Poly[dipotassium [(μ6-2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetra­yltetra­kis­(methyl­ene)]tetra­kis­(sulfanedi­yl)}tetra­acetato)­disilver(I)] 5.2-hydrate]

Pacifico, J.; Stoeckli-Evans, H.

doi:10.1107/S2414314622000773

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 2| February 2022| x220077

https://doi.org/10.1107/S2414314622000773

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Poly[dipotassium [(μ₆-2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetraacetato)disilver(I)] 5.2-hydrate]

Jessica Pacifico ^a and Helen Stoeckli-Evans ^b ^*

^aInstitute of Chemistry, University of Neuchâtel, Av. de Bellevax 51, CH-2000 Neuchâtel, Switzerland, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 13 December 2021; accepted 22 January 2022; online 1 February 2022)

The reaction of AgNO₃ with the ligand 2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetraacetic acid in the presence of a potassium acetate buffer lead to the formation of a silver(I)–potassium–organic framework, poly[dipotassium [(μ₆-2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetraacetato)disilver(I)] 5.2-hydrate], {K₂[Ag₂(C₁₆H₁₆N₂O₈S₄)]·5.2H₂O}_n, (I). The asymmetric unit is composed of half a binuclear silver complex located about a center of symmetry, a potassium cation and 2.6 disordered water molecules. The whole binuclear silver complex is generated by inversion symmetry with the pyrazine ring being located about an inversion centre. The ligand coordinates in a bis-tetradentate manner. The binuclear silver complex anions are linked via bridging Ag⋯S⋯Ag zigzag bonds, forming a network lying parallel to the bc plane. The networks are linked by O_carboxylate⋯K⁺⋯O_carboxylate bridging bonds to form a framework. The disordered water molecules are present near to the K⁺ cations.

Keywords: crystal structure; pyrazine; carboxylate; tetrakis; silver–potassium–organic framework.

CCDC reference: 2143798

Structure description

The title ligand, tetrakis-substituted pyrazine carboxylic acid, 2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetraacetic acid (H₄L1), is one of a series of tetrakis-substituted pyrazine ligands containing N_xS₄ and N₂S₄O₈ donor atoms (Pacifico, 2003 ).

H₄L1 is the tetraacetic acid analogue of 3,3′,3′′,3′′′-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetrapropionic acid (H₄L2), for which two triclinic polymorphs and two potassium–organic frameworks have been reported (Pacifico & Stoeckli-Evans, 2021b ). Reaction of H₄L1 with NiCl₂ lead to the formation of a binuclear complex, {[(H₂O)₂Ni₂(C₁₆H₂₀N₂O₈S₄)]·7(H₂O)}, whose crystal structure has been reported (Pacifico & Stoeckli-Evans, 2021b).

The reaction of H₄L1 (Pacifico & Stoeckli-Evans, 2021a) with AgNO₃ in the presence of a potassium acetate buffer resulted in deprotonation of the ligand and the formation of a heterobimetallic silver(I)–potassium–organic framework (I).

The asymmetric unit of I consists of half a binuclear silver complex, with the ligand coordinating in a bis-tetradentate manner (Fig. 1), a potassium cation and 2.6 disordered water molecules. Selected bond lengths and bond angles involving atom Ag1 are given in Table 1. The binuclear silver complex anions are linked via bridging Ag⋯S⋯Ag zigzag bonds to form a network lying parallel to the bc plane (Fig. 2). The silver ion has a sixfold AgS₃O₂N coordination sphere. The bond lengths involving Ag1 fall within the limits observed for the various type of bond when searching the Cambridge Structural Database (CSD, last update September 2021; Groom et al., 2016 ). For example, there were over 600 hits for the Ag—N_pyrazine bond length that varies from 2.02 to 2.739 Å [mean value 2.321 (89) Å, median 2.304 Å and a skew of 0.866]. In I this value is 2.550 (5) Å. For Ag—O_carboxylate there were over 2,800 hits with the bond lengths varying from 1.967 to 3.089 Å [mean value 2.377 (147) Å, median 2.352 Å and a skew value of 0.532]. In I the Ag—O_carboxylate bond lengths are almost equal; 2.470 (5) and 2.466 (6) Å. Finally for the Ag—S(CH2)₂— bond-length type there were over 1,000 hits with the bond length varying from 2.361 to 3.583 Å [mean value 2.596 (98) Å, median 2.565 Å and a skew value of 1.645]. In I the Ag—S(CH2)₂– bond lengths vary from 2.604 (2) to 2.926 (2) Å, both values involve the bridging atom S1, while distance Ag1—S2ⁱⁱ is 2.824 (2) Å (Table 1).

