3—P1—C2—C22	−66.8 (3)
C3—P1—C1—C12	158.8 (2)	C1—P1—C2—C22	172.2 (2)
C2—P1—C1—C12	−79.2 (3)	S1—P1—C2—C22	51.7 (2)
S1—P1—C1—C12	34.1 (3)	C2—P1—C3—C32	65.5 (3)
C3—P1—C1—C11	−80.2 (2)	C1—P1—C3—C32	−172.0 (3)
C2—P1—C1—C11	41.7 (3)	S1—P1—C3—C32	−46.5 (3)
S1—P1—C1—C11	155.07 (19)	C2—P1—C3—C31	−63.0 (3)
C3—P1—C1—C13	39.1 (3)	C1—P1—C3—C31	59.6 (3)
C2—P1—C1—C13	161.0 (2)	S1—P1—C3—C31	−174.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl3	1.00	2.70	3.427 (3)	130
C3—H3···Cl2ⁱ	1.00	2.95	3.665 (3)	129
C21—H21C···Cl2ⁱⁱ	0.98	2.99	3.706 (4)	131
C22—H22A···Cl2ⁱⁱ	0.98	2.94	3.675 (4)	133
C13—H13C···Cl3ⁱⁱⁱ	0.98	2.99	3.832 (4)	145

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Trichlorido[di-tert-butyl(propan-2-yl)phosphane sulfide-κS]gold(III) (11a) top

Crystal data top

[AuCl₃(C₁₁H₂₅PS)]	Z = 2
M_r = 523.66	F(000) = 504
Triclinic, P1	D_x = 2.011 Mg m⁻³
a = 8.6034 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7779 (4) Å	Cell parameters from 31596 reflections
c = 11.4231 (4) Å	θ = 2.2–30.8°
α = 78.876 (3)°	µ = 9.16 mm⁻¹
β = 71.456 (4)°	T = 100 K
γ = 72.702 (4)°	Plate, red
V = 864.69 (7) Å³	0.15 × 0.15 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	5155 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4939 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.038
ω scan	θ_max = 30.8°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→12
T_min = 0.577, T_max = 1.000	k = −14→14
68815 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.036	w = 1/[σ²(F_o²) + (0.0168P)² + 0.7385P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.003
5155 reflections	Δρ_max = 1.64 e Å⁻³
163 parameters	Δρ_min = −0.93 e Å⁻³
0 restraints	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015), F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00097 (14)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.46476 (2)	0.35014 (2)	0.24072 (2)	0.01322 (3)
Cl1	0.53637 (8)	0.12179 (5)	0.34127 (5)	0.02358 (11)
Cl2	0.73242 (6)	0.37151 (5)	0.21222 (5)	0.02016 (10)
Cl3	0.20542 (7)	0.31734 (5)	0.25815 (5)	0.02182 (10)
S1	0.40624 (6)	0.58036 (5)	0.13465 (4)	0.01345 (9)
P1	0.21575 (6)	0.72281 (5)	0.24712 (4)	0.00958 (8)
C1	0.2568 (2)	0.7093 (2)	0.40129 (16)	0.0120 (3)
C2	0.2277 (2)	0.8996 (2)	0.15054 (16)	0.0129 (3)
C3	0.0119 (2)	0.6799 (2)	0.27290 (18)	0.0144 (4)
H3	0.028473	0.577669	0.311603	0.017*
C11	0.1566 (3)	0.8445 (2)	0.46903 (18)	0.0166 (4)
H11A	0.175463	0.830339	0.551228	0.025*
H11B	0.035482	0.860654	0.478365	0.025*
H11C	0.195308	0.928404	0.420505	0.025*
C12	0.4458 (2)	0.6884 (2)	0.38625 (18)	0.0160 (4)
H12A	0.464884	0.674279	0.468368	0.024*
H12B	0.481411	0.773860	0.338457	0.024*
H12C	0.511838	0.603622	0.342337	0.024*
C13	0.2023 (3)	0.5771 (2)	0.48235 (17)	0.0154 (4)
H13A	0.261577	0.491274	0.438534	0.023*
H13B	0.079670	0.592422	0.499118	0.023*
H13C	0.230881	0.563523	0.560995	0.023*
C21	0.2573 (3)	0.8834 (2)	0.01298 (18)	0.0187 (4)
H21A	0.249579	0.978272	−0.035494	0.028*
H21B	0.170971	0.841459	0.005595	0.028*
H21C	0.370012	0.820130	−0.018603	0.028*
C22	0.0615 (3)	1.0154 (2)	0.19359 (19)	0.0172 (4)
H22A	0.073803	1.109141	0.148052	0.026*
H22B	0.036261	1.020447	0.282805	0.026*
H22C	−0.031281	0.990337	0.177297	0.026*
C23	0.3768 (3)	0.9485 (2)	0.15964 (19)	0.0179 (4)
H23A	0.481893	0.873138	0.135293	0.027*
H23B	0.357471	0.966281	0.245317	0.027*
H23C	0.386403	1.037364	0.104132	0.027*
C31	−0.0281 (3)	0.6790 (2)	0.1513 (2)	0.0231 (4)
H31A	−0.116373	0.627857	0.168074	0.035*
H31B	0.074582	0.630193	0.092018	0.035*
H31C	−0.067901	0.778349	0.116337	0.035*
C32	−0.1431 (3)	0.7650 (2)	0.3650 (2)	0.0204 (4)
H32A	−0.166224	0.867347	0.333210	0.031*
H32B	−0.120054	0.753022	0.445560	0.031*
H32C	−0.241804	0.728860	0.374972	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01600 (5)	0.01034 (4)	0.01333 (4)	0.00004 (3)	−0.00561 (3)	−0.00404 (2)
Cl1	0.0333 (3)	0.0125 (2)	0.0272 (2)	−0.00151 (19)	−0.0165 (2)	−0.00033 (18)
Cl2	0.0157 (2)	0.0205 (2)	0.0245 (2)	0.00003 (18)	−0.00744 (18)	−0.00704 (18)
Cl3	0.0195 (2)	0.0144 (2)	0.0338 (3)	−0.00423 (18)	−0.0088 (2)	−0.00533 (18)
S1	0.0157 (2)	0.0119 (2)	0.01053 (18)	−0.00038 (16)	−0.00253 (16)	−0.00305 (15)
P1	0.0100 (2)	0.00913 (19)	0.00972 (19)	−0.00157 (16)	−0.00349 (16)	−0.00143 (15)
C1	0.0121 (9)	0.0137 (8)	0.0104 (7)	−0.0006 (7)	−0.0049 (6)	−0.0026 (6)
C2	0.0159 (9)	0.0111 (8)	0.0114 (8)	−0.0040 (7)	−0.0039 (7)	0.0006 (6)
C3	0.0118 (9)	0.0122 (8)	0.0209 (9)	−0.0040 (7)	−0.0074 (7)	0.0008 (7)
C11	0.0174 (10)	0.0167 (9)	0.0146 (8)	0.0000 (7)	−0.0041 (7)	−0.0067 (7)
C12	0.0121 (9)	0.0194 (9)	0.0176 (9)	−0.0008 (7)	−0.0066 (7)	−0.0053 (7)
C13	0.0185 (10)	0.0145 (9)	0.0115 (8)	−0.0015 (7)	−0.0050 (7)	−0.0003 (6)
C21	0.0268 (11)	0.0170 (9)	0.0128 (8)	−0.0073 (8)	−0.0065 (8)	0.0017 (7)
C22	0.0186 (10)	0.0113 (8)	0.0205 (9)	−0.0012 (7)	−0.0074 (8)	0.0004 (7)
C23	0.0198 (10)	0.0167 (9)	0.0179 (9)	−0.0086 (8)	−0.0034 (7)	0.0000 (7)
C31	0.0244 (12)	0.0246 (11)	0.0282 (11)	−0.0105 (9)	−0.0169 (9)	0.0023 (8)
C32	0.0096 (9)	0.0199 (10)	0.0283 (10)	−0.0027 (7)	−0.0033 (8)	0.0007 (8)

Geometric parameters (Å, º) top

Au1—Cl2	2.2881 (5)	C12—H12B	0.9800
Au1—Cl3	2.2889 (5)	C12—H12C	0.9800
Au1—Cl1	2.3080 (5)	C13—H13A	0.9800
Au1—S1	2.3346 (5)	C13—H13B	0.9800
S1—P1	2.0665 (6)	C13—H13C	0.9800
P1—C3	1.8442 (19)	C21—H21A	0.9800
P1—C2	1.8741 (18)	C21—H21B	0.9800
P1—C1	1.8765 (18)	C21—H21C	0.9800
C1—C12	1.534 (3)	C22—H22A	0.9800
C1—C13	1.540 (3)	C22—H22B	0.9800
C1—C11	1.543 (3)	C22—H22C	0.9800
C2—C23	1.535 (3)	C23—H23A	0.9800
C2—C22	1.541 (3)	C23—H23B	0.9800
C2—C21	1.542 (3)	C23—H23C	0.9800
C3—C31	1.535 (3)	C31—H31A	0.9800
C3—C32	1.537 (3)	C31—H31B	0.9800
C3—H3	1.0000	C31—H31C	0.9800
C11—H11A	0.9800	C32—H32A	0.9800
C11—H11B	0.9800	C32—H32B	0.9800
C11—H11C	0.9800	C32—H32C	0.9800
C12—H12A	0.9800

Cl2—Au1—Cl3	175.769 (17)	C1—C12—H12C	109.5
Cl2—Au1—Cl1	89.44 (2)	H12A—C12—H12C	109.5
Cl3—Au1—Cl1	89.35 (2)	H12B—C12—H12C	109.5
Cl2—Au1—S1	87.963 (19)	C1—C13—H13A	109.5
Cl3—Au1—S1	93.175 (19)	C1—C13—H13B	109.5
Cl1—Au1—S1	177.237 (19)	H13A—C13—H13B	109.5
P1—S1—Au1	111.35 (2)	C1—C13—H13C	109.5
C3—P1—C2	112.66 (9)	H13A—C13—H13C	109.5
C3—P1—C1	108.88 (9)	H13B—C13—H13C	109.5
C2—P1—C1	113.61 (8)	C2—C21—H21A	109.5
C3—P1—S1	109.17 (7)	C2—C21—H21B	109.5
C2—P1—S1	101.48 (6)	H21A—C21—H21B	109.5
C1—P1—S1	110.81 (6)	C2—C21—H21C	109.5
C12—C1—C13	108.33 (16)	H21A—C21—H21C	109.5
C12—C1—C11	108.22 (16)	H21B—C21—H21C	109.5
C13—C1—C11	108.84 (15)	C2—C22—H22A	109.5
C12—C1—P1	111.17 (13)	C2—C22—H22B	109.5
C13—C1—P1	108.09 (13)	H22A—C22—H22B	109.5
C11—C1—P1	112.11 (13)	C2—C22—H22C	109.5
C23—C2—C22	109.55 (16)	H22A—C22—H22C	109.5
C23—C2—C21	107.67 (16)	H22B—C22—H22C	109.5
C22—C2—C21	108.83 (16)	C2—C23—H23A	109.5
C23—C2—P1	110.43 (13)	C2—C23—H23B	109.5
C22—C2—P1	110.44 (13)	H23A—C23—H23B	109.5
C21—C2—P1	109.85 (13)	C2—C23—H23C	109.5
C31—C3—C32	110.93 (17)	H23A—C23—H23C	109.5
C31—C3—P1	112.85 (14)	H23B—C23—H23C	109.5
C32—C3—P1	116.89 (14)	C3—C31—H31A	109.5
C31—C3—H3	105.0	C3—C31—H31B	109.5
C32—C3—H3	105.0	H31A—C31—H31B	109.5
P1—C3—H3	105.0	C3—C31—H31C	109.5
C1—C11—H11A	109.5	H31A—C31—H31C	109.5
C1—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	C3—C32—H32A	109.5
C1—C11—H11C	109.5	C3—C32—H32B	109.5
H11A—C11—H11C	109.5	H32A—C32—H32B	109.5
H11B—C11—H11C	109.5	C3—C32—H32C	109.5
C1—C12—H12A	109.5	H32A—C32—H32C	109.5
C1—C12—H12B	109.5	H32B—C32—H32C	109.5
H12A—C12—H12B	109.5

Cl2—Au1—S1—P1	−117.55 (3)	C1—P1—C2—C23	41.02 (16)
Cl3—Au1—S1—P1	66.53 (3)	S1—P1—C2—C23	−77.95 (13)
Au1—S1—P1—C3	−71.70 (7)	C3—P1—C2—C22	44.11 (16)
Au1—S1—P1—C2	169.16 (6)	C1—P1—C2—C22	−80.31 (15)
Au1—S1—P1—C1	48.21 (7)	S1—P1—C2—C22	160.72 (12)
C3—P1—C1—C12	159.11 (13)	C3—P1—C2—C21	−75.95 (16)
C2—P1—C1—C12	−74.46 (15)	C1—P1—C2—C21	159.63 (13)
S1—P1—C1—C12	39.02 (14)	S1—P1—C2—C21	40.66 (14)
C3—P1—C1—C13	40.34 (15)	C2—P1—C3—C31	56.54 (17)
C2—P1—C1—C13	166.77 (12)	C1—P1—C3—C31	−176.48 (14)
S1—P1—C1—C13	−79.75 (13)	S1—P1—C3—C31	−55.39 (15)
C3—P1—C1—C11	−79.62 (15)	C2—P1—C3—C32	−73.88 (16)
C2—P1—C1—C11	46.82 (16)	C1—P1—C3—C32	53.10 (16)
S1—P1—C1—C11	160.30 (12)	S1—P1—C3—C32	174.19 (13)
C3—P1—C2—C23	165.44 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Au1	0.98	2.71	3.6142 (19)	154
C12—H12C···S1	0.98	2.86	3.391 (2)	115
C3—H3···Cl3	1.00	2.62	3.451 (2)	140
C12—H12C···Cl2	0.98	2.81	3.788 (2)	174
C13—H13C···Cl2ⁱ	0.98	2.91	3.851 (2)	161

Symmetry code: (i) −x+1, −y+1, −z+1.

Trichlorido[di-tert-butyl(propan-2-yl)phosphane sulfide-κS]gold(III) chloroform-d monosilvate (11aa) top

Crystal data top

[AuCl₃(C₁₁H₂₅PS)]·CDCl₃	Z = 2
M_r = 644.03	F(000) = 620
Triclinic, P1	D_x = 2.031 Mg m⁻³
a = 9.6382 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2787 (3) Å	Cell parameters from 35195 reflections
c = 11.8483 (5) Å	θ = 2.3–30.9°
α = 75.115 (3)°	µ = 7.91 mm⁻¹
β = 68.875 (4)°	T = 101 K
γ = 89.728 (3)°	Plate, dichroic red / orange
V = 1053.13 (8) Å³	0.15 × 0.06 × 0.05 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	6247 independent reflections
Radiation source: fine-focus sealed tube	5976 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.038
ω scan	θ_max = 30.9°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −13→13
T_min = 0.454, T_max = 1.000	k = −14→14
76947 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.033	w = 1/[σ²(F_o²) + (0.0135P)² + 0.8433P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
6247 reflections	Δρ_max = 1.02 e Å⁻³
199 parameters	Δρ_min = −0.95 e Å⁻³
0 restraints	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015), F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00133 (9)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.71266 (2)	0.36753 (2)	0.29738 (2)	0.01055 (3)
Cl1	0.85075 (5)	0.38930 (5)	0.41619 (4)	0.01711 (9)
Cl2	0.62356 (5)	0.57177 (5)	0.31290 (5)	0.01741 (9)
Cl3	0.81385 (5)	0.16897 (5)	0.27791 (4)	0.01599 (9)
S1	0.58436 (5)	0.35877 (5)	0.16572 (4)	0.01218 (8)
P1	0.41142 (5)	0.20633 (5)	0.24806 (4)	0.00919 (8)
C1	0.28613 (19)	0.21927 (19)	0.40702 (17)	0.0122 (3)
C2	0.3218 (2)	0.23846 (19)	0.12786 (17)	0.0124 (3)
C3	0.4907 (2)	0.04179 (18)	0.26592 (18)	0.0130 (3)
H3	0.553904	0.045302	0.316195	0.016*
C11	0.1340 (2)	0.1352 (2)	0.45315 (18)	0.0163 (4)
H11A	0.080315	0.173434	0.397891	0.024*
H11B	0.074531	0.137380	0.539288	0.024*
H11C	0.150519	0.041430	0.451538	0.024*
C12	0.2587 (2)	0.3669 (2)	0.40576 (19)	0.0171 (4)
H12A	0.203030	0.371837	0.491747	0.026*
H12B	0.200708	0.400980	0.353136	0.026*
H12C	0.354755	0.422152	0.371587	0.026*
C13	0.3657 (2)	0.1650 (2)	0.49907 (18)	0.0168 (4)
H13A	0.304536	0.174026	0.582547	0.025*
H13B	0.463110	0.216998	0.468932	0.025*
H13C	0.379886	0.069480	0.504286	0.025*
C21	0.4419 (2)	0.2753 (2)	−0.00570 (18)	0.0168 (4)
H21A	0.498151	0.361608	−0.021724	0.025*
H21B	0.393993	0.283422	−0.067086	0.025*
H21C	0.510291	0.204345	−0.013415	0.025*
C22	0.2238 (2)	0.1106 (2)	0.14607 (19)	0.0164 (4)
H22A	0.172467	0.130120	0.086540	0.025*
H22B	0.149695	0.083415	0.232245	0.025*
H22C	0.287056	0.037131	0.130972	0.025*
C23	0.2252 (2)	0.3569 (2)	0.13874 (19)	0.0175 (4)
H23A	0.191371	0.380526	0.067932	0.026*
H23B	0.284111	0.435102	0.137323	0.026*
H23C	0.138221	0.330673	0.217906	0.026*
C31	0.5994 (2)	0.0242 (2)	0.1402 (2)	0.0194 (4)
H31A	0.542761	0.004996	0.091357	0.029*
H31B	0.658640	−0.051177	0.156429	0.029*
H31C	0.666269	0.107416	0.092779	0.029*
C32	0.3807 (2)	−0.0861 (2)	0.3403 (2)	0.0188 (4)
H32A	0.435800	−0.166423	0.339373	0.028*
H32B	0.307285	−0.090300	0.301368	0.028*
H32C	0.329015	−0.082875	0.427331	0.028*
C99	0.9953 (2)	0.7075 (2)	0.19499 (19)	0.0174 (4)
D99	0.908901	0.650866	0.267327	0.021*
Cl4	1.15235 (7)	0.69803 (6)	0.23818 (6)	0.03287 (13)
Cl5	1.02700 (7)	0.64377 (7)	0.06444 (5)	0.03256 (13)
Cl6	0.94906 (6)	0.87534 (5)	0.16252 (6)	0.02991 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.00947 (3)	0.00984 (4)	0.01275 (4)	−0.00047 (2)	−0.00505 (2)	−0.00240 (2)
Cl1	0.0184 (2)	0.0171 (2)	0.0213 (2)	0.00185 (17)	−0.01281 (18)	−0.00659 (18)
Cl2	0.0179 (2)	0.0133 (2)	0.0260 (2)	0.00321 (16)	−0.01179 (18)	−0.00836 (18)
Cl3	0.01472 (19)	0.0135 (2)	0.0228 (2)	0.00333 (16)	−0.00933 (17)	−0.00660 (17)
S1	0.01193 (18)	0.0116 (2)	0.01239 (19)	−0.00215 (15)	−0.00557 (16)	−0.00065 (16)
P1	0.00947 (18)	0.0086 (2)	0.0102 (2)	0.00033 (15)	−0.00460 (16)	−0.00252 (16)
C1	0.0111 (7)	0.0147 (9)	0.0112 (8)	0.0001 (6)	−0.0038 (6)	−0.0045 (7)
C2	0.0139 (8)	0.0125 (9)	0.0126 (8)	0.0009 (6)	−0.0074 (7)	−0.0029 (7)
C3	0.0146 (8)	0.0104 (8)	0.0168 (9)	0.0029 (6)	−0.0089 (7)	−0.0037 (7)
C11	0.0116 (8)	0.0188 (10)	0.0167 (9)	−0.0022 (7)	−0.0029 (7)	−0.0049 (7)
C12	0.0163 (8)	0.0169 (10)	0.0192 (9)	0.0021 (7)	−0.0051 (7)	−0.0093 (8)
C13	0.0170 (9)	0.0215 (10)	0.0116 (8)	0.0005 (7)	−0.0059 (7)	−0.0031 (7)
C21	0.0206 (9)	0.0180 (10)	0.0128 (8)	0.0012 (7)	−0.0079 (7)	−0.0034 (7)
C22	0.0183 (9)	0.0157 (9)	0.0192 (9)	−0.0001 (7)	−0.0111 (7)	−0.0055 (7)
C23	0.0179 (9)	0.0155 (9)	0.0229 (10)	0.0046 (7)	−0.0122 (8)	−0.0049 (8)
C31	0.0216 (9)	0.0184 (10)	0.0230 (10)	0.0086 (8)	−0.0102 (8)	−0.0112 (8)
C32	0.0227 (9)	0.0109 (9)	0.0251 (10)	−0.0003 (7)	−0.0134 (8)	−0.0025 (8)
C99	0.0163 (8)	0.0164 (10)	0.0190 (9)	0.0002 (7)	−0.0071 (7)	−0.0034 (8)
Cl4	0.0319 (3)	0.0245 (3)	0.0538 (4)	0.0034 (2)	−0.0308 (3)	−0.0084 (3)
Cl5	0.0323 (3)	0.0471 (4)	0.0242 (3)	0.0140 (3)	−0.0109 (2)	−0.0191 (3)
Cl6	0.0246 (2)	0.0168 (2)	0.0473 (3)	0.0038 (2)	−0.0153 (2)	−0.0042 (2)

Geometric parameters (Å, º) top

Au1—Cl3	2.2871 (5)	C13—H13A	0.9800
Au1—Cl2	2.2903 (5)	C13—H13B	0.9800
Au1—Cl1	2.3060 (4)	C13—H13C	0.9800
Au1—S1	2.3312 (4)	C21—H21A	0.9800
S1—P1	2.0622 (6)	C21—H21B	0.9800
P1—C3	1.8465 (19)	C21—H21C	0.9800
P1—C1	1.8737 (18)	C22—H22A	0.9800
P1—C2	1.8778 (18)	C22—H22B	0.9800
C1—C12	1.537 (3)	C22—H22C	0.9800
C1—C13	1.541 (2)	C23—H23A	0.9800
C1—C11	1.545 (2)	C23—H23B	0.9800
C2—C23	1.532 (3)	C23—H23C	0.9800
C2—C21	1.538 (3)	C31—H31A	0.9800
C2—C22	1.544 (3)	C31—H31B	0.9800
C3—C31	1.536 (3)	C31—H31C	0.9800
C3—C32	1.540 (3)	C32—H32A	0.9800
C3—H3	1.0000	C32—H32B	0.9800
C11—H11A	0.9800	C32—H32C	0.9800
C11—H11B	0.9800	C99—Cl5	1.758 (2)
C11—H11C	0.9800	C99—Cl4	1.759 (2)
C12—H12A	0.9800	C99—Cl6	1.761 (2)
C12—H12B	0.9800	C99—D99	1.0000
C12—H12C	0.9800

Cl3—Au1—Cl2	177.050 (16)	C1—C13—H13A	109.5
Cl3—Au1—Cl1	88.505 (17)	C1—C13—H13B	109.5
Cl2—Au1—Cl1	89.783 (17)	H13A—C13—H13B	109.5
Cl3—Au1—S1	92.936 (17)	C1—C13—H13C	109.5
Cl2—Au1—S1	88.609 (16)	H13A—C13—H13C	109.5
Cl1—Au1—S1	175.816 (16)	H13B—C13—H13C	109.5
P1—S1—Au1	111.96 (2)	C2—C21—H21A	109.5
C3—P1—C1	108.94 (8)	C2—C21—H21B	109.5
C3—P1—C2	112.62 (8)	H21A—C21—H21B	109.5
C1—P1—C2	114.39 (8)	C2—C21—H21C	109.5
C3—P1—S1	108.73 (6)	H21A—C21—H21C	109.5
C1—P1—S1	110.75 (6)	H21B—C21—H21C	109.5
C2—P1—S1	101.09 (6)	C2—C22—H22A	109.5
C12—C1—C13	108.22 (15)	C2—C22—H22B	109.5
C12—C1—C11	108.90 (15)	H22A—C22—H22B	109.5
C13—C1—C11	109.41 (15)	C2—C22—H22C	109.5
C12—C1—P1	111.28 (13)	H22A—C22—H22C	109.5
C13—C1—P1	107.56 (12)	H22B—C22—H22C	109.5
C11—C1—P1	111.40 (12)	C2—C23—H23A	109.5
C23—C2—C21	107.64 (15)	C2—C23—H23B	109.5
C23—C2—C22	109.35 (15)	H23A—C23—H23B	109.5
C21—C2—C22	108.61 (15)	C2—C23—H23C	109.5
C23—C2—P1	110.76 (13)	H23A—C23—H23C	109.5
C21—C2—P1	110.35 (12)	H23B—C23—H23C	109.5
C22—C2—P1	110.07 (12)	C3—C31—H31A	109.5
C31—C3—C32	110.45 (16)	C3—C31—H31B	109.5
C31—C3—P1	112.59 (13)	H31A—C31—H31B	109.5
C32—C3—P1	117.44 (13)	C3—C31—H31C	109.5
C31—C3—H3	105.0	H31A—C31—H31C	109.5
C32—C3—H3	105.0	H31B—C31—H31C	109.5
P1—C3—H3	105.0	C3—C32—H32A	109.5
C1—C11—H11A	109.5	C3—C32—H32B	109.5
C1—C11—H11B	109.5	H32A—C32—H32B	109.5
H11A—C11—H11B	109.5	C3—C32—H32C	109.5
C1—C11—H11C	109.5	H32A—C32—H32C	109.5
H11A—C11—H11C	109.5	H32B—C32—H32C	109.5
H11B—C11—H11C	109.5	Cl5—C99—Cl4	110.93 (11)
C1—C12—H12A	109.5	Cl5—C99—Cl6	110.46 (11)
C1—C12—H12B	109.5	Cl4—C99—Cl6	110.43 (11)
H12A—C12—H12B	109.5	Cl5—C99—D99	108.3
C1—C12—H12C	109.5	Cl4—C99—D99	108.3
H12A—C12—H12C	109.5	Cl6—C99—D99	108.3
H12B—C12—H12C	109.5

Cl3—Au1—S1—P1	69.79 (3)	C1—P1—C2—C23	40.95 (16)
Cl2—Au1—S1—P1	−112.73 (3)	S1—P1—C2—C23	−78.08 (13)
Au1—S1—P1—C3	−66.93 (7)	C3—P1—C2—C21	−74.85 (15)
Au1—S1—P1—C1	52.74 (7)	C1—P1—C2—C21	160.04 (13)
Au1—S1—P1—C2	174.37 (6)	S1—P1—C2—C21	41.01 (14)
C3—P1—C1—C12	161.09 (12)	C3—P1—C2—C22	45.01 (15)
C2—P1—C1—C12	−71.89 (14)	C1—P1—C2—C22	−80.10 (15)
S1—P1—C1—C12	41.54 (13)	S1—P1—C2—C22	160.87 (12)
C3—P1—C1—C13	42.71 (14)	C1—P1—C3—C31	−178.11 (13)
C2—P1—C1—C13	169.73 (12)	C2—P1—C3—C31	53.87 (15)
S1—P1—C1—C13	−76.84 (13)	S1—P1—C3—C31	−57.31 (14)
C3—P1—C1—C11	−77.18 (14)	C1—P1—C3—C32	51.93 (16)
C2—P1—C1—C11	49.84 (16)	C2—P1—C3—C32	−76.10 (16)
S1—P1—C1—C11	163.27 (11)	S1—P1—C3—C32	172.72 (12)
C3—P1—C2—C23	166.06 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···Au1	0.98	2.68	3.6027 (19)	156
C21—H21A···S1	0.98	2.63	3.1082 (19)	110
C12—H12C···S1	0.98	2.86	3.411 (2)	116
C3—H3···Cl3	1.00	2.65	3.4471 (18)	137
C12—H12C···Cl2	0.98	2.78	3.755 (2)	171
C99—D99···Cl1	1.00	2.74	3.537 (2)	137
C99—D99···Cl2	1.00	2.69	3.489 (2)	137
C12—H12A···Cl1ⁱ	0.98	2.91	3.596 (2)	128

Symmetry code: (i) −x+1, −y+1, −z+1.

Trichlorido(tri-tert-butylphosphane sulfide-κS)gold(III) dichloromethane monosolvate (12a) top

Crystal data top

[AuCl₃(C₁₂H₂₇PS)]·CH₂Cl₂	Z = 2
M_r = 622.61	F(000) = 604
Triclinic, P1	D_x = 1.924 Mg m⁻³
a = 8.4202 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2194 (4) Å	Cell parameters from 47731 reflections
c = 11.8355 (4) Å	θ = 2.8–30.6°
α = 98.398 (3)°	µ = 7.63 mm⁻¹
β = 101.174 (3)°	T = 100 K
γ = 95.991 (3)°	Block, red
V = 1074.95 (7) Å³	0.15 × 0.1 × 0.1 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	6558 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6124 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.054
ω–scan	θ_max = 31.1°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→12
T_min = 0.783, T_max = 1.000	k = −16→16
157605 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.037	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0147P)² + 0.9642P] where P = (F_o² + 2F_c²)/3
6558 reflections	(Δ/σ)_max = 0.002
199 parameters	Δρ_max = 1.76 e Å⁻³
0 restraints	Δρ_min = −1.01 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.53561 (2)	0.65489 (2)	0.29756 (2)	0.01423 (3)
P1	0.63223 (6)	0.33330 (4)	0.26499 (4)	0.01110 (9)
S1	0.55574 (6)	0.47197 (4)	0.36749 (4)	0.01588 (10)
Cl1	0.51329 (8)	0.84355 (5)	0.24639 (6)	0.03068 (13)
Cl2	0.78232 (7)	0.73160 (5)	0.41951 (5)	0.02751 (12)
Cl3	0.28358 (6)	0.58666 (4)	0.18025 (5)	0.01819 (10)
C1	0.6853 (2)	0.23096 (17)	0.37810 (18)	0.0147 (4)
C2	0.8182 (2)	0.38937 (18)	0.21024 (18)	0.0156 (4)
C3	0.4579 (2)	0.25575 (17)	0.14205 (18)	0.0152 (4)
C11	0.7890 (3)	0.13553 (18)	0.3356 (2)	0.0189 (4)
H11A	0.896288	0.176237	0.332015	0.028*
H11B	0.733736	0.091959	0.257732	0.028*
H11C	0.803183	0.077662	0.390133	0.028*
C12	0.5282 (3)	0.16507 (19)	0.4010 (2)	0.0187 (4)
H12A	0.556046	0.121650	0.466725	0.028*
H12B	0.472365	0.106869	0.331072	0.028*
H12C	0.456061	0.224697	0.419971	0.028*
C13	0.7792 (3)	0.3055 (2)	0.49633 (19)	0.0204 (4)
H13A	0.806888	0.250522	0.552104	0.031*
H13B	0.710742	0.362704	0.526409	0.031*
H13C	0.879701	0.350796	0.485668	0.031*
C21	0.8590 (3)	0.2910 (2)	0.1190 (2)	0.0210 (4)
H21A	0.959839	0.320758	0.096282	0.031*
H21B	0.769214	0.272475	0.049961	0.031*
H21C	0.873861	0.217124	0.152734	0.031*
C22	0.9645 (3)	0.4278 (2)	0.3140 (2)	0.0217 (4)
H22A	1.055508	0.469794	0.288068	0.033*
H22B	0.998283	0.355582	0.344279	0.033*
H22C	0.933090	0.482692	0.375708	0.033*
C23	0.7922 (3)	0.50296 (19)	0.1537 (2)	0.0198 (4)
H23A	0.785061	0.571139	0.213648	0.030*
H23B	0.690694	0.486182	0.093839	0.030*
H23C	0.884367	0.523857	0.117485	0.030*
C31	0.4816 (3)	0.12534 (18)	0.0939 (2)	0.0209 (4)
H31A	0.392796	0.091382	0.026551	0.031*
H31B	0.480460	0.074977	0.154879	0.031*
H31C	0.586512	0.126580	0.069678	0.031*
C32	0.2951 (2)	0.25318 (19)	0.1836 (2)	0.0186 (4)
H32A	0.277011	0.336554	0.210355	0.028*
H32B	0.299746	0.207114	0.248201	0.028*
H32C	0.205260	0.214234	0.118818	0.028*
C33	0.4420 (3)	0.32898 (19)	0.04080 (19)	0.0191 (4)
H33A	0.538213	0.325449	0.005922	0.029*
H33B	0.434062	0.413848	0.070728	0.029*
H33C	0.343501	0.294182	−0.018603	0.029*
C99	1.0588 (4)	0.8679 (2)	0.2453 (2)	0.0322 (6)
H99A	0.963855	0.820052	0.262990	0.039*
H99B	1.141490	0.813027	0.234783	0.039*
Cl4	1.14230 (7)	0.98659 (5)	0.36326 (5)	0.02400 (11)
Cl5	0.99590 (10)	0.92468 (7)	0.11422 (6)	0.04378 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01635 (4)	0.01008 (3)	0.01700 (5)	0.00177 (2)	0.00743 (3)	−0.00052 (2)
P1	0.0114 (2)	0.0111 (2)	0.0110 (2)	0.00285 (16)	0.00292 (18)	0.00101 (17)
S1	0.0220 (2)	0.0139 (2)	0.0133 (2)	0.00565 (17)	0.00704 (19)	0.00088 (17)
Cl1	0.0464 (3)	0.0118 (2)	0.0372 (3)	0.0048 (2)	0.0158 (3)	0.0055 (2)
Cl2	0.0202 (2)	0.0244 (3)	0.0320 (3)	−0.00319 (19)	0.0049 (2)	−0.0094 (2)
Cl3	0.0174 (2)	0.0178 (2)	0.0199 (3)	0.00508 (17)	0.00395 (19)	0.00340 (18)
C1	0.0158 (9)	0.0145 (8)	0.0148 (10)	0.0040 (7)	0.0026 (8)	0.0052 (7)
C2	0.0149 (9)	0.0168 (9)	0.0174 (11)	0.0031 (7)	0.0079 (8)	0.0041 (7)
C3	0.0148 (9)	0.0131 (8)	0.0157 (10)	0.0031 (7)	0.0012 (8)	−0.0016 (7)
C11	0.0204 (10)	0.0179 (9)	0.0206 (11)	0.0084 (8)	0.0043 (8)	0.0063 (8)
C12	0.0190 (9)	0.0193 (9)	0.0197 (11)	0.0018 (7)	0.0063 (8)	0.0071 (8)
C13	0.0225 (10)	0.0235 (10)	0.0150 (11)	0.0048 (8)	0.0008 (9)	0.0054 (8)
C21	0.0214 (10)	0.0226 (10)	0.0229 (12)	0.0087 (8)	0.0117 (9)	0.0034 (8)
C22	0.0152 (9)	0.0253 (10)	0.0239 (12)	−0.0011 (8)	0.0044 (9)	0.0047 (9)
C23	0.0231 (10)	0.0186 (9)	0.0212 (12)	0.0036 (8)	0.0109 (9)	0.0058 (8)
C31	0.0230 (10)	0.0152 (9)	0.0208 (12)	0.0048 (8)	−0.0004 (9)	−0.0037 (8)
C32	0.0114 (8)	0.0190 (9)	0.0237 (12)	0.0019 (7)	0.0012 (8)	0.0013 (8)
C33	0.0217 (10)	0.0204 (10)	0.0144 (11)	0.0069 (8)	0.0011 (8)	0.0010 (8)
C99	0.0485 (15)	0.0211 (11)	0.0241 (13)	0.0000 (10)	0.0032 (12)	0.0043 (9)
Cl4	0.0240 (2)	0.0242 (2)	0.0232 (3)	0.00542 (19)	0.0015 (2)	0.0053 (2)
Cl5	0.0588 (5)	0.0443 (4)	0.0230 (3)	0.0033 (3)	−0.0035 (3)	0.0075 (3)