Table 1
Selected geometric parameters (Å, °)

Ag1—N1	2.550 (5)	K1—O1	3.289 (6)
Ag1—O1ⁱ	2.470 (5)	K1—O2	2.729 (6)
Ag1—O4ⁱⁱ	2.466 (6)	K1—O3^iv	2.724 (6)
Ag1—S1	2.926 (2)	K1—O3^v	2.751 (6)
Ag1—S1ⁱⁱⁱ	2.604 (2)	K1—O4^vi	2.608 (6)
Ag1—S2ⁱⁱ	2.824 (2)

O4ⁱⁱ—Ag1—O1ⁱ	90.01 (19)	S1ⁱⁱⁱ—Ag1—S1	87.60 (4)
O4ⁱⁱ—Ag1—N1	110.25 (18)	S2ⁱⁱ—Ag1—S1	122.15 (6)
O1ⁱ—Ag1—N1	84.78 (17)	Ag1ⁱ—S1—Ag1	129.26 (7)
O4ⁱⁱ—Ag1—S1ⁱⁱⁱ	96.08 (14)	O4^vi—K1—O3^iv	94.50 (18)
O1ⁱ—Ag1—S1ⁱⁱⁱ	108.15 (12)	O4^vi—K1—O2	89.60 (19)
N1—Ag1—S1ⁱⁱⁱ	150.87 (13)	O3^iv—K1—O2	170.9 (2)
O4ⁱⁱ—Ag1—S2ⁱⁱ	69.66 (14)	O4^vi—K1—O3^v	116.0 (2)
O1ⁱ—Ag1—S2ⁱⁱ	138.52 (12)	O3^iv—K1—O3^v	86.76 (14)
N1—Ag1—S2ⁱⁱ	70.23 (12)	O2—K1—O3^v	98.72 (18)
S1ⁱⁱⁱ—Ag1—S2ⁱⁱ	109.63 (5)	O4^vi—K1—O1	71.53 (16)
O4ⁱⁱ—Ag1—S1	165.62 (14)	O3^iv—K1—O1	146.36 (18)
O1ⁱ—Ag1—S1	75.65 (14)	O2—K1—O1	42.72 (15)
N1—Ag1—S1	70.04 (12)	O3^v—K1—O1	73.37 (15)

N1—C1—C3—S1	−61.4 (7)	S2—C7—C8—O4	1.5 (10)
N1ⁱⁱ—C2—C6—S2	−70.4 (7)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) ; (v) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the silver complex dianion of compound I, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. For clarity, the potassium cation and the disordered water molecules have been omitted. [Symmetry codes: (i) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x, −y + 1, −z + 1; (iii) −x, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Figure 2
A view along the a-axis of the network of the silver complex dianions in compound I. The silver atoms are shown as silver balls. For clarity, the potassium ions, the disordered water molecules, and the C-bound H atoms have been omitted.

The three chelate rings are far from flat, as indicated by the torsion angles given in Table 1. This is also shown by the mean planes of the chelate rings calculated using PLATON (Spek, 2020 ): ring Ag1/N1/C2/C3/S1 is twisted on bond S1—C3, ring Ag1/N1/C2ⁱⁱ/C6ⁱⁱ/S2ⁱⁱ has an envelope conformation with atom S2ⁱⁱ as the flap, and ring Agⁱⁱ/S2/C7/C8/O4 has an envelope conformation with atom Ag1ⁱⁱ as the flap [symmetry code: (ii) −x, −y + 1, −z + 1].