Geometric parameters (Å, º) top

Au1—Cl3	2.2860 (5)	C13—H13B	0.9800
Au1—Cl2	2.2894 (6)	C13—H13C	0.9800
Au1—Cl1	2.3013 (5)	C21—H21A	0.9800
Au1—S1	2.3323 (5)	C21—H21B	0.9800
P1—C3	1.888 (2)	C21—H21C	0.9800
P1—C2	1.8906 (19)	C22—H22A	0.9800
P1—C1	1.906 (2)	C22—H22B	0.9800
P1—S1	2.0658 (6)	C22—H22C	0.9800
C1—C12	1.537 (3)	C23—H23A	0.9800
C1—C11	1.540 (3)	C23—H23B	0.9800
C1—C13	1.541 (3)	C23—H23C	0.9800
C2—C22	1.536 (3)	C31—H31A	0.9800
C2—C23	1.540 (3)	C31—H31B	0.9800
C2—C21	1.542 (3)	C31—H31C	0.9800
C3—C31	1.538 (3)	C32—H32A	0.9800
C3—C33	1.542 (3)	C32—H32B	0.9800
C3—C32	1.542 (3)	C32—H32C	0.9800
C11—H11A	0.9800	C33—H33A	0.9800
C11—H11B	0.9800	C33—H33B	0.9800
C11—H11C	0.9800	C33—H33C	0.9800
C12—H12A	0.9800	C99—Cl4	1.760 (3)
C12—H12B	0.9800	C99—Cl5	1.770 (3)
C12—H12C	0.9800	C99—H99A	0.9900
C13—H13A	0.9800	C99—H99B	0.9900

Cl3—Au1—Cl2	176.996 (18)	C1—C13—H13C	109.5
Cl3—Au1—Cl1	88.53 (2)	H13A—C13—H13C	109.5
Cl2—Au1—Cl1	89.55 (2)	H13B—C13—H13C	109.5
Cl3—Au1—S1	93.402 (18)	C2—C21—H21A	109.5
Cl2—Au1—S1	88.30 (2)	C2—C21—H21B	109.5
Cl1—Au1—S1	174.441 (19)	H21A—C21—H21B	109.5
C3—P1—C2	112.33 (9)	C2—C21—H21C	109.5
C3—P1—C1	111.29 (9)	H21A—C21—H21C	109.5
C2—P1—C1	111.38 (9)	H21B—C21—H21C	109.5
C3—P1—S1	110.17 (6)	C2—C22—H22A	109.5
C2—P1—S1	111.66 (6)	C2—C22—H22B	109.5
C1—P1—S1	99.33 (6)	H22A—C22—H22B	109.5
P1—S1—Au1	117.50 (3)	C2—C22—H22C	109.5
C12—C1—C11	108.93 (16)	H22A—C22—H22C	109.5
C12—C1—C13	106.51 (17)	H22B—C22—H22C	109.5
C11—C1—C13	109.07 (17)	C2—C23—H23A	109.5
C12—C1—P1	110.11 (14)	C2—C23—H23B	109.5
C11—C1—P1	110.82 (14)	H23A—C23—H23B	109.5
C13—C1—P1	111.28 (13)	C2—C23—H23C	109.5
C22—C2—C23	106.45 (17)	H23A—C23—H23C	109.5
C22—C2—C21	110.01 (17)	H23B—C23—H23C	109.5
C23—C2—C21	108.11 (17)	C3—C31—H31A	109.5
C22—C2—P1	109.39 (14)	C3—C31—H31B	109.5
C23—C2—P1	111.29 (13)	H31A—C31—H31B	109.5
C21—C2—P1	111.46 (14)	C3—C31—H31C	109.5
C31—C3—C33	108.18 (17)	H31A—C31—H31C	109.5
C31—C3—C32	109.39 (16)	H31B—C31—H31C	109.5
C33—C3—C32	106.69 (17)	C3—C32—H32A	109.5
C31—C3—P1	112.55 (14)	C3—C32—H32B	109.5
C33—C3—P1	109.73 (13)	H32A—C32—H32B	109.5
C32—C3—P1	110.12 (14)	C3—C32—H32C	109.5
C1—C11—H11A	109.5	H32A—C32—H32C	109.5
C1—C11—H11B	109.5	H32B—C32—H32C	109.5
H11A—C11—H11B	109.5	C3—C33—H33A	109.5
C1—C11—H11C	109.5	C3—C33—H33B	109.5
H11A—C11—H11C	109.5	H33A—C33—H33B	109.5
H11B—C11—H11C	109.5	C3—C33—H33C	109.5
C1—C12—H12A	109.5	H33A—C33—H33C	109.5
C1—C12—H12B	109.5	H33B—C33—H33C	109.5
H12A—C12—H12B	109.5	Cl4—C99—Cl5	111.42 (13)
C1—C12—H12C	109.5	Cl4—C99—H99A	109.3
H12A—C12—H12C	109.5	Cl5—C99—H99A	109.3
H12B—C12—H12C	109.5	Cl4—C99—H99B	109.3
C1—C13—H13A	109.5	Cl5—C99—H99B	109.3
C1—C13—H13B	109.5	H99A—C99—H99B	108.0
H13A—C13—H13B	109.5

C3—P1—S1—Au1	−78.75 (7)	S1—P1—C2—C22	66.86 (15)
C2—P1—S1—Au1	46.80 (8)	C3—P1—C2—C23	73.86 (16)
C1—P1—S1—Au1	164.36 (6)	C1—P1—C2—C23	−160.53 (14)
Cl3—Au1—S1—P1	82.19 (3)	S1—P1—C2—C23	−50.49 (16)
Cl2—Au1—S1—P1	−100.28 (3)	C3—P1—C2—C21	−46.91 (17)
C3—P1—C1—C12	−41.56 (16)	C1—P1—C2—C21	78.70 (17)
C2—P1—C1—C12	−167.75 (13)	S1—P1—C2—C21	−171.26 (13)
S1—P1—C1—C12	74.48 (14)	C2—P1—C3—C31	77.86 (17)
C3—P1—C1—C11	79.02 (16)	C1—P1—C3—C31	−47.81 (17)
C2—P1—C1—C11	−47.17 (16)	S1—P1—C3—C31	−156.98 (13)
S1—P1—C1—C11	−164.93 (13)	C2—P1—C3—C33	−42.66 (16)
C3—P1—C1—C13	−159.43 (13)	C1—P1—C3—C33	−168.32 (13)
C2—P1—C1—C13	74.39 (16)	S1—P1—C3—C33	82.51 (13)
S1—P1—C1—C13	−43.38 (14)	C2—P1—C3—C32	−159.80 (13)
C3—P1—C2—C22	−168.80 (13)	C1—P1—C3—C32	74.54 (15)
C1—P1—C2—C22	−43.18 (16)	S1—P1—C3—C32	−34.64 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23A···Au1	0.98	2.69	3.438 (2)	134
C13—H13B···S1	0.98	2.61	3.131 (2)	114
C32—H32A···S1	0.98	2.83	3.323 (2)	112
C23—H23A···Cl2	0.98	2.82	3.778 (2)	168
C32—H32A···Cl3	0.98	2.88	3.759 (2)	150
C33—H33B···Cl3	0.98	2.73	3.623 (2)	152
C99—H99A···Cl2	0.99	2.84	3.749 (3)	153
C99—H99B···Cl3ⁱ	0.99	2.96	3.903 (3)	160
C22—H22A···Cl3ⁱ	0.98	2.82	3.791 (2)	171

Symmetry code: (i) x+1, y, z.

(tert-Butyldipropan-2-ylphosphane selenide-κS)trichloridogold(III) (14a) top

Crystal data top

[AuCl₃(C₁₀H₂₃PSe)]	F(000) = 1048
M_r = 556.53	D_x = 2.231 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.92516 (18) Å	Cell parameters from 44121 reflections
b = 14.5559 (4) Å	θ = 2.8–29.0°
c = 14.3635 (4) Å	µ = 11.64 mm⁻¹
β = 91.264 (2)°	T = 100 K
V = 1656.54 (7) Å³	Block, red
Z = 4	0.15 × 0.15 × 0.1 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	4112 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
Detector resolution: 16.1419 pixels mm^-1	θ_max = 28.3°, θ_min = 2.8°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	k = −19→19
T_min = 0.483, T_max = 1.000	l = −19→19
196706 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + 30.9095P] where P = (F_o² + 2F_c²)/3
S = 1.32	(Δ/σ)_max = 0.001
4112 reflections	Δρ_max = 3.81 e Å⁻³
152 parameters	Δρ_min = −2.41 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.45922 (4)	0.06629 (2)	0.31589 (2)	0.01738 (8)
Cl1	0.4313 (3)	0.01307 (15)	0.16364 (15)	0.0276 (4)
Cl2	0.1741 (2)	0.08748 (16)	0.31991 (16)	0.0292 (5)
Cl3	0.7414 (2)	0.03567 (14)	0.31613 (14)	0.0239 (4)
Se1	0.47042 (10)	0.12099 (5)	0.47644 (6)	0.01951 (17)
P1	0.6495 (2)	0.23732 (13)	0.48512 (13)	0.0145 (4)
C1	0.6072 (12)	0.3269 (5)	0.3948 (6)	0.0240 (17)
C2	0.6083 (10)	0.2813 (6)	0.6029 (6)	0.0207 (16)
H2	0.693302	0.330393	0.617188	0.025*
C3	0.8687 (10)	0.1988 (6)	0.4766 (6)	0.0240 (17)
H3	0.883705	0.180911	0.410097	0.029*
C11	0.6701 (12)	0.4210 (6)	0.4307 (6)	0.0270 (18)
H11A	0.651327	0.467517	0.382269	0.041*
H11B	0.790957	0.417208	0.446273	0.041*
H11C	0.608111	0.438057	0.486405	0.041*
C12	0.4190 (13)	0.3337 (7)	0.3704 (8)	0.039 (2)
H12A	0.356324	0.347367	0.426822	0.058*
H12B	0.379581	0.275247	0.343994	0.058*
H12C	0.400336	0.382903	0.324754	0.058*
C13	0.7024 (16)	0.3017 (7)	0.3058 (7)	0.040 (3)
H13A	0.660326	0.242939	0.281512	0.061*
H13B	0.823381	0.296514	0.320588	0.061*
H13C	0.684125	0.349746	0.258870	0.061*
C21	0.4334 (11)	0.3234 (6)	0.6129 (6)	0.0265 (18)
H21A	0.347661	0.275184	0.606145	0.040*
H21B	0.414959	0.370033	0.564578	0.040*
H21C	0.425261	0.351900	0.674447	0.040*
C22	0.6290 (15)	0.2065 (7)	0.6771 (6)	0.040 (3)
H22A	0.600785	0.231711	0.738109	0.060*
H22B	0.746135	0.184855	0.678801	0.060*
H22C	0.553465	0.155102	0.662001	0.060*
C31	0.9989 (13)	0.2759 (8)	0.4970 (10)	0.054 (3)
H31A	0.987031	0.297574	0.561092	0.081*
H31B	0.978980	0.327034	0.453743	0.081*
H31C	1.113213	0.251872	0.488980	0.081*
C32	0.9129 (13)	0.1140 (8)	0.5341 (7)	0.039 (3)
H32A	1.014400	0.085151	0.509559	0.059*
H32B	0.818852	0.070321	0.530678	0.059*
H32C	0.933871	0.131909	0.599105	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01636 (13)	0.01447 (14)	0.02152 (15)	−0.00068 (11)	0.00488 (10)	−0.00236 (11)
Cl1	0.0283 (10)	0.0306 (11)	0.0237 (10)	0.0010 (8)	−0.0005 (8)	−0.0059 (8)
Cl2	0.0167 (9)	0.0371 (12)	0.0340 (11)	0.0028 (8)	0.0031 (8)	−0.0006 (9)
Cl3	0.0179 (8)	0.0261 (10)	0.0281 (10)	0.0015 (7)	0.0052 (7)	−0.0103 (8)
Se1	0.0227 (4)	0.0153 (4)	0.0209 (4)	−0.0047 (3)	0.0098 (3)	−0.0021 (3)
P1	0.0151 (8)	0.0122 (8)	0.0162 (9)	0.0010 (7)	0.0047 (7)	−0.0006 (7)
C1	0.039 (5)	0.012 (3)	0.022 (4)	0.002 (3)	0.011 (3)	0.002 (3)
C2	0.022 (4)	0.019 (4)	0.021 (4)	0.002 (3)	0.006 (3)	−0.004 (3)
C3	0.017 (4)	0.024 (4)	0.031 (4)	0.005 (3)	0.003 (3)	−0.007 (4)
C11	0.034 (5)	0.016 (4)	0.031 (5)	0.001 (3)	0.011 (4)	0.004 (3)
C12	0.048 (6)	0.022 (5)	0.045 (6)	0.007 (4)	−0.017 (5)	0.003 (4)
C13	0.075 (8)	0.021 (5)	0.027 (5)	0.005 (5)	0.022 (5)	0.001 (4)
C21	0.029 (4)	0.027 (4)	0.024 (4)	0.005 (3)	0.013 (3)	−0.001 (3)
C22	0.064 (7)	0.041 (6)	0.016 (4)	0.021 (5)	0.001 (4)	−0.005 (4)
C31	0.025 (5)	0.047 (7)	0.091 (10)	0.004 (5)	0.002 (5)	−0.034 (7)
C32	0.036 (5)	0.050 (6)	0.031 (5)	0.031 (5)	0.003 (4)	0.003 (5)

Geometric parameters (Å, º) top

Au1—Cl3	2.2803 (19)	C1—C12	1.528 (13)
Au1—Cl2	2.283 (2)	C1—C13	1.543 (12)
Au1—Cl1	2.326 (2)	C1—C11	1.543 (12)
Au1—Se1	2.4393 (8)	C2—C21	1.524 (11)
Se1—P1	2.211 (2)	C2—C22	1.530 (13)
P1—C3	1.832 (8)	C3—C32	1.522 (13)
P1—C2	1.845 (8)	C3—C31	1.548 (13)
P1—C1	1.864 (8)

Cl3—Au1—Cl2	176.18 (8)	C12—C1—C13	108.6 (9)
Cl3—Au1—Cl1	90.53 (7)	C12—C1—C11	109.0 (7)
Cl2—Au1—Cl1	89.72 (8)	C13—C1—C11	109.1 (7)
Cl3—Au1—Se1	92.70 (5)	C12—C1—P1	111.4 (6)
Cl2—Au1—Se1	86.98 (6)	C13—C1—P1	109.1 (6)
Cl1—Au1—Se1	176.59 (6)	C11—C1—P1	109.7 (6)
P1—Se1—Au1	108.25 (6)	C21—C2—C22	107.7 (7)
C3—P1—C2	110.8 (4)	C21—C2—P1	113.9 (6)
C3—P1—C1	108.9 (4)	C22—C2—P1	111.9 (6)
C2—P1—C1	111.3 (4)	C32—C3—C31	109.9 (9)
C3—P1—Se1	111.7 (3)	C32—C3—P1	114.8 (6)
C2—P1—Se1	101.0 (3)	C31—C3—P1	113.3 (6)
C1—P1—Se1	113.0 (3)

Cl3—Au1—Se1—P1	58.66 (8)	Se1—P1—C1—C11	152.6 (5)
Cl2—Au1—Se1—P1	−125.16 (8)	C3—P1—C2—C21	174.3 (6)
Au1—Se1—P1—C3	−72.6 (3)	C1—P1—C2—C21	53.0 (7)
Au1—Se1—P1—C2	169.6 (3)	Se1—P1—C2—C21	−67.1 (6)
Au1—Se1—P1—C1	50.7 (3)	C3—P1—C2—C22	−63.2 (8)
C3—P1—C1—C12	156.7 (6)	C1—P1—C2—C22	175.5 (7)
C2—P1—C1—C12	−81.0 (7)	Se1—P1—C2—C22	55.3 (7)
Se1—P1—C1—C12	31.9 (7)	C2—P1—C3—C32	67.7 (8)
C3—P1—C1—C13	36.8 (8)	C1—P1—C3—C32	−169.6 (7)
C2—P1—C1—C13	159.2 (7)	Se1—P1—C3—C32	−44.0 (7)
Se1—P1—C1—C13	−88.0 (7)	C2—P1—C3—C31	−59.6 (9)
C3—P1—C1—C11	−82.6 (6)	C1—P1—C3—C31	63.0 (9)
C2—P1—C1—C11	39.8 (7)	Se1—P1—C3—C31	−171.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl3	1.00	2.74	3.445 (9)	128
C3—H3···Cl2ⁱ	1.00	2.99	3.714 (8)	130
C21—H21C···Cl2ⁱⁱ	0.98	2.98	3.730 (10)	135
C22—H22A···Cl2ⁱⁱ	0.98	2.94	3.646 (11)	130
C13—H13C···Cl3ⁱⁱⁱ	0.98	2.98	3.860 (10)	151

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Trichlorido[di-tert-butyl(propan-2-yl)phosphane selenide-κS]gold(III) (15a) top

Crystal data top

[AuCl₃(C₁₁H₂₅PSe)]	Z = 2
M_r = 570.55	F(000) = 540
Triclinic, P1	D_x = 2.164 Mg m⁻³
a = 8.5878 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8435 (4) Å	Cell parameters from 26441 reflections
c = 11.5022 (5) Å	θ = 2.2–30.8°
α = 78.391 (3)°	µ = 11.01 mm⁻¹
β = 71.168 (4)°	T = 100 K
γ = 73.463 (4)°	Block, dark red
V = 875.78 (7) Å³	0.18 × 0.15 × 0.12 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	5231 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4984 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.032
ω scans	θ_max = 30.9°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→12
T_min = 0.700, T_max = 1.000	k = −14→14
54532 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.014	H-atom parameters constrained
wR(F²) = 0.030	w = 1/[σ²(F_o²) + (0.0102P)² + 0.6517P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.002
5231 reflections	Δρ_max = 0.84 e Å⁻³
163 parameters	Δρ_min = −0.73 e Å⁻³
0 restraints	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015), F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00113 (8)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.47065 (2)	0.34817 (2)	0.24083 (2)	0.01225 (3)
Cl1	0.53440 (7)	0.12047 (5)	0.34417 (5)	0.02266 (10)
Cl2	0.73944 (6)	0.36884 (5)	0.21249 (4)	0.01954 (9)
Cl3	0.20708 (6)	0.32192 (5)	0.25905 (5)	0.02097 (9)
Se1	0.41932 (2)	0.58622 (2)	0.12550 (2)	0.01264 (4)
P1	0.21270 (5)	0.73111 (5)	0.24893 (4)	0.00884 (8)
C1	0.2579 (2)	0.71444 (18)	0.40126 (15)	0.0110 (3)
C2	0.2204 (2)	0.90901 (18)	0.15358 (16)	0.0119 (3)
C3	0.0106 (2)	0.68238 (19)	0.27683 (17)	0.0139 (3)
H3	0.029641	0.580448	0.314717	0.017*
C11	0.1588 (2)	0.8456 (2)	0.47037 (16)	0.0154 (3)
H11A	0.178588	0.829709	0.551846	0.023*
H11B	0.037554	0.860209	0.480689	0.023*
H11C	0.197124	0.930249	0.422547	0.023*
C12	0.4474 (2)	0.6965 (2)	0.38347 (17)	0.0160 (4)
H12A	0.467866	0.684501	0.464383	0.024*
H12B	0.482936	0.781360	0.333425	0.024*
H12C	0.512449	0.612140	0.341234	0.024*
C13	0.2056 (2)	0.58019 (19)	0.48112 (16)	0.0151 (3)
H13A	0.261624	0.497634	0.434914	0.023*
H13B	0.082529	0.594352	0.501794	0.023*
H13C	0.239410	0.563197	0.557428	0.023*
C21	0.2454 (3)	0.8959 (2)	0.01674 (16)	0.0171 (4)
H21A	0.235623	0.990931	−0.030806	0.026*
H21B	0.158520	0.852840	0.011331	0.026*
H21C	0.357828	0.835579	−0.017068	0.026*
C22	0.0541 (2)	1.01974 (19)	0.19973 (17)	0.0164 (4)
H22A	0.031062	1.022339	0.288534	0.025*
H22B	−0.039081	0.993275	0.185004	0.025*
H22C	0.064293	1.114141	0.155043	0.025*
C23	0.3698 (2)	0.9605 (2)	0.15942 (17)	0.0164 (4)
H23A	0.377807	1.049299	0.103710	0.025*
H23B	0.474790	0.887482	0.134006	0.025*
H23C	0.352286	0.977511	0.244277	0.025*
C31	−0.0328 (3)	0.6819 (2)	0.15753 (19)	0.0222 (4)
H31A	−0.121644	0.630111	0.176110	0.033*
H31B	0.068516	0.634926	0.097399	0.033*
H31C	−0.072920	0.780409	0.122908	0.033*
C32	−0.1437 (2)	0.7623 (2)	0.37100 (19)	0.0191 (4)
H32A	−0.169270	0.864012	0.339953	0.029*
H32B	−0.118272	0.750211	0.450156	0.029*
H32C	−0.241604	0.723426	0.382853	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01513 (4)	0.00940 (3)	0.01254 (4)	0.00065 (2)	−0.00576 (2)	−0.00410 (2)
Cl1	0.0321 (3)	0.0122 (2)	0.0273 (2)	−0.00214 (18)	−0.0176 (2)	0.00029 (17)
Cl2	0.0152 (2)	0.0192 (2)	0.0244 (2)	0.00072 (16)	−0.00806 (17)	−0.00586 (17)
Cl3	0.0193 (2)	0.0132 (2)	0.0327 (3)	−0.00315 (16)	−0.00950 (19)	−0.00519 (18)
Se1	0.01521 (8)	0.01085 (8)	0.00931 (7)	0.00077 (6)	−0.00215 (6)	−0.00334 (6)
P1	0.00901 (19)	0.00871 (19)	0.00890 (18)	−0.00114 (15)	−0.00311 (15)	−0.00166 (14)
C1	0.0116 (8)	0.0127 (8)	0.0084 (7)	−0.0003 (6)	−0.0034 (6)	−0.0031 (6)
C2	0.0139 (8)	0.0100 (7)	0.0116 (8)	−0.0028 (6)	−0.0038 (6)	−0.0006 (6)
C3	0.0121 (8)	0.0128 (8)	0.0183 (8)	−0.0040 (6)	−0.0071 (7)	0.0009 (6)
C11	0.0169 (8)	0.0144 (8)	0.0133 (8)	0.0007 (7)	−0.0031 (7)	−0.0062 (6)
C12	0.0123 (8)	0.0210 (9)	0.0159 (8)	0.0001 (7)	−0.0066 (7)	−0.0065 (7)
C13	0.0173 (8)	0.0148 (8)	0.0110 (8)	−0.0013 (7)	−0.0037 (7)	−0.0007 (6)
C21	0.0238 (10)	0.0153 (8)	0.0117 (8)	−0.0047 (7)	−0.0061 (7)	0.0015 (6)
C22	0.0171 (9)	0.0109 (8)	0.0195 (9)	0.0004 (7)	−0.0066 (7)	−0.0007 (7)
C23	0.0169 (9)	0.0154 (8)	0.0171 (9)	−0.0062 (7)	−0.0027 (7)	−0.0026 (7)
C31	0.0235 (10)	0.0226 (10)	0.0275 (10)	−0.0089 (8)	−0.0157 (8)	0.0004 (8)
C32	0.0098 (8)	0.0177 (9)	0.0263 (10)	−0.0019 (7)	−0.0038 (7)	0.0011 (7)

Geometric parameters (Å, º) top

Au1—Cl2	2.2871 (5)	C12—H12B	0.9800
Au1—Cl3	2.2889 (5)	C12—H12C	0.9800
Au1—Cl1	2.3207 (5)	C13—H13A	0.9800
Au1—Se1	2.4460 (2)	C13—H13B	0.9800
Se1—P1	2.2240 (5)	C13—H13C	0.9800
P1—C3	1.8435 (18)	C21—H21A	0.9800
P1—C2	1.8762 (18)	C21—H21B	0.9800
P1—C1	1.8802 (17)	C21—H21C	0.9800
C1—C12	1.535 (2)	C22—H22A	0.9800
C1—C11	1.541 (2)	C22—H22B	0.9800
C1—C13	1.541 (2)	C22—H22C	0.9800
C2—C23	1.532 (3)	C23—H23A	0.9800
C2—C22	1.539 (2)	C23—H23B	0.9800
C2—C21	1.545 (2)	C23—H23C	0.9800
C3—C31	1.535 (3)	C31—H31A	0.9800
C3—C32	1.539 (3)	C31—H31B	0.9800
C3—H3	1.0000	C31—H31C	0.9800
C11—H11A	0.9800	C32—H32A	0.9800
C11—H11B	0.9800	C32—H32B	0.9800
C11—H11C	0.9800	C32—H32C	0.9800
C12—H12A	0.9800

Cl2—Au1—Cl3	176.794 (17)	C1—C12—H12C	109.5
Cl2—Au1—Cl1	89.966 (18)	H12A—C12—H12C	109.5
Cl3—Au1—Cl1	89.946 (18)	H12B—C12—H12C	109.5
Cl2—Au1—Se1	87.383 (14)	C1—C13—H13A	109.5
Cl3—Au1—Se1	92.617 (13)	C1—C13—H13B	109.5
Cl1—Au1—Se1	176.951 (14)	H13A—C13—H13B	109.5
P1—Se1—Au1	108.487 (14)	C1—C13—H13C	109.5
C3—P1—C2	112.81 (8)	H13A—C13—H13C	109.5
C3—P1—C1	108.96 (8)	H13B—C13—H13C	109.5
C2—P1—C1	114.08 (8)	C2—C21—H21A	109.5
C3—P1—Se1	109.45 (6)	C2—C21—H21B	109.5
C2—P1—Se1	101.19 (6)	H21A—C21—H21B	109.5
C1—P1—Se1	110.07 (5)	C2—C21—H21C	109.5
C12—C1—C11	108.31 (15)	H21A—C21—H21C	109.5
C12—C1—C13	108.25 (14)	H21B—C21—H21C	109.5
C11—C1—C13	109.14 (14)	C2—C22—H22A	109.5
C12—C1—P1	111.25 (11)	C2—C22—H22B	109.5
C11—C1—P1	111.89 (12)	H22A—C22—H22B	109.5
C13—C1—P1	107.91 (12)	C2—C22—H22C	109.5
C23—C2—C22	109.72 (15)	H22A—C22—H22C	109.5
C23—C2—C21	107.75 (14)	H22B—C22—H22C	109.5
C22—C2—C21	108.65 (15)	C2—C23—H23A	109.5
C23—C2—P1	110.50 (12)	C2—C23—H23B	109.5
C22—C2—P1	110.36 (12)	H23A—C23—H23B	109.5
C21—C2—P1	109.82 (12)	C2—C23—H23C	109.5
C31—C3—C32	110.83 (15)	H23A—C23—H23C	109.5
C31—C3—P1	113.41 (13)	H23B—C23—H23C	109.5
C32—C3—P1	116.45 (13)	C3—C31—H31A	109.5
C31—C3—H3	105.0	C3—C31—H31B	109.5
C32—C3—H3	105.0	H31A—C31—H31B	109.5
P1—C3—H3	105.0	C3—C31—H31C	109.5
C1—C11—H11A	109.5	H31A—C31—H31C	109.5
C1—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	C3—C32—H32A	109.5
C1—C11—H11C	109.5	C3—C32—H32B	109.5
H11A—C11—H11C	109.5	H32A—C32—H32B	109.5
H11B—C11—H11C	109.5	C3—C32—H32C	109.5
C1—C12—H12A	109.5	H32A—C32—H32C	109.5
C1—C12—H12B	109.5	H32B—C32—H32C	109.5
H12A—C12—H12B	109.5

Cl2—Au1—Se1—P1	−118.493 (18)	C1—P1—C2—C23	41.28 (14)
Cl3—Au1—Se1—P1	64.717 (19)	Se1—P1—C2—C23	−76.86 (12)
Au1—Se1—P1—C3	−69.97 (6)	C3—P1—C2—C22	44.79 (15)
Au1—Se1—P1—C2	170.76 (6)	C1—P1—C2—C22	−80.24 (14)
Au1—Se1—P1—C1	49.76 (6)	Se1—P1—C2—C22	161.62 (11)
C3—P1—C1—C12	158.15 (12)	C3—P1—C2—C21	−74.96 (14)
C2—P1—C1—C12	−74.80 (14)	C1—P1—C2—C21	160.01 (12)
Se1—P1—C1—C12	38.13 (14)	Se1—P1—C2—C21	41.87 (13)
C3—P1—C1—C11	−80.54 (14)	C2—P1—C3—C31	56.35 (16)
C2—P1—C1—C11	46.50 (15)	C1—P1—C3—C31	−175.89 (13)
Se1—P1—C1—C11	159.43 (11)	Se1—P1—C3—C31	−55.48 (14)
C3—P1—C1—C13	39.54 (14)	C2—P1—C3—C32	−74.05 (15)
C2—P1—C1—C13	166.59 (11)	C1—P1—C3—C32	53.71 (15)
Se1—P1—C1—C13	−80.49 (11)	Se1—P1—C3—C32	174.13 (12)
C3—P1—C2—C23	166.31 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Au1	0.98	2.76	3.6818 (18)	158
C21—H21C···Se1	0.98	2.68	3.1887 (19)	113
C12—H12C···Se1	0.98	2.92	3.4566 (18)	116
C3—H3···Cl3	1.00	2.65	3.4842 (19)	141
C12—H12C···Cl2	0.98	2.94	3.9145 (19)	174
C13—H13C···Cl2ⁱ	0.98	2.93	3.8489 (19)	157

Symmetry code: (i) −x+1, −y+1, −z+1.