Selected bond lengths and bond angles involving atom K1 are also given in Table 1. The strongest K⁺⋯O_carboxylate bonds lengths vary from 2.608 (6) to 2.751 (6) Å, and there is one weak contact K1⋯O1 at 3.289 (6) Å (Fig. 3). A search of the CSD for carboxylato–potassium complexes revealed that in the potassium–organic frameworks catena-[(μ₄-3,5,6-tricarboxypyrazine-2-carboxylato)potassium] (CSD refcode UBUPAK; Masci et al., 2010 ), and catena-[(μ-6-carboxypyridine-2-carboxylato)potassium] (MUMPIW; Li et al., 2020 ), the K⁺⋯O bond lengths vary from 2.7951 (11) to 2.8668 (13) Å in UBUPAK and from 2.8197 (14) to 3.0449 (15) Å in MUMPIW. In UBUPAK the K⁺ cation has a coordination number of 8 (KO₈) and a distorted dodecahedral geometry, while in MUMPIW the K⁺ ion has a coordination number of 7 (KO₆N) and has an edge-sharing pentagonal antiprism geometry. In I, the stronger K⋯O bond lengths are shorter and, owing to the presence of the disordered water molecules, it is not clear what the K⁺ ion coordination number or geometry are.

Figure 3
A view of the environment of the potassium cation in compound I. [X(red) regions of disordered water molecules; symmetry codes: (iii) −x, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) −x + 1, −y + 1, −z + 1; (v) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vi) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .]

In the crystal of I, the networks of the binuclear silver complex anions are linked by the bridging O_carboxylate⋯K⁺⋯O_carboxylate bonds to form a framework (Fig. 4; Table 1). The disordered water molecules are present near to the K⁺ cations.

Figure 4
A view along the b-axis of the crystal packing of compound I. The silver atoms are shown as small silver balls and the potassium ions as large purple balls. The blue ellipse indicates the region occupied by the disordered water molecules. For clarity, the C-bound H atoms have been omitted.

Synthesis and crystallization

The synthesis of the ligand H₄L1 has been described (Pacifico & Stoeckli-Evans, 2021a).

Synthesis of poly{(μ-2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)] tetrakis(sulfanediyl)}tetraacetato)}-bis[silver(I)]-bis[potassium] 5.2(hydrate)} (I):

AgNO₃ (20.5 mg, 0.121 mmol, 2 eq) and H₄L1 (30 mg, 0.060 mmol, 1 eq) were mixed in 20 ml of a 1M potassium acetate buffer solution. The mixture was left at 323 K under stirring and nitrogen conditions for 1 h. The mixture was then filtered and left to evaporate in air for six weeks, yielding yellow rod-like crystals of compound I (m.p. 553 K decomposition).

Analysis for C₁₆H₁₆Ag₂N₂O₈S₄, K₂, 5.2(H₂O), M_w = 880.175 g mol⁻¹: Calculated (%): C 21.88, H 2.99, N 3.18. Found (%): C 23.03, H 2.91, N 3.03. The small deviation is probably due to the loss of water molecules of crystallization.

ESI–MS: unstable under mass spectroscopy experimental conditions.

IR (KBr disc, cm⁻¹) ν: 3401(s), 2938(m), 1599(s), 1385(s), 1223(m).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The occupancy factors for the disordered water molecules were initially freely refined and then fixed at rounded values; the final total is 5.2(H₂O). It was not possible to locate the H atoms of the disordered water molecules of crystallization. The residual electron density peaks of 1.14 and −1.10 eÅ³ are at distances of 0.96 and 0.91 Å, respectively, from atom Ag1.

Table 2
Experimental details

Crystal data
Chemical formula	K₂[Ag₂(C₁₆H₁₆N₂O₈S₄)]5.2H₂O
M_r	880.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	13.386 (3), 6.0085 (7), 17.843 (3)
β (°)	108.657 (15)
V (Å³)	1359.7 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.12
Crystal size (mm)	0.24 × 0.13 × 0.05

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Multi-scan (MULABS; Spek, 2020)
T_min, T_max	0.611, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9305, 2316, 2088
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.591

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.114, 1.17
No. of reflections	2316
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −1.10
Computer programs: X-AREA (Stoe & Cie, 2002 ), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008 ), PLATON (Spek, 2020) and Mercury (Macrae et al., 2020 ), SHELXL2018/3 (Sheldrick, 2015 ), PLATON (Spek, 2020) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2143798

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314622000773/im4015sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622000773/im4015Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

Poly[dipotassium [(µ₆-2,2',2'',2'''-{[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetraacetato)disilver(I)] 5.2-hydrate] top

Crystal data top

K₂[Ag₂(C₁₆H₁₆N₂O₈S₄)]5.2H₂O	F(000) = 852
M_r = 880.17	D_x = 2.097 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.386 (3) Å	Cell parameters from 17882 reflections
b = 6.0085 (7) Å	θ = 1.6–24.9°
c = 17.843 (3) Å	µ = 2.12 mm⁻¹
β = 108.657 (15)°	T = 153 K
V = 1359.7 (4) Å³	Rod, yellow
Z = 2	0.24 × 0.13 × 0.05 mm