Trichlorido[di-tert-butyl(propan-2-yl)phosphane selenide-κS]gold(III) chloroform-d monosolvate (15aa) top

Crystal data top

[AuCl₃(C₁₁H₂₅PSe)]·CDCl₃	Z = 2
M_r = 690.93	F(000) = 656
Triclinic, P1	D_x = 2.152 Mg m⁻³
a = 8.5343 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7185 (3) Å	Cell parameters from 34566 reflections
c = 14.0759 (4) Å	θ = 2.2–30.8°
α = 74.398 (2)°	µ = 9.42 mm⁻¹
β = 78.121 (2)°	T = 100 K
γ = 73.257 (2)°	Tablet, red
V = 1066.31 (5) Å³	0.4 × 0.25 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	6287 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6060 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.040
ω scans	θ_max = 30.8°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→11
T_min = 0.151, T_max = 1.000	k = −13→13
76069 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0179P)² + 2.4716P] where P = (F_o² + 2F_c²)/3
6287 reflections	(Δ/σ)_max = 0.001
235 parameters	Δρ_max = 1.88 e Å⁻³
39 restraints	Δρ_min = −1.30 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Au1	0.19009 (2)	0.76455 (2)	0.29588 (2)	0.01280 (3)
Se1	0.31024 (3)	0.58178 (3)	0.19374 (2)	0.01509 (5)
Cl1	0.06715 (8)	0.94493 (7)	0.38594 (5)	0.02097 (13)
Cl2	−0.06581 (8)	0.75760 (7)	0.27413 (5)	0.01900 (12)
Cl3	0.44411 (8)	0.78057 (7)	0.31290 (5)	0.02113 (13)
P1	0.43631 (7)	0.37535 (7)	0.29102 (4)	0.00998 (11)
C1	0.2963 (3)	0.3257 (3)	0.40964 (18)	0.0121 (4)
C2	0.4876 (3)	0.2413 (3)	0.20853 (19)	0.0145 (4)
C3	0.6212 (3)	0.4055 (3)	0.32273 (19)	0.0147 (5)
H3	0.579371	0.492572	0.354051	0.018*
C11	0.3539 (3)	0.1623 (3)	0.46191 (19)	0.0164 (5)
H11A	0.280779	0.141114	0.524606	0.025*
H11B	0.467264	0.142210	0.475766	0.025*
H11C	0.350289	0.099770	0.418588	0.025*
C12	0.1176 (3)	0.3544 (3)	0.3902 (2)	0.0174 (5)
H12A	0.047017	0.330491	0.453586	0.026*
H12B	0.114078	0.292454	0.346449	0.026*
H12C	0.077929	0.458417	0.358281	0.026*
C13	0.2968 (3)	0.4237 (3)	0.47907 (18)	0.0155 (5)
H13A	0.258643	0.527574	0.446277	0.023*
H13B	0.409134	0.405259	0.494072	0.023*
H13C	0.222798	0.400609	0.541098	0.023*
C21	0.5491 (4)	0.3147 (3)	0.1006 (2)	0.0231 (6)
H21A	0.587049	0.240826	0.059935	0.035*
H21B	0.640676	0.356461	0.100995	0.035*
H21C	0.458495	0.393467	0.072699	0.035*
C22	0.6250 (3)	0.1067 (3)	0.2467 (2)	0.0196 (5)
H22A	0.590896	0.063570	0.316669	0.029*
H22B	0.726761	0.137778	0.240897	0.029*
H22C	0.644756	0.033218	0.206881	0.029*
C23	0.3345 (4)	0.1911 (3)	0.2054 (2)	0.0201 (5)
H23A	0.361551	0.127902	0.157554	0.030*
H23B	0.245281	0.277625	0.184829	0.030*
H23C	0.298648	0.135850	0.271644	0.030*
C31	0.7423 (4)	0.4521 (3)	0.2310 (2)	0.0238 (6)
H31A	0.816732	0.497748	0.249454	0.036*
H31B	0.680530	0.523186	0.179360	0.036*
H31C	0.807063	0.365276	0.205380	0.036*
C32	0.7134 (3)	0.2816 (3)	0.4007 (2)	0.0192 (5)
H32A	0.756384	0.191589	0.374977	0.029*
H32B	0.637176	0.262735	0.462303	0.029*
H32C	0.805331	0.311493	0.414288	0.029*
C99	−0.1097 (9)	0.8164 (8)	0.0177 (5)	0.0278 (16)	0.525 (4)
D99	−0.055137	0.830295	0.069726	0.033*	0.525 (4)
Cl4	−0.3237 (7)	0.8542 (6)	0.0573 (4)	0.0381 (9)	0.525 (4)
Cl5	−0.0625 (3)	0.9393 (2)	−0.09447 (12)	0.0435 (7)	0.525 (4)
Cl6	−0.0308 (2)	0.6342 (3)	0.00484 (14)	0.0420 (6)	0.525 (4)
C99'	−0.1635 (10)	0.8634 (8)	0.0319 (6)	0.0296 (19)	0.475 (4)
D99'	−0.126484	0.882844	0.088950	0.036*	0.475 (4)
Cl4'	−0.3518 (8)	0.8272 (8)	0.0703 (6)	0.0483 (14)	0.475 (4)
Cl5'	−0.1902 (5)	1.0248 (3)	−0.06191 (19)	0.0700 (13)	0.475 (4)
Cl6'	−0.0189 (3)	0.7176 (4)	−0.0073 (3)	0.0579 (8)	0.475 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01412 (5)	0.00834 (5)	0.01369 (5)	−0.00048 (3)	−0.00226 (3)	−0.00097 (3)
Se1	0.01999 (12)	0.01043 (11)	0.01201 (11)	0.00044 (9)	−0.00387 (9)	−0.00108 (8)
Cl1	0.0216 (3)	0.0152 (3)	0.0250 (3)	−0.0012 (2)	0.0004 (2)	−0.0090 (2)
Cl2	0.0154 (3)	0.0172 (3)	0.0222 (3)	−0.0003 (2)	−0.0059 (2)	−0.0025 (2)
Cl3	0.0174 (3)	0.0139 (3)	0.0333 (3)	−0.0034 (2)	−0.0038 (2)	−0.0075 (2)
P1	0.0093 (3)	0.0086 (3)	0.0116 (3)	−0.0015 (2)	−0.0014 (2)	−0.0022 (2)
C1	0.0100 (10)	0.0103 (10)	0.0133 (10)	−0.0010 (8)	−0.0008 (8)	−0.0002 (8)
C2	0.0171 (11)	0.0118 (11)	0.0153 (11)	−0.0031 (9)	−0.0015 (9)	−0.0055 (9)
C3	0.0114 (10)	0.0151 (11)	0.0201 (12)	−0.0048 (9)	−0.0016 (9)	−0.0070 (9)
C11	0.0159 (11)	0.0117 (11)	0.0180 (11)	−0.0022 (9)	−0.0026 (9)	0.0015 (9)
C12	0.0096 (10)	0.0185 (12)	0.0219 (12)	−0.0037 (9)	−0.0021 (9)	−0.0009 (10)
C13	0.0158 (11)	0.0153 (11)	0.0133 (11)	−0.0011 (9)	−0.0005 (9)	−0.0039 (9)
C21	0.0325 (15)	0.0219 (13)	0.0133 (11)	−0.0051 (12)	0.0026 (10)	−0.0073 (10)
C22	0.0189 (12)	0.0150 (12)	0.0246 (13)	0.0015 (10)	−0.0036 (10)	−0.0096 (10)
C23	0.0238 (13)	0.0179 (12)	0.0227 (13)	−0.0058 (10)	−0.0082 (10)	−0.0070 (10)
C31	0.0191 (13)	0.0278 (15)	0.0274 (14)	−0.0140 (11)	0.0043 (11)	−0.0077 (12)
C32	0.0111 (11)	0.0204 (13)	0.0272 (13)	0.0009 (9)	−0.0078 (10)	−0.0084 (11)
C99	0.033 (4)	0.037 (5)	0.017 (3)	−0.018 (4)	−0.003 (3)	−0.002 (3)
Cl4	0.044 (2)	0.0402 (17)	0.0314 (16)	−0.0052 (13)	−0.0013 (12)	−0.0194 (15)
Cl5	0.0657 (14)	0.0527 (13)	0.0210 (7)	−0.0413 (11)	−0.0127 (8)	0.0107 (7)
Cl6	0.0357 (9)	0.0418 (13)	0.0336 (8)	−0.0004 (9)	0.0073 (7)	−0.0026 (8)
C99'	0.044 (5)	0.024 (4)	0.016 (3)	−0.002 (3)	−0.002 (3)	−0.005 (3)
Cl4'	0.040 (2)	0.058 (3)	0.041 (2)	−0.0050 (17)	−0.0056 (15)	−0.0084 (18)
Cl5'	0.141 (3)	0.0371 (13)	0.0460 (14)	−0.0363 (17)	−0.0559 (18)	0.0142 (10)
Cl6'	0.0431 (13)	0.0568 (19)	0.0751 (18)	0.0098 (13)	−0.0053 (11)	−0.0429 (16)

Geometric parameters (Å, º) top

Au1—Cl3	2.2825 (7)	C13—H13C	0.9800
Au1—Cl2	2.2889 (6)	C21—H21A	0.9800
Au1—Cl1	2.3172 (6)	C21—H21B	0.9800
Au1—Se1	2.4476 (3)	C21—H21C	0.9800
Se1—P1	2.2232 (6)	C22—H22A	0.9800
P1—C3	1.844 (3)	C22—H22B	0.9800
P1—C2	1.874 (2)	C22—H22C	0.9800
P1—C1	1.878 (2)	C23—H23A	0.9800
C1—C12	1.537 (3)	C23—H23B	0.9800
C1—C13	1.538 (3)	C23—H23C	0.9800
C1—C11	1.541 (3)	C31—H31A	0.9800
C2—C23	1.533 (4)	C31—H31B	0.9800
C2—C22	1.540 (4)	C31—H31C	0.9800
C2—C21	1.548 (4)	C32—H32A	0.9800
C3—C31	1.532 (4)	C32—H32B	0.9800
C3—C32	1.540 (4)	C32—H32C	0.9800
C3—H3	1.0000	C99—Cl6	1.748 (7)
C11—H11A	0.9800	C99—Cl4	1.756 (8)
C11—H11B	0.9800	C99—Cl5	1.756 (7)
C11—H11C	0.9800	C99—D99	1.0000
C12—H12A	0.9800	C99'—Cl4'	1.692 (9)
C12—H12B	0.9800	C99'—Cl6'	1.723 (7)
C12—H12C	0.9800	C99'—Cl5'	1.749 (8)
C13—H13A	0.9800	C99'—D99'	1.0000
C13—H13B	0.9800

Cl3—Au1—Cl2	177.64 (2)	C1—C13—H13C	109.5
Cl3—Au1—Cl1	89.67 (2)	H13A—C13—H13C	109.5
Cl2—Au1—Cl1	89.66 (2)	H13B—C13—H13C	109.5
Cl3—Au1—Se1	92.332 (18)	C2—C21—H21A	109.5
Cl2—Au1—Se1	88.238 (18)	C2—C21—H21B	109.5
Cl1—Au1—Se1	176.855 (18)	H21A—C21—H21B	109.5
P1—Se1—Au1	107.617 (18)	C2—C21—H21C	109.5
C3—P1—C2	112.97 (12)	H21A—C21—H21C	109.5
C3—P1—C1	108.44 (11)	H21B—C21—H21C	109.5
C2—P1—C1	114.23 (11)	C2—C22—H22A	109.5
C3—P1—Se1	108.64 (9)	C2—C22—H22B	109.5
C2—P1—Se1	101.78 (8)	H22A—C22—H22B	109.5
C1—P1—Se1	110.54 (8)	C2—C22—H22C	109.5
C12—C1—C13	108.0 (2)	H22A—C22—H22C	109.5
C12—C1—C11	108.3 (2)	H22B—C22—H22C	109.5
C13—C1—C11	109.4 (2)	C2—C23—H23A	109.5
C12—C1—P1	111.35 (17)	C2—C23—H23B	109.5
C13—C1—P1	108.18 (17)	H23A—C23—H23B	109.5
C11—C1—P1	111.60 (16)	C2—C23—H23C	109.5
C23—C2—C22	109.8 (2)	H23A—C23—H23C	109.5
C23—C2—C21	107.5 (2)	H23B—C23—H23C	109.5
C22—C2—C21	108.7 (2)	C3—C31—H31A	109.5
C23—C2—P1	110.79 (18)	C3—C31—H31B	109.5
C22—C2—P1	109.77 (17)	H31A—C31—H31B	109.5
C21—C2—P1	110.23 (18)	C3—C31—H31C	109.5
C31—C3—C32	110.6 (2)	H31A—C31—H31C	109.5
C31—C3—P1	113.10 (19)	H31B—C31—H31C	109.5
C32—C3—P1	116.51 (18)	C3—C32—H32A	109.5
C31—C3—H3	105.2	C3—C32—H32B	109.5
C32—C3—H3	105.2	H32A—C32—H32B	109.5
P1—C3—H3	105.2	C3—C32—H32C	109.5
C1—C11—H11A	109.5	H32A—C32—H32C	109.5
C1—C11—H11B	109.5	H32B—C32—H32C	109.5
H11A—C11—H11B	109.5	Cl6—C99—Cl4	111.3 (4)
C1—C11—H11C	109.5	Cl6—C99—Cl5	110.4 (4)
H11A—C11—H11C	109.5	Cl4—C99—Cl5	110.9 (4)
H11B—C11—H11C	109.5	Cl6—C99—D99	108.0
C1—C12—H12A	109.5	Cl4—C99—D99	108.0
C1—C12—H12B	109.5	Cl5—C99—D99	108.0
H12A—C12—H12B	109.5	Cl4'—C99'—Cl6'	111.9 (5)
C1—C12—H12C	109.5	Cl4'—C99'—Cl5'	106.4 (5)
H12A—C12—H12C	109.5	Cl6'—C99'—Cl5'	112.7 (5)
H12B—C12—H12C	109.5	Cl4'—C99'—D99'	108.6
C1—C13—H13A	109.5	Cl6'—C99'—D99'	108.6
C1—C13—H13B	109.5	Cl5'—C99'—D99'	108.6
H13A—C13—H13B	109.5

Cl3—Au1—Se1—P1	68.16 (3)	C1—P1—C2—C23	41.5 (2)
Cl2—Au1—Se1—P1	−114.14 (3)	Se1—P1—C2—C23	−77.67 (18)
Au1—Se1—P1—C3	−69.90 (9)	C3—P1—C2—C22	44.6 (2)
Au1—Se1—P1—C2	170.69 (8)	C1—P1—C2—C22	−80.0 (2)
Au1—Se1—P1—C1	48.97 (9)	Se1—P1—C2—C22	160.85 (17)
C3—P1—C1—C12	159.02 (17)	C3—P1—C2—C21	−75.1 (2)
C2—P1—C1—C12	−74.0 (2)	C1—P1—C2—C21	160.34 (18)
Se1—P1—C1—C12	40.02 (19)	Se1—P1—C2—C21	41.2 (2)
C3—P1—C1—C13	40.54 (19)	C2—P1—C3—C31	54.3 (2)
C2—P1—C1—C13	167.49 (16)	C1—P1—C3—C31	−178.01 (19)
Se1—P1—C1—C13	−78.46 (16)	Se1—P1—C3—C31	−57.8 (2)
C3—P1—C1—C11	−79.9 (2)	C2—P1—C3—C32	−75.4 (2)
C2—P1—C1—C11	47.1 (2)	C1—P1—C3—C32	52.2 (2)
Se1—P1—C1—C11	161.13 (15)	Se1—P1—C3—C32	172.41 (16)
C3—P1—C2—C23	166.03 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C99—D99···Cl2	1.00	2.76	3.580 (7)	139
C13—H13A···Au1	0.98	2.69	3.618 (3)	158
C21—H21C···Se1	0.98	2.70	3.208 (3)	112
C3—H3···Cl3	1.00	2.65	3.497 (3)	142
C13—H13C···Cl2ⁱ	0.98	2.92	3.866 (3)	163

Symmetry code: (i) −x, −y+1, −z+1.

Tribromrido(tripropan-2-ylphosphane sulfide-κS)gold(III) (9b) top

Crystal data top

[AuBr₃(C₁₀H₂₃PS)]	F(000) = 1160
M_r = 628.98	D_x = 2.564 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1341 (2) Å	Cell parameters from 22624 reflections
b = 7.9039 (2) Å	θ = 2.2–30.8°
c = 22.6420 (4) Å	µ = 16.58 mm⁻¹
β = 94.519 (2)°	T = 100 K
V = 1629.56 (6) Å³	Plate, red
Z = 4	0.15 × 0.1 × 0.1 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	4964 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4633 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.037
ω scans	θ_max = 30.9°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −13→13
T_min = 0.486, T_max = 1.000	k = −11→11
64266 measured reflections	l = −32→31

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.038	w = 1/[σ²(F_o²) + (0.007P)² + 3.9739P] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max = 0.003
4964 reflections	Δρ_max = 1.58 e Å⁻³
143 parameters	Δρ_min = −0.95 e Å⁻³
0 restraints	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015), F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00043 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.14463 (2)	0.72099 (2)	0.36757 (2)	0.01115 (3)
Br1	−0.10011 (3)	0.84484 (4)	0.36034 (2)	0.02107 (7)
Br3	0.11734 (3)	0.65623 (4)	0.26267 (2)	0.01764 (6)
Br2	0.17679 (4)	0.81030 (4)	0.47063 (2)	0.02013 (7)
P1	0.36854 (8)	0.35281 (10)	0.37465 (3)	0.01090 (13)
S1	0.38356 (8)	0.61179 (9)	0.37761 (3)	0.01358 (13)
C1	0.5535 (3)	0.2875 (4)	0.40279 (14)	0.0171 (6)
H1	0.562788	0.316948	0.445876	0.021*
C2	0.3126 (3)	0.2763 (4)	0.30005 (12)	0.0131 (5)
H2	0.221692	0.340584	0.286679	0.016*
C3	0.2412 (3)	0.2647 (4)	0.42503 (13)	0.0153 (6)
H3	0.252010	0.138946	0.423206	0.018*
C11	0.5728 (4)	0.0942 (5)	0.39940 (16)	0.0269 (8)
H11A	0.577770	0.060273	0.357972	0.040*
H11B	0.489227	0.038208	0.415724	0.040*
H11C	0.663821	0.061200	0.422335	0.040*
C12	0.6787 (3)	0.3807 (5)	0.37507 (15)	0.0256 (7)
H12A	0.772171	0.354456	0.397475	0.038*
H12B	0.661110	0.502875	0.376156	0.038*
H12C	0.682852	0.344092	0.333872	0.038*
C21	0.4268 (3)	0.3213 (4)	0.25618 (13)	0.0173 (6)
H21A	0.514162	0.250385	0.264097	0.026*
H21B	0.454273	0.440703	0.260875	0.026*
H21C	0.384802	0.301537	0.215597	0.026*
C22	0.2702 (3)	0.0890 (4)	0.29712 (14)	0.0173 (6)
H22A	0.240437	0.057944	0.256012	0.026*
H22B	0.188340	0.068959	0.321750	0.026*
H22C	0.354579	0.020019	0.311729	0.026*
C31	0.2794 (4)	0.3151 (5)	0.48959 (14)	0.0241 (7)
H31A	0.276855	0.438616	0.493159	0.036*
H31B	0.378065	0.274003	0.502450	0.036*
H31C	0.207962	0.265013	0.514538	0.036*
C32	0.0805 (3)	0.3034 (4)	0.40569 (14)	0.0184 (6)
H32A	0.016833	0.226482	0.425981	0.028*
H32B	0.063393	0.287823	0.362757	0.028*
H32C	0.058238	0.420545	0.415930	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01252 (5)	0.01097 (5)	0.00987 (5)	0.00095 (4)	0.00031 (3)	0.00136 (4)
Br1	0.01612 (14)	0.02620 (16)	0.02102 (15)	0.00786 (12)	0.00227 (11)	0.00523 (13)
Br3	0.02175 (14)	0.01905 (15)	0.01134 (13)	0.00400 (11)	−0.00357 (10)	−0.00144 (11)
Br2	0.02871 (16)	0.02110 (16)	0.01053 (13)	0.00543 (12)	0.00127 (11)	−0.00117 (11)
P1	0.0092 (3)	0.0123 (3)	0.0112 (3)	0.0014 (3)	0.0009 (2)	0.0005 (3)
S1	0.0114 (3)	0.0131 (3)	0.0160 (3)	−0.0012 (2)	−0.0003 (2)	−0.0010 (3)
C1	0.0136 (13)	0.0215 (15)	0.0158 (14)	0.0045 (12)	−0.0021 (10)	−0.0017 (12)
C2	0.0128 (12)	0.0145 (13)	0.0119 (12)	−0.0007 (11)	0.0008 (10)	−0.0012 (11)
C3	0.0168 (13)	0.0150 (14)	0.0148 (13)	0.0004 (11)	0.0051 (11)	0.0042 (11)
C11	0.0230 (16)	0.0259 (18)	0.0300 (18)	0.0146 (14)	−0.0100 (14)	−0.0072 (15)
C12	0.0097 (14)	0.042 (2)	0.0248 (17)	0.0024 (13)	−0.0009 (12)	−0.0009 (15)
C21	0.0197 (14)	0.0202 (15)	0.0124 (13)	−0.0022 (12)	0.0036 (11)	−0.0003 (11)
C22	0.0161 (14)	0.0159 (14)	0.0197 (15)	−0.0013 (11)	0.0007 (11)	−0.0024 (12)
C31	0.0288 (17)	0.0304 (19)	0.0135 (14)	−0.0009 (14)	0.0045 (12)	0.0039 (13)
C32	0.0150 (13)	0.0180 (16)	0.0230 (15)	−0.0009 (11)	0.0071 (11)	0.0016 (12)

Geometric parameters (Å, º) top

Au1—S1	2.3413 (7)	C11—H11B	0.9800
Au1—Br3	2.4233 (3)	C11—H11C	0.9800
Au1—Br2	2.4333 (3)	C12—H12A	0.9800
Au1—Br1	2.4341 (3)	C12—H12B	0.9800
P1—C2	1.828 (3)	C12—H12C	0.9800
P1—C3	1.830 (3)	C21—H21A	0.9800
P1—C1	1.832 (3)	C21—H21B	0.9800
P1—S1	2.0523 (10)	C21—H21C	0.9800
C1—C12	1.536 (4)	C22—H22A	0.9800
C1—C11	1.540 (5)	C22—H22B	0.9800
C1—H1	1.0000	C22—H22C	0.9800
C2—C22	1.531 (4)	C31—H31A	0.9800
C2—C21	1.538 (4)	C31—H31B	0.9800
C2—H2	1.0000	C31—H31C	0.9800
C3—C31	1.529 (4)	C32—H32A	0.9800
C3—C32	1.529 (4)	C32—H32B	0.9800
C3—H3	1.0000	C32—H32C	0.9800
C11—H11A	0.9800

S1—Au1—Br3	92.317 (19)	C1—C11—H11C	109.5
S1—Au1—Br2	88.43 (2)	H11A—C11—H11C	109.5
Br3—Au1—Br2	175.188 (12)	H11B—C11—H11C	109.5
S1—Au1—Br1	177.35 (2)	C1—C12—H12A	109.5
Br3—Au1—Br1	89.771 (11)	C1—C12—H12B	109.5
Br2—Au1—Br1	89.350 (11)	H12A—C12—H12B	109.5
C2—P1—C3	107.76 (14)	C1—C12—H12C	109.5
C2—P1—C1	114.26 (14)	H12A—C12—H12C	109.5
C3—P1—C1	106.86 (14)	H12B—C12—H12C	109.5
C2—P1—S1	111.90 (10)	C2—C21—H21A	109.5
C3—P1—S1	113.79 (11)	C2—C21—H21B	109.5
C1—P1—S1	102.26 (11)	H21A—C21—H21B	109.5
P1—S1—Au1	107.77 (4)	C2—C21—H21C	109.5
C12—C1—C11	111.3 (3)	H21A—C21—H21C	109.5
C12—C1—P1	114.8 (2)	H21B—C21—H21C	109.5
C11—C1—P1	111.6 (2)	C2—C22—H22A	109.5
C12—C1—H1	106.2	C2—C22—H22B	109.5
C11—C1—H1	106.2	H22A—C22—H22B	109.5
P1—C1—H1	106.2	C2—C22—H22C	109.5
C22—C2—C21	112.2 (2)	H22A—C22—H22C	109.5
C22—C2—P1	114.3 (2)	H22B—C22—H22C	109.5
C21—C2—P1	111.5 (2)	C3—C31—H31A	109.5
C22—C2—H2	106.1	C3—C31—H31B	109.5
C21—C2—H2	106.1	H31A—C31—H31B	109.5
P1—C2—H2	106.1	C3—C31—H31C	109.5
C31—C3—C32	111.3 (3)	H31A—C31—H31C	109.5
C31—C3—P1	112.8 (2)	H31B—C31—H31C	109.5
C32—C3—P1	112.9 (2)	C3—C32—H32A	109.5
C31—C3—H3	106.4	C3—C32—H32B	109.5
C32—C3—H3	106.4	H32A—C32—H32B	109.5
P1—C3—H3	106.4	C3—C32—H32C	109.5
C1—C11—H11A	109.5	H32A—C32—H32C	109.5
C1—C11—H11B	109.5	H32B—C32—H32C	109.5
H11A—C11—H11B	109.5

C2—P1—S1—Au1	72.07 (10)	C1—P1—C2—C22	75.9 (2)
C3—P1—S1—Au1	−50.38 (12)	S1—P1—C2—C22	−168.53 (17)
C1—P1—S1—Au1	−165.21 (10)	C3—P1—C2—C21	−171.3 (2)
Br3—Au1—S1—P1	−74.36 (4)	C1—P1—C2—C21	−52.7 (3)
Br2—Au1—S1—P1	110.40 (4)	S1—P1—C2—C21	62.9 (2)
C2—P1—C1—C12	74.0 (3)	C2—P1—C3—C31	178.2 (2)
C3—P1—C1—C12	−166.9 (2)	C1—P1—C3—C31	54.9 (3)
S1—P1—C1—C12	−47.1 (2)	S1—P1—C3—C31	−57.2 (2)
C2—P1—C1—C11	−53.8 (3)	C2—P1—C3—C32	−54.6 (3)
C3—P1—C1—C11	65.3 (3)	C1—P1—C3—C32	−177.8 (2)
S1—P1—C1—C11	−174.9 (2)	S1—P1—C3—C32	70.1 (2)
C3—P1—C2—C22	−42.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32C···Au1	0.98	2.76	3.473 (3)	131
C12—H12B···S1	0.98	2.68	3.261 (3)	118
C2—H2···Br3	1.00	2.71	3.560 (3)	143
C22—H22B···Au1ⁱ	0.98	2.98	3.551 (3)	119
C21—H21C···Br1ⁱⁱ	0.98	3.02	3.829 (3)	141
C3—H3···Br2ⁱ	1.00	2.91	3.796 (3)	148
C32—H32A···Br2ⁱⁱⁱ	0.98	3.06	3.900 (3)	145
C11—H11C···Br2^iv	0.98	2.91	3.661 (3)	134

Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1.

Tribromido[di-tert-butyl(propan-2-yl)phosphane sulfide-κS]gold(III) (11b) top

Crystal data top

[AuBr₃(C₁₁H₂₅PS)]	Z = 2
M_r = 657.04	F(000) = 612
Triclinic, P1	D_x = 2.451 Mg m⁻³
a = 8.6067 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1161 (12) Å	Cell parameters from 29495 reflections
c = 11.5123 (12) Å	θ = 2.6–30.8°
α = 77.873 (10)°	µ = 15.18 mm⁻¹
β = 70.257 (10)°	T = 100 K
γ = 71.867 (10)°	Block, red-brown
V = 890.37 (18) Å³	0.2 × 0.2 × 0.2 mm

Data collection top

Oxford Diffaction Xcalibur, Eos diffractometer	5297 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5057 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.038
ω scan	θ_max = 30.9°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→12
T_min = 0.447, T_max = 1.000	k = −14→14
65025 measured reflections	l = −16→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.036	w = 1/[σ²(F_o²) + (0.0122P)² + 1.1802P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.002
5297 reflections	Δρ_max = 1.08 e Å⁻³
163 parameters	Δρ_min = −1.43 e Å⁻³
0 restraints	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015), F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00557 (11)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.46412 (2)	0.35795 (2)	0.23440 (2)	0.00889 (3)
Br1	0.53350 (3)	0.12322 (2)	0.34392 (2)	0.01652 (5)
Br2	0.74993 (3)	0.37590 (2)	0.20749 (2)	0.01400 (5)
Br3	0.19529 (3)	0.32221 (2)	0.23936 (2)	0.01676 (5)
P1	0.21504 (7)	0.72300 (6)	0.24517 (5)	0.00701 (10)
S1	0.40792 (7)	0.58600 (6)	0.13111 (5)	0.00991 (10)
C1	0.2527 (3)	0.7059 (2)	0.3996 (2)	0.0098 (4)
C2	0.2271 (3)	0.8961 (2)	0.1503 (2)	0.0104 (4)
C3	0.0095 (3)	0.6834 (2)	0.2715 (2)	0.0105 (4)
H3	0.027169	0.582577	0.306905	0.013*
C11	0.1481 (3)	0.8353 (2)	0.4690 (2)	0.0141 (5)
H11A	0.188266	0.917296	0.422652	0.021*
H11B	0.162709	0.818416	0.552175	0.021*
H11C	0.026852	0.852351	0.476344	0.021*
C12	0.4426 (3)	0.6869 (3)	0.3846 (2)	0.0146 (5)
H12A	0.512084	0.606051	0.339530	0.022*
H12B	0.459923	0.671395	0.466740	0.022*
H12C	0.476683	0.771305	0.337815	0.022*
C13	0.2010 (3)	0.5748 (2)	0.4781 (2)	0.0132 (4)
H13A	0.227809	0.559330	0.556900	0.020*
H13B	0.264247	0.493282	0.432585	0.020*
H13C	0.077974	0.588312	0.494739	0.020*
C21	0.2602 (3)	0.8846 (2)	0.0122 (2)	0.0147 (5)
H21A	0.373120	0.821183	−0.019419	0.022*
H21B	0.256084	0.977510	−0.035458	0.022*
H21C	0.172280	0.847983	0.003539	0.022*
C22	0.0581 (3)	1.0081 (2)	0.1944 (2)	0.0144 (5)
H22A	0.070696	1.100103	0.150803	0.022*
H22B	0.029741	1.009738	0.284121	0.022*
H22C	−0.033703	0.985600	0.176468	0.022*
C23	0.3757 (3)	0.9422 (2)	0.1601 (2)	0.0150 (5)
H23A	0.386915	1.028408	0.104086	0.023*
H23B	0.481998	0.868304	0.136720	0.023*
H23C	0.353000	0.959173	0.245746	0.023*
C31	−0.0315 (3)	0.6906 (3)	0.1500 (2)	0.0172 (5)
H31A	−0.071273	0.788820	0.117928	0.026*
H31B	−0.121040	0.642829	0.166014	0.026*
H31C	0.071737	0.644795	0.088671	0.026*
C32	−0.1474 (3)	0.7621 (3)	0.3675 (2)	0.0158 (5)
H32A	−0.246278	0.727637	0.377566	0.024*
H32B	−0.172299	0.862586	0.338601	0.024*
H32C	−0.123437	0.746175	0.447427	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01042 (5)	0.00647 (4)	0.00921 (4)	−0.00031 (3)	−0.00286 (3)	−0.00260 (3)
Br1	0.02234 (13)	0.00864 (10)	0.01814 (11)	−0.00152 (9)	−0.00895 (9)	0.00053 (8)
Br2	0.01064 (11)	0.01396 (10)	0.01718 (11)	−0.00019 (8)	−0.00497 (8)	−0.00448 (8)
Br3	0.01402 (11)	0.01009 (10)	0.02811 (13)	−0.00327 (8)	−0.00674 (10)	−0.00517 (9)
P1	0.0074 (2)	0.0062 (2)	0.0072 (2)	−0.00126 (19)	−0.00218 (19)	−0.00103 (18)
S1	0.0113 (3)	0.0084 (2)	0.0075 (2)	−0.00064 (19)	−0.00086 (19)	−0.00185 (18)
C1	0.0117 (10)	0.0100 (9)	0.0074 (9)	−0.0006 (8)	−0.0040 (8)	−0.0019 (7)
C2	0.0134 (11)	0.0073 (9)	0.0095 (10)	−0.0029 (8)	−0.0026 (8)	0.0001 (7)
C3	0.0100 (10)	0.0084 (9)	0.0142 (10)	−0.0033 (8)	−0.0053 (8)	0.0009 (8)
C11	0.0151 (11)	0.0132 (10)	0.0134 (11)	−0.0012 (9)	−0.0032 (9)	−0.0058 (8)
C12	0.0110 (11)	0.0185 (11)	0.0146 (11)	−0.0003 (9)	−0.0062 (9)	−0.0043 (9)
C13	0.0181 (12)	0.0103 (10)	0.0091 (10)	−0.0017 (9)	−0.0040 (8)	−0.0001 (8)
C21	0.0217 (12)	0.0119 (10)	0.0107 (10)	−0.0053 (9)	−0.0054 (9)	0.0009 (8)
C22	0.0159 (11)	0.0077 (10)	0.0180 (11)	−0.0010 (8)	−0.0053 (9)	−0.0008 (8)
C23	0.0167 (12)	0.0127 (10)	0.0170 (11)	−0.0077 (9)	−0.0040 (9)	−0.0003 (9)
C31	0.0186 (12)	0.0180 (11)	0.0210 (12)	−0.0081 (10)	−0.0125 (10)	0.0011 (9)
C32	0.0084 (11)	0.0144 (11)	0.0217 (12)	−0.0023 (9)	−0.0024 (9)	−0.0006 (9)