Data collection top

Stoe IPDS 2 diffractometer	2316 independent reflections
Radiation source: fine-focus sealed tube	2088 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.043
φ + ω scans	θ_max = 24.8°, θ_min = 2.4°
Absorption correction: multi-scan (MULABS; Spek, 2020)	h = −15→15
T_min = 0.611, T_max = 1.000	k = −7→6
9305 measured reflections	l = −20→21

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0335P)² + 8.3123P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
2316 reflections	Δρ_max = 1.14 e Å⁻³
218 parameters	Δρ_min = −1.10 e Å⁻³
0 restraints	Extinction correction: (SHELXL2018/3; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0058 (8)

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.

Refinement. The C-bound H atoms were included in calculated positions and treated as riding on their parent C atom: C—H = 0.99 Å with U_iso(H) = 1.2U_eq(C).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ag1	−0.11736 (5)	0.22235 (9)	0.29645 (3)	0.0422 (2)
K1	0.42397 (15)	−0.0830 (3)	0.31383 (13)	0.0662 (6)
S1	0.07736 (14)	0.4594 (3)	0.30640 (9)	0.0383 (4)
S2	0.13892 (15)	1.0313 (3)	0.57635 (11)	0.0456 (5)
O1	0.1777 (5)	0.0832 (8)	0.2686 (3)	0.0534 (13)
O2	0.2813 (5)	−0.0081 (9)	0.3913 (3)	0.0602 (15)
O3	0.4123 (4)	1.1764 (10)	0.7406 (4)	0.0625 (15)
O4	0.3022 (5)	0.8947 (10)	0.7311 (3)	0.0617 (15)
N1	−0.0564 (4)	0.4506 (9)	0.4235 (3)	0.0363 (13)
C1	0.0288 (5)	0.5773 (10)	0.4399 (3)	0.0335 (14)
C2	0.0881 (5)	0.6285 (10)	0.5180 (4)	0.0367 (15)
C3	0.0533 (6)	0.6731 (11)	0.3695 (4)	0.0392 (15)
H3A	0.116280	0.769845	0.388415	0.047*
H3B	−0.006596	0.766385	0.338485	0.047*
C4	0.1990 (6)	0.3419 (12)	0.3732 (4)	0.0486 (18)
H4A	0.258373	0.444967	0.377860	0.058*
H4B	0.192240	0.321755	0.426414	0.058*
C5	0.2207 (6)	0.1200 (12)	0.3415 (5)	0.0478 (18)
C6	0.1824 (6)	0.7758 (11)	0.5427 (4)	0.0397 (15)
H6A	0.208510	0.805366	0.497629	0.048*
H6B	0.239747	0.706121	0.585903	0.048*
C7	0.2611 (6)	1.1711 (12)	0.6282 (5)	0.0508 (18)
H7A	0.303971	1.179423	0.592207	0.061*
H7B	0.244080	1.325716	0.638995	0.061*
C8	0.3293 (6)	1.0693 (13)	0.7059 (5)	0.052 (2)
O1W	0.479 (2)	0.483 (5)	0.3773 (16)	0.072 (7)	0.3
O2W	0.4522 (18)	0.660 (4)	0.0890 (13)	0.071 (6)	0.3
O3W	0.4365 (15)	0.538 (4)	0.0344 (9)	0.123 (7)	0.5
O4W	0.4421 (18)	0.285 (3)	0.0195 (13)	0.105 (7)	0.4
O5W	0.4629 (16)	0.844 (4)	0.0802 (13)	0.057 (5)	0.3
O6W	0.451 (3)	0.951 (7)	0.115 (2)	0.198 (17)	0.5
O7W	0.556 (4)	0.047 (9)	0.009 (3)	0.23 (3)	0.3