Geometric parameters (Å, º) top

Au1—S1	2.3477 (6)	C12—H12B	0.9800
Au1—Br3	2.4310 (3)	C12—H12C	0.9800
Au1—Br2	2.4330 (3)	C13—H13A	0.9800
Au1—Br1	2.4399 (4)	C13—H13B	0.9800
P1—C3	1.847 (2)	C13—H13C	0.9800
P1—C2	1.872 (2)	C21—H21A	0.9800
P1—C1	1.877 (2)	C21—H21B	0.9800
P1—S1	2.0640 (8)	C21—H21C	0.9800
C1—C12	1.537 (3)	C22—H22A	0.9800
C1—C13	1.538 (3)	C22—H22B	0.9800
C1—C11	1.543 (3)	C22—H22C	0.9800
C2—C23	1.535 (3)	C23—H23A	0.9800
C2—C21	1.541 (3)	C23—H23B	0.9800
C2—C22	1.541 (3)	C23—H23C	0.9800
C3—C31	1.536 (3)	C31—H31A	0.9800
C3—C32	1.540 (3)	C31—H31B	0.9800
C3—H3	1.0000	C31—H31C	0.9800
C11—H11A	0.9800	C32—H32A	0.9800
C11—H11B	0.9800	C32—H32B	0.9800
C11—H11C	0.9800	C32—H32C	0.9800
C12—H12A	0.9800

S1—Au1—Br3	93.532 (19)	C1—C12—H12C	109.5
S1—Au1—Br2	87.959 (19)	H12A—C12—H12C	109.5
Br3—Au1—Br2	172.720 (9)	H12B—C12—H12C	109.5
S1—Au1—Br1	177.293 (16)	C1—C13—H13A	109.5
Br3—Au1—Br1	89.099 (14)	C1—C13—H13B	109.5
Br2—Au1—Br1	89.510 (14)	H13A—C13—H13B	109.5
C3—P1—C2	112.57 (10)	C1—C13—H13C	109.5
C3—P1—C1	108.53 (11)	H13A—C13—H13C	109.5
C2—P1—C1	113.56 (10)	H13B—C13—H13C	109.5
C3—P1—S1	109.09 (8)	C2—C21—H21A	109.5
C2—P1—S1	101.70 (7)	C2—C21—H21B	109.5
C1—P1—S1	111.23 (7)	H21A—C21—H21B	109.5
P1—S1—Au1	111.56 (3)	C2—C21—H21C	109.5
C12—C1—C13	108.27 (19)	H21A—C21—H21C	109.5
C12—C1—C11	107.87 (19)	H21B—C21—H21C	109.5
C13—C1—C11	109.49 (19)	C2—C22—H22A	109.5
C12—C1—P1	111.22 (15)	C2—C22—H22B	109.5
C13—C1—P1	107.83 (15)	H22A—C22—H22B	109.5
C11—C1—P1	112.09 (15)	C2—C22—H22C	109.5
C23—C2—C21	107.46 (19)	H22A—C22—H22C	109.5
C23—C2—C22	109.62 (19)	H22B—C22—H22C	109.5
C21—C2—C22	108.69 (19)	C2—C23—H23A	109.5
C23—C2—P1	110.46 (16)	C2—C23—H23B	109.5
C21—C2—P1	110.21 (15)	H23A—C23—H23B	109.5
C22—C2—P1	110.34 (16)	C2—C23—H23C	109.5
C31—C3—C32	110.81 (19)	H23A—C23—H23C	109.5
C31—C3—P1	112.74 (17)	H23B—C23—H23C	109.5
C32—C3—P1	117.05 (16)	C3—C31—H31A	109.5
C31—C3—H3	105.0	C3—C31—H31B	109.5
C32—C3—H3	105.0	H31A—C31—H31B	109.5
P1—C3—H3	105.0	C3—C31—H31C	109.5
C1—C11—H11A	109.5	H31A—C31—H31C	109.5
C1—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	C3—C32—H32A	109.5
C1—C11—H11C	109.5	C3—C32—H32B	109.5
H11A—C11—H11C	109.5	H32A—C32—H32B	109.5
H11B—C11—H11C	109.5	C3—C32—H32C	109.5
C1—C12—H12A	109.5	H32A—C32—H32C	109.5
C1—C12—H12B	109.5	H32B—C32—H32C	109.5
H12A—C12—H12B	109.5

C3—P1—S1—Au1	−70.82 (8)	C1—P1—C2—C23	41.03 (19)
C2—P1—S1—Au1	170.07 (8)	S1—P1—C2—C23	−78.55 (15)
C1—P1—S1—Au1	48.86 (9)	C3—P1—C2—C21	−76.56 (18)
Br3—Au1—S1—P1	70.22 (3)	C1—P1—C2—C21	159.61 (16)
Br2—Au1—S1—P1	−116.91 (3)	S1—P1—C2—C21	40.03 (17)
C3—P1—C1—C12	160.43 (16)	C3—P1—C2—C22	43.48 (19)
C2—P1—C1—C12	−73.58 (18)	C1—P1—C2—C22	−80.34 (18)
S1—P1—C1—C12	40.42 (17)	S1—P1—C2—C22	160.08 (15)
C3—P1—C1—C13	41.86 (17)	C2—P1—C3—C31	54.96 (19)
C2—P1—C1—C13	167.86 (15)	C1—P1—C3—C31	−178.47 (16)
S1—P1—C1—C13	−78.15 (15)	S1—P1—C3—C31	−57.14 (17)
C3—P1—C1—C11	−78.73 (18)	C2—P1—C3—C32	−75.32 (19)
C2—P1—C1—C11	47.3 (2)	C1—P1—C3—C32	51.24 (19)
S1—P1—C1—C11	161.26 (14)	S1—P1—C3—C32	172.58 (15)
C3—P1—C2—C23	164.85 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···Au1	0.98	2.69	3.607 (2)	156
C21—H21A···S1	0.98	2.63	3.109 (2)	110
C12—H12A···S1	0.98	2.89	3.417 (2)	114
C3—H3···Br3	1.00	2.71	3.546 (2)	141
C12—H12A···Br2	0.98	2.89	3.863 (2)	174
C13—H13A···Br2ⁱ	0.98	3.00	3.931 (2)	159

Symmetry code: (i) −x+1, −y+1, −z+1.

Tribromido(tripropan-2-ylphosphane selenide-κS)gold(III) (13b) top

Crystal data top

[AuBr₃(C₉H₂₁PSe)]	Z = 2
M_r = 675.88	F(000) = 616
Triclinic, P1	D_x = 2.760 Mg m⁻³
a = 8.3928 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1417 (4) Å	Cell parameters from 15280 reflections
c = 10.7567 (4) Å	θ = 2.2–30.9°
α = 94.419 (3)°	µ = 18.72 mm⁻¹
β = 105.612 (3)°	T = 100 K
γ = 110.113 (3)°	Plate, dichroic pale brown / black
V = 813.33 (5) Å³	0.2 × 0.1 × 0.01 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	4825 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4278 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.059
ω scan	θ_max = 31.0°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −11→12
T_min = 0.200, T_max = 1.000	k = −14→14
44535 measured reflections	l = −14→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0378P)² + 1.6418P] where P = (F_o² + 2F_c²)/3
4825 reflections	(Δ/σ)_max = 0.001
142 parameters	Δρ_max = 1.43 e Å⁻³
0 restraints	Δρ_min = −1.49 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.69422 (2)	0.57788 (2)	0.18566 (2)	0.01164 (6)
Br1	0.83155 (6)	0.83965 (5)	0.25275 (5)	0.02209 (10)
Br3	0.40852 (5)	0.58195 (4)	0.19223 (4)	0.01647 (9)
Br2	0.97546 (5)	0.57176 (5)	0.17238 (5)	0.02254 (10)
P1	0.48156 (13)	0.21791 (11)	0.26640 (10)	0.01046 (19)
Se1	0.56222 (5)	0.31839 (4)	0.10650 (4)	0.01349 (9)
C1	0.4341 (5)	0.0298 (4)	0.2060 (4)	0.0144 (8)
H1	0.544743	0.026681	0.189699	0.017*
C2	0.2956 (5)	0.2543 (4)	0.2980 (4)	0.0131 (7)
H2	0.338155	0.360716	0.321681	0.016*
C3	0.6650 (5)	0.2762 (4)	0.4225 (4)	0.0122 (7)
H3	0.619362	0.219320	0.486244	0.015*
C11	0.3991 (7)	−0.0633 (5)	0.3087 (5)	0.0241 (10)
H11A	0.289038	−0.065939	0.325605	0.036*
H11B	0.499672	−0.022943	0.390446	0.036*
H11C	0.386077	−0.160493	0.275910	0.036*
C12	0.2817 (7)	−0.0355 (5)	0.0745 (5)	0.0288 (11)
H12A	0.278900	−0.128698	0.039686	0.043*
H12B	0.301865	0.028362	0.011491	0.043*
H12C	0.167277	−0.047530	0.088602	0.043*
C21	0.1296 (5)	0.2087 (5)	0.1770 (4)	0.0176 (8)
H21A	0.064233	0.105155	0.162763	0.026*
H21B	0.165974	0.233390	0.099863	0.026*
H21C	0.052253	0.258177	0.190817	0.026*
C22	0.2491 (5)	0.1964 (5)	0.4180 (4)	0.0170 (8)
H22A	0.159561	0.229361	0.436607	0.025*
H22B	0.357276	0.231354	0.494636	0.025*
H22C	0.200989	0.091614	0.398734	0.025*
C31	0.8257 (6)	0.2440 (5)	0.4101 (5)	0.0224 (9)
H31A	0.871399	0.294863	0.345388	0.034*
H31B	0.789032	0.140919	0.381437	0.034*
H31C	0.919803	0.275568	0.495506	0.034*
C32	0.7203 (6)	0.4337 (5)	0.4804 (4)	0.0178 (8)
H32A	0.803324	0.455971	0.569887	0.027*
H32B	0.613970	0.452440	0.482590	0.027*
H32C	0.778982	0.493540	0.425864	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01092 (8)	0.01220 (8)	0.01097 (8)	0.00286 (6)	0.00402 (6)	0.00270 (6)
Br1	0.0235 (2)	0.0131 (2)	0.0234 (2)	−0.00006 (16)	0.00726 (17)	0.00196 (16)
Br3	0.01689 (19)	0.0151 (2)	0.0233 (2)	0.00837 (15)	0.01141 (16)	0.00740 (16)
Br2	0.01151 (18)	0.0285 (2)	0.0274 (2)	0.00615 (17)	0.00769 (17)	0.00587 (19)
P1	0.0096 (4)	0.0100 (4)	0.0109 (4)	0.0028 (3)	0.0035 (3)	0.0006 (4)
Se1	0.01722 (19)	0.01294 (19)	0.01227 (19)	0.00549 (15)	0.00815 (15)	0.00196 (14)
C1	0.0175 (18)	0.0105 (18)	0.0163 (19)	0.0066 (15)	0.0058 (15)	0.0012 (15)
C2	0.0118 (17)	0.0117 (18)	0.0154 (19)	0.0044 (14)	0.0046 (14)	0.0003 (14)
C3	0.0094 (16)	0.0180 (19)	0.0080 (17)	0.0043 (14)	0.0023 (13)	0.0025 (14)
C11	0.035 (3)	0.012 (2)	0.025 (2)	0.0063 (18)	0.011 (2)	0.0037 (17)
C12	0.034 (3)	0.022 (2)	0.019 (2)	0.006 (2)	−0.0006 (19)	−0.0088 (18)
C21	0.0115 (18)	0.022 (2)	0.017 (2)	0.0045 (16)	0.0031 (15)	0.0033 (16)
C22	0.0128 (18)	0.022 (2)	0.018 (2)	0.0056 (16)	0.0086 (15)	0.0055 (16)
C31	0.0123 (19)	0.025 (2)	0.026 (2)	0.0068 (17)	0.0032 (17)	−0.0025 (19)
C32	0.0167 (19)	0.016 (2)	0.0151 (19)	0.0032 (16)	0.0022 (15)	−0.0011 (16)

Geometric parameters (Å, º) top

Au1—Br2	2.4241 (4)	C11—H11B	0.9800
Au1—Br3	2.4321 (4)	C11—H11C	0.9800
Au1—Se1	2.4535 (4)	C12—H12A	0.9800
Au1—Br1	2.4597 (5)	C12—H12B	0.9800
P1—C2	1.831 (4)	C12—H12C	0.9800
P1—C1	1.835 (4)	C21—H21A	0.9800
P1—C3	1.835 (4)	C21—H21B	0.9800
P1—Se1	2.2085 (11)	C21—H21C	0.9800
C1—C11	1.531 (6)	C22—H22A	0.9800
C1—C12	1.541 (6)	C22—H22B	0.9800
C1—H1	1.0000	C22—H22C	0.9800
C2—C21	1.529 (5)	C31—H31A	0.9800
C2—C22	1.547 (6)	C31—H31B	0.9800
C2—H2	1.0000	C31—H31C	0.9800
C3—C32	1.528 (6)	C32—H32A	0.9800
C3—C31	1.529 (6)	C32—H32B	0.9800
C3—H3	1.0000	C32—H32C	0.9800
C11—H11A	0.9800

Br2—Au1—Br3	178.373 (15)	C1—C11—H11C	109.5
Br2—Au1—Se1	87.616 (16)	H11A—C11—H11C	109.5
Br3—Au1—Se1	91.709 (14)	H11B—C11—H11C	109.5
Br2—Au1—Br1	90.566 (17)	C1—C12—H12A	109.5
Br3—Au1—Br1	90.031 (16)	C1—C12—H12B	109.5
Se1—Au1—Br1	176.522 (15)	H12A—C12—H12B	109.5
C2—P1—C1	115.50 (19)	C1—C12—H12C	109.5
C2—P1—C3	107.15 (18)	H12A—C12—H12C	109.5
C1—P1—C3	107.53 (19)	H12B—C12—H12C	109.5
C2—P1—Se1	112.81 (14)	C2—C21—H21A	109.5
C1—P1—Se1	101.08 (14)	C2—C21—H21B	109.5
C3—P1—Se1	112.75 (13)	H21A—C21—H21B	109.5
P1—Se1—Au1	107.24 (3)	C2—C21—H21C	109.5
C11—C1—C12	110.4 (4)	H21A—C21—H21C	109.5
C11—C1—P1	112.1 (3)	H21B—C21—H21C	109.5
C12—C1—P1	113.9 (3)	C2—C22—H22A	109.5
C11—C1—H1	106.6	C2—C22—H22B	109.5
C12—C1—H1	106.6	H22A—C22—H22B	109.5
P1—C1—H1	106.6	C2—C22—H22C	109.5
C21—C2—C22	111.7 (3)	H22A—C22—H22C	109.5
C21—C2—P1	113.5 (3)	H22B—C22—H22C	109.5
C22—C2—P1	113.3 (3)	C3—C31—H31A	109.5
C21—C2—H2	105.8	C3—C31—H31B	109.5
C22—C2—H2	105.8	H31A—C31—H31B	109.5
P1—C2—H2	105.8	C3—C31—H31C	109.5
C32—C3—C31	111.2 (3)	H31A—C31—H31C	109.5
C32—C3—P1	112.2 (3)	H31B—C31—H31C	109.5
C31—C3—P1	112.0 (3)	C3—C32—H32A	109.5
C32—C3—H3	107.0	C3—C32—H32B	109.5
C31—C3—H3	107.0	H32A—C32—H32B	109.5
P1—C3—H3	107.0	C3—C32—H32C	109.5
C1—C11—H11A	109.5	H32A—C32—H32C	109.5
C1—C11—H11B	109.5	H32B—C32—H32C	109.5
H11A—C11—H11B	109.5

C2—P1—Se1—Au1	67.97 (14)	C3—P1—C2—C21	−178.9 (3)
C1—P1—Se1—Au1	−168.10 (13)	Se1—P1—C2—C21	56.5 (3)
C3—P1—Se1—Au1	−53.58 (15)	C1—P1—C2—C22	69.7 (3)
Br2—Au1—Se1—P1	114.96 (3)	C3—P1—C2—C22	−50.1 (3)
Br3—Au1—Se1—P1	−66.53 (3)	Se1—P1—C2—C22	−174.7 (2)
C2—P1—C1—C11	−65.9 (4)	C2—P1—C3—C32	−57.0 (3)
C3—P1—C1—C11	53.7 (4)	C1—P1—C3—C32	178.3 (3)
Se1—P1—C1—C11	172.0 (3)	Se1—P1—C3—C32	67.7 (3)
C2—P1—C1—C12	60.4 (4)	C2—P1—C3—C31	177.1 (3)
C3—P1—C1—C12	179.9 (3)	C1—P1—C3—C31	52.3 (4)
Se1—P1—C1—C12	−61.7 (3)	Se1—P1—C3—C31	−58.2 (3)
C1—P1—C2—C21	−59.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32C···Au1	0.98	2.77	3.578 (5)	140
C12—H12B···Se1	0.98	2.90	3.479 (5)	119
C2—H2···Br3	1.00	2.71	3.497 (4)	136
C11—H11C···Br3ⁱ	0.98	2.78	3.752 (5)	171
C32—H32A···Br2ⁱⁱ	0.98	2.99	3.933 (4)	163

Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1.