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0620 (4)	0.0363 (3)	0.0386 (3)	−0.0055 (2)	0.0305 (3)	−0.0060 (2)
K1	0.0607 (11)	0.0602 (12)	0.0891 (14)	0.0039 (9)	0.0400 (10)	0.0048 (10)
S1	0.0579 (11)	0.0325 (8)	0.0332 (8)	−0.0005 (7)	0.0266 (8)	−0.0006 (7)
S2	0.0552 (11)	0.0347 (9)	0.0531 (11)	−0.0041 (8)	0.0261 (9)	−0.0089 (8)
O1	0.082 (4)	0.037 (3)	0.050 (3)	0.003 (3)	0.034 (3)	−0.002 (2)
O2	0.069 (4)	0.053 (3)	0.067 (3)	0.011 (3)	0.033 (3)	0.015 (3)
O3	0.059 (4)	0.059 (4)	0.075 (4)	−0.012 (3)	0.030 (3)	−0.018 (3)
O4	0.070 (4)	0.057 (3)	0.064 (4)	−0.007 (3)	0.030 (3)	0.005 (3)
N1	0.057 (4)	0.031 (3)	0.028 (3)	−0.002 (3)	0.024 (2)	−0.001 (2)
C1	0.050 (4)	0.028 (3)	0.030 (3)	0.000 (3)	0.025 (3)	−0.004 (3)
C2	0.055 (4)	0.027 (3)	0.039 (3)	0.001 (3)	0.031 (3)	−0.001 (3)
C3	0.064 (4)	0.032 (3)	0.030 (3)	−0.003 (3)	0.028 (3)	−0.001 (3)
C4	0.063 (5)	0.045 (4)	0.045 (4)	0.002 (4)	0.028 (4)	0.004 (3)
C5	0.059 (5)	0.034 (4)	0.065 (5)	0.003 (3)	0.040 (4)	0.010 (4)
C6	0.059 (4)	0.032 (3)	0.039 (3)	−0.005 (3)	0.030 (3)	−0.007 (3)
C7	0.065 (5)	0.036 (4)	0.058 (5)	−0.010 (3)	0.030 (4)	−0.005 (3)
C8	0.057 (5)	0.045 (4)	0.069 (5)	−0.013 (4)	0.039 (4)	−0.019 (4)
O1W	0.081 (17)	0.052 (12)	0.066 (14)	0.000 (13)	0.000 (13)	0.017 (11)
O2W	0.084 (15)	0.055 (14)	0.060 (13)	−0.001 (11)	0.003 (11)	−0.004 (11)
O3W	0.123 (15)	0.18 (2)	0.065 (10)	0.040 (14)	0.024 (9)	−0.005 (12)
O4W	0.113 (17)	0.077 (13)	0.111 (16)	0.001 (12)	0.016 (13)	0.011 (12)
O5W	0.044 (11)	0.043 (12)	0.062 (13)	0.006 (9)	−0.015 (9)	0.000 (10)
O6W	0.22 (4)	0.16 (3)	0.21 (3)	0.05 (3)	0.06 (3)	−0.01 (3)
O7W	0.21 (5)	0.21 (5)	0.16 (4)	0.08 (5)	−0.09 (4)	−0.02 (4)

Geometric parameters (Å, º) top

Ag1—N1	2.550 (5)	O4—C8	1.241 (9)
Ag1—O1ⁱ	2.470 (5)	N1—C1	1.324 (8)
Ag1—O4ⁱⁱ	2.466 (6)	N1—C2ⁱⁱ	1.334 (8)
Ag1—S1	2.926 (2)	C1—C2	1.399 (9)
Ag1—S1ⁱⁱⁱ	2.604 (2)	C1—C3	1.509 (8)
Ag1—S2ⁱⁱ	2.824 (2)	C2—C6	1.489 (10)
Ag1—K1ⁱ	4.113 (2)	C3—H3A	0.9900
K1—O2W^iv	2.46 (2)	C3—H3B	0.9900
K1—O1	3.289 (6)	C4—C5	1.512 (10)
K1—O2	2.729 (6)	C4—H4A	0.9900
K1—O3^v	2.724 (6)	C4—H4B	0.9900
K1—O3^vi	2.751 (6)	C6—H6A	0.9900
K1—O4^vii	2.608 (6)	C6—H6B	0.9900
K1—O1W^viii	2.84 (3)	C7—C8	1.523 (12)
K1—O3W^iv	2.848 (17)	C7—H7A	0.9900
K1—O4W^iv	3.05 (2)	C7—H7B	0.9900
K1—C5	3.162 (7)	O1W—O6W^iv	0.93 (4)
K1—O5W^iv	3.26 (2)	O1W—O5W^iv	1.22 (4)
K1—O6W^ix	3.30 (4)	O2W—O5W	1.13 (3)
S1—C3	1.803 (6)	O2W—O3W	1.19 (3)
S1—C4	1.824 (8)	O2W—O6W	1.81 (4)
S2—C7	1.808 (8)	O3W—O4W	1.55 (3)
S2—C6	1.811 (7)	O5W—O6W	0.94 (4)
O1—C5	1.263 (9)	O5W—O7W^x	1.66 (6)
O2—C5	1.256 (9)	O7W—O7W^xi	1.53 (11)
O3—C8	1.262 (9)