Tribromido[di-tert-butyl(propan-2-yl)phosphane selenide-κS]gold(III) (15b) top

Crystal data top

[AuBr₃(C₁₁H₂₅PSe)]	Z = 2
M_r = 703.93	F(000) = 648
Triclinic, P1	D_x = 2.586 Mg m⁻³
a = 8.6000 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2045 (7) Å	Cell parameters from 9711 reflections
c = 11.5987 (7) Å	θ = 2.6–30.7°
α = 77.475 (6)°	µ = 16.85 mm⁻¹
β = 69.764 (6)°	T = 100 K
γ = 72.601 (6)°	Lath, dichroic black / orange
V = 904.02 (11) Å³	0.2 × 0.06 × 0.04 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	5282 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4719 reflections with I > 2σ(I)
Detector resolution: 16.1419 pixels mm^-1	R_int = 0.033
ω scans	θ_max = 30.8°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −12→12
T_min = 0.376, T_max = 1.000	k = −14→14
25566 measured reflections	l = −16→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.011P)² + 0.1908P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.036	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 1.04 e Å⁻³
5282 reflections	Δρ_min = −0.80 e Å⁻³
163 parameters	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015), F_c^* = kF_c[1 + 0.001 F_c²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00115 (6)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.47180 (2)	0.35576 (2)	0.23406 (2)	0.01020 (3)
Br1	0.53346 (3)	0.12201 (3)	0.34571 (2)	0.01753 (6)
Br2	0.75742 (3)	0.37440 (3)	0.20826 (2)	0.01554 (6)
Br3	0.19859 (3)	0.32636 (3)	0.24007 (3)	0.01777 (6)
P1	0.21219 (8)	0.73040 (7)	0.24676 (6)	0.00837 (12)
Se1	0.42295 (3)	0.59094 (3)	0.12166 (2)	0.01100 (5)
C1	0.2529 (3)	0.7103 (3)	0.3998 (2)	0.0105 (5)
C2	0.2206 (3)	0.9043 (3)	0.1533 (2)	0.0121 (5)
C3	0.0086 (3)	0.6854 (3)	0.2742 (2)	0.0120 (5)
H3	0.028316	0.585158	0.308624	0.014*
C11	0.1482 (3)	0.8360 (3)	0.4709 (2)	0.0144 (5)
H11A	0.185931	0.919044	0.424127	0.022*
H11B	0.165555	0.818824	0.552543	0.022*
H11C	0.026587	0.849945	0.481054	0.022*
C12	0.4427 (3)	0.6939 (3)	0.3826 (2)	0.0145 (5)
H12A	0.511328	0.612298	0.340854	0.022*
H12B	0.459941	0.682562	0.463805	0.022*
H12C	0.478089	0.776527	0.332290	0.022*
C13	0.2029 (3)	0.5779 (3)	0.4767 (2)	0.0138 (5)
H13A	0.234962	0.558998	0.553047	0.021*
H13B	0.262708	0.499890	0.428497	0.021*
H13C	0.079221	0.590537	0.497531	0.021*
C21	0.2509 (3)	0.8956 (3)	0.0155 (2)	0.0152 (5)
H21A	0.365047	0.836963	−0.018616	0.023*
H21B	0.242429	0.988685	−0.030855	0.023*
H21C	0.164595	0.855704	0.008515	0.023*
C22	0.0512 (3)	1.0113 (3)	0.2003 (2)	0.0159 (5)
H22A	0.060599	1.102954	0.154970	0.024*
H22B	0.026812	1.013658	0.288936	0.024*
H22C	−0.041513	0.985354	0.186872	0.024*
C23	0.3687 (3)	0.9527 (3)	0.1604 (2)	0.0152 (5)
H23A	0.376770	1.040134	0.106096	0.023*
H23B	0.475735	0.882506	0.133773	0.023*
H23C	0.348598	0.966518	0.245897	0.023*
C31	−0.0347 (3)	0.6930 (3)	0.1546 (2)	0.0181 (6)
H31A	−0.073019	0.790210	0.122437	0.027*
H31B	−0.125850	0.645820	0.172381	0.027*
H31C	0.067180	0.647990	0.092845	0.027*
C32	−0.1478 (3)	0.7586 (3)	0.3717 (2)	0.0179 (6)
H32A	−0.246013	0.722341	0.382432	0.027*
H32B	−0.174112	0.858328	0.344102	0.027*
H32C	−0.122923	0.741852	0.450686	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01150 (5)	0.00826 (5)	0.01035 (5)	−0.00006 (4)	−0.00365 (3)	−0.00294 (3)
Br1	0.02268 (13)	0.01024 (13)	0.01990 (14)	−0.00161 (11)	−0.01002 (11)	0.00022 (10)
Br2	0.01258 (12)	0.01528 (13)	0.01902 (13)	−0.00035 (10)	−0.00666 (10)	−0.00385 (11)
Br3	0.01498 (12)	0.01201 (13)	0.02826 (15)	−0.00277 (10)	−0.00777 (11)	−0.00519 (11)
P1	0.0086 (3)	0.0075 (3)	0.0088 (3)	−0.0009 (2)	−0.0030 (2)	−0.0015 (2)
Se1	0.01263 (12)	0.00941 (12)	0.00860 (11)	0.00004 (10)	−0.00190 (9)	−0.00236 (9)
C1	0.0109 (11)	0.0105 (12)	0.0103 (12)	−0.0004 (10)	−0.0038 (9)	−0.0039 (10)
C2	0.0133 (12)	0.0104 (12)	0.0129 (12)	−0.0028 (10)	−0.0046 (10)	−0.0015 (10)
C3	0.0133 (12)	0.0088 (12)	0.0159 (13)	−0.0028 (10)	−0.0070 (10)	−0.0009 (10)
C11	0.0179 (13)	0.0122 (13)	0.0122 (12)	−0.0002 (10)	−0.0044 (10)	−0.0047 (10)
C12	0.0117 (12)	0.0202 (14)	0.0136 (13)	0.0006 (11)	−0.0080 (10)	−0.0056 (11)
C13	0.0176 (13)	0.0111 (13)	0.0109 (12)	0.0008 (10)	−0.0062 (10)	−0.0009 (10)
C21	0.0196 (13)	0.0131 (13)	0.0112 (12)	−0.0032 (11)	−0.0043 (10)	0.0004 (10)
C22	0.0158 (12)	0.0114 (13)	0.0184 (13)	−0.0003 (10)	−0.0049 (10)	−0.0023 (11)
C23	0.0180 (13)	0.0126 (13)	0.0157 (13)	−0.0064 (11)	−0.0041 (10)	−0.0010 (10)
C31	0.0173 (13)	0.0194 (15)	0.0218 (14)	−0.0052 (11)	−0.0116 (11)	−0.0005 (12)
C32	0.0098 (12)	0.0177 (14)	0.0227 (14)	−0.0027 (11)	−0.0029 (10)	0.0002 (12)

Geometric parameters (Å, º) top

Au1—Br2	2.4302 (3)	C12—H12B	0.9800
Au1—Br3	2.4320 (3)	C12—H12C	0.9800
Au1—Br1	2.4549 (3)	C13—H13A	0.9800
Au1—Se1	2.4606 (3)	C13—H13B	0.9800
P1—C3	1.847 (2)	C13—H13C	0.9800
P1—C2	1.875 (3)	C21—H21A	0.9800
P1—C1	1.883 (3)	C21—H21B	0.9800
P1—Se1	2.2247 (7)	C21—H21C	0.9800
C1—C12	1.536 (3)	C22—H22A	0.9800
C1—C13	1.538 (3)	C22—H22B	0.9800
C1—C11	1.546 (3)	C22—H22C	0.9800
C2—C23	1.530 (3)	C23—H23A	0.9800
C2—C22	1.539 (3)	C23—H23B	0.9800
C2—C21	1.546 (3)	C23—H23C	0.9800
C3—C32	1.536 (3)	C31—H31A	0.9800
C3—C31	1.536 (3)	C31—H31B	0.9800
C3—H3	1.0000	C31—H31C	0.9800
C11—H11A	0.9800	C32—H32A	0.9800
C11—H11B	0.9800	C32—H32B	0.9800
C11—H11C	0.9800	C32—H32C	0.9800
C12—H12A	0.9800

Br2—Au1—Br3	174.078 (10)	C1—C12—H12C	109.5
Br2—Au1—Br1	90.066 (11)	H12A—C12—H12C	109.5
Br3—Au1—Br1	89.729 (12)	H12B—C12—H12C	109.5
Br2—Au1—Se1	87.317 (11)	C1—C13—H13A	109.5
Br3—Au1—Se1	92.892 (11)	C1—C13—H13B	109.5
Br1—Au1—Se1	177.377 (9)	H13A—C13—H13B	109.5
C3—P1—C2	112.60 (11)	C1—C13—H13C	109.5
C3—P1—C1	108.84 (11)	H13A—C13—H13C	109.5
C2—P1—C1	114.02 (11)	H13B—C13—H13C	109.5
C3—P1—Se1	109.35 (9)	C2—C21—H21A	109.5
C2—P1—Se1	101.46 (8)	C2—C21—H21B	109.5
C1—P1—Se1	110.34 (8)	H21A—C21—H21B	109.5
P1—Se1—Au1	108.81 (2)	C2—C21—H21C	109.5
C12—C1—C13	108.1 (2)	H21A—C21—H21C	109.5
C12—C1—C11	108.1 (2)	H21B—C21—H21C	109.5
C13—C1—C11	109.8 (2)	C2—C22—H22A	109.5
C12—C1—P1	111.46 (16)	C2—C22—H22B	109.5
C13—C1—P1	107.66 (17)	H22A—C22—H22B	109.5
C11—C1—P1	111.76 (17)	C2—C22—H22C	109.5
C23—C2—C22	109.7 (2)	H22A—C22—H22C	109.5
C23—C2—C21	107.4 (2)	H22B—C22—H22C	109.5
C22—C2—C21	108.6 (2)	C2—C23—H23A	109.5
C23—C2—P1	110.52 (17)	C2—C23—H23B	109.5
C22—C2—P1	110.37 (17)	H23A—C23—H23B	109.5
C21—C2—P1	110.18 (18)	C2—C23—H23C	109.5
C32—C3—C31	110.6 (2)	H23A—C23—H23C	109.5
C32—C3—P1	116.61 (18)	H23B—C23—H23C	109.5
C31—C3—P1	113.40 (17)	C3—C31—H31A	109.5
C32—C3—H3	105.0	C3—C31—H31B	109.5
C31—C3—H3	105.0	H31A—C31—H31B	109.5
P1—C3—H3	105.0	C3—C31—H31C	109.5
C1—C11—H11A	109.5	H31A—C31—H31C	109.5
C1—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	C3—C32—H32A	109.5
C1—C11—H11C	109.5	C3—C32—H32B	109.5
H11A—C11—H11C	109.5	H32A—C32—H32B	109.5
H11B—C11—H11C	109.5	C3—C32—H32C	109.5
C1—C12—H12A	109.5	H32A—C32—H32C	109.5
C1—C12—H12B	109.5	H32B—C32—H32C	109.5
H12A—C12—H12B	109.5

C3—P1—Se1—Au1	−69.41 (9)	C1—P1—C2—C23	41.2 (2)
C2—P1—Se1—Au1	171.47 (8)	Se1—P1—C2—C23	−77.43 (17)
C1—P1—Se1—Au1	50.27 (9)	C3—P1—C2—C22	44.3 (2)
Br2—Au1—Se1—P1	−117.58 (2)	C1—P1—C2—C22	−80.3 (2)
Br3—Au1—Se1—P1	68.34 (2)	Se1—P1—C2—C22	161.06 (16)
C3—P1—C1—C12	159.36 (17)	C3—P1—C2—C21	−75.64 (19)
C2—P1—C1—C12	−74.0 (2)	C1—P1—C2—C21	159.73 (16)
Se1—P1—C1—C12	39.38 (19)	Se1—P1—C2—C21	41.14 (17)
C3—P1—C1—C13	41.02 (19)	C2—P1—C3—C32	−75.6 (2)
C2—P1—C1—C13	167.64 (15)	C1—P1—C3—C32	51.9 (2)
Se1—P1—C1—C13	−78.96 (16)	Se1—P1—C3—C32	172.46 (16)
C3—P1—C1—C11	−79.61 (19)	C2—P1—C3—C31	54.6 (2)
C2—P1—C1—C11	47.0 (2)	C1—P1—C3—C31	−177.92 (18)
Se1—P1—C1—C11	160.40 (15)	Se1—P1—C3—C31	−57.3 (2)
C3—P1—C2—C23	165.79 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···Au1	0.98	2.74	3.679 (3)	160
C21—H21A···Se1	0.98	2.69	3.197 (3)	113
C12—H12A···Se1	0.98	2.96	3.484 (3)	115
C3—H3···Br3	1.00	2.75	3.585 (3)	142
C12—H12A···Br2	0.98	3.01	3.980 (3)	173
C13—H13A···Br2ⁱ	0.98	3.02	3.929 (3)	156

Symmetry code: (i) −x+1, −y+1, −z+1.

Compositions of the R₁R₂R₃PEAuX₃ structures presented in this paper (see Scheme) top

Compound	R₁	R₂	R₃	E	X	Comments
9a	ⁱPr	ⁱPr	ⁱPr	S	Cl
10a	ⁱPr	ⁱPr	^tBu	S	Cl
10aa	ⁱPr	ⁱPr	^tBu	S	Cl	Second polymorph of 10a
11a	ⁱPr	^tBu	^tBu	S	Cl
11aa	ⁱPr	^tBu	^tBu	S	Cl	CDCl₃ solvate of 11a
12a	^tBu	^tBu	^tBu	S	Cl	CH₂Cl₂ solvate
14a	ⁱPr	ⁱPr	^tBu	Se	Cl
15a	ⁱPr	^tBu	^tBu	Se	Cl
15aa	ⁱPr	^tBu	^tBu	Se	Cl	CDCl₃ solvate of 15a
9b	ⁱPr	ⁱPr	ⁱPr	S	Br
11b	ⁱPr	^tBu	^tBu	S	Br
13b	ⁱPr	ⁱPr	ⁱPr	Se	Br
15b	ⁱPr	^tBu	^tBu	Se	Br

Acknowledgements

We thank the Open Access Publication Funds of the Technical University of Braunschweig for financial support.

References

Breshears, A. T., Behrle, A. C., Barnes, C. L., Laber, C. H., Baker, G. A. & Walensky, J. R. (2015). Polyhedron, 100, 333–343. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1998). XP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Döring, C. & Jones, P. G. (2016). Z. Anorg. Allg. Chem. 642, 930–936. Google Scholar
Döring, C. & Jones, P. G. (2023). Acta Cryst. E79, 1017–1027. Web of Science CSD CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hofmann, D. W. M. (2002). Acta Cryst. B58, 489–493. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kitaigorodskii, A. I. (1961). Organic Chemical Crystallography. New York: Consultants Bureau. Google Scholar
Kuckmann, T. J., Dornhaus, F., Bolte, M., Lerner, H.-W., Holthausen, M. C. & Wagner, M. (2007). Eur. J. Inorg. Chem. pp. 1989–2003. Google Scholar
Rigaku OD (2020). CrysAlis PRO, Version 1.171.41.93a (and several earlier versions for which we do not give separate references). Rigaku Oxford Diffraction (formerly Oxford Diffraction and Agilent Technologies), Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Taouss, C., Jones, P. G., Upmann, D. & Bockfeld, D. (2015). Z. Naturforsch. B, 70, 911–927. Web of Science CSD CrossRef CAS Google Scholar
Upmann, D. (2015). Phosphanchalkogenide und ihre Edelmetall-komplexe. Dissertation, Technical University of Braunschweig, Germany (ISBN: 978-3-8439-1972-2). Google Scholar
Upmann, D. & Jones, P. G. (2013). Dalton Trans. 42, 7526–7528. Web of Science CSD CrossRef CAS PubMed Google Scholar
Upmann, D., Jones, P. G., Bockfeld, D. & Târcoveanu, E. (2024). Acta Cryst. E80, 34–49. Web of Science CSD CrossRef IUCr Journals Google Scholar
Upmann, D., Koneczny, M., Rass, J. & Jones, P. G. (2019). Z. Naturforsch. B, 74, 389–404. Web of Science CSD CrossRef CAS Google Scholar
Upmann, D., Näther, C., Jess, I. & Jones, P. G. (2017). Z. Anorg. Allg. Chem. 643, 311–316. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 80| Part 4| April 2024| Pages 355-369

https://doi.org/10.1107/S2056989024002032

Open

access