O4ⁱⁱ—Ag1—O1ⁱ	90.01 (19)	C7—S2—C6	103.3 (4)
O4ⁱⁱ—Ag1—N1	110.25 (18)	C7—S2—Ag1ⁱⁱ	98.5 (3)
O1ⁱ—Ag1—N1	84.78 (17)	C6—S2—Ag1ⁱⁱ	86.3 (2)
O4ⁱⁱ—Ag1—S1ⁱⁱⁱ	96.08 (14)	C5—O1—Ag1ⁱⁱⁱ	127.6 (5)
O1ⁱ—Ag1—S1ⁱⁱⁱ	108.15 (12)	C5—O1—K1	73.1 (4)
N1—Ag1—S1ⁱⁱⁱ	150.87 (13)	Ag1ⁱⁱⁱ—O1—K1	90.02 (15)
O4ⁱⁱ—Ag1—S2ⁱⁱ	69.66 (14)	C5—O2—K1	98.2 (4)
O1ⁱ—Ag1—S2ⁱⁱ	138.52 (12)	C8—O3—K1^v	113.7 (5)
N1—Ag1—S2ⁱⁱ	70.23 (12)	C8—O3—K1^xii	126.4 (5)
S1ⁱⁱⁱ—Ag1—S2ⁱⁱ	109.63 (5)	K1^v—O3—K1^xii	115.0 (2)
O4ⁱⁱ—Ag1—S1	165.62 (14)	C8—O4—Ag1ⁱⁱ	124.0 (6)
O1ⁱ—Ag1—S1	75.65 (14)	C8—O4—K1^xiii	127.6 (5)
N1—Ag1—S1	70.04 (12)	Ag1ⁱⁱ—O4—K1^xiii	108.3 (2)
S1ⁱⁱⁱ—Ag1—S1	87.60 (4)	C1—N1—C2ⁱⁱ	119.9 (6)
S2ⁱⁱ—Ag1—S1	122.15 (6)	C1—N1—Ag1	120.9 (4)
O4ⁱⁱ—Ag1—K1ⁱ	37.02 (14)	C2ⁱⁱ—N1—Ag1	114.4 (4)
O1ⁱ—Ag1—K1ⁱ	53.08 (13)	N1—C1—C2	121.4 (5)
N1—Ag1—K1ⁱ	105.00 (13)	N1—C1—C3	115.9 (6)
S1ⁱⁱⁱ—Ag1—K1ⁱ	103.54 (5)	C2—C1—C3	122.7 (6)
S2ⁱⁱ—Ag1—K1ⁱ	101.25 (5)	N1ⁱⁱ—C2—C1	118.7 (6)
S1—Ag1—K1ⁱ	128.60 (5)	N1ⁱⁱ—C2—C6	115.6 (6)
Ag1ⁱ—S1—Ag1	129.26 (7)	C1—C2—C6	125.6 (5)
O2W^iv—K1—O4^vii	169.6 (6)	C1—C3—S1	112.2 (4)
O2W^iv—K1—O3^v	86.3 (6)	C1—C3—H3A	109.2
O4^vii—K1—O3^v	94.50 (18)	S1—C3—H3A	109.2
O2W^iv—K1—O2	88.2 (6)	C1—C3—H3B	109.2
O4^vii—K1—O2	89.60 (19)	S1—C3—H3B	109.2
O3^v—K1—O2	170.9 (2)	H3A—C3—H3B	107.9
O2W^iv—K1—O3^vi	74.4 (6)	C5—C4—S1	109.6 (5)
O4^vii—K1—O3^vi	116.0 (2)	C5—C4—H4A	109.7
O3^v—K1—O3^vi	86.76 (14)	S1—C4—H4A	109.7
O2—K1—O3^vi	98.72 (18)	C5—C4—H4B	109.7
O2W^iv—K1—O1W^viii	103.5 (8)	S1—C4—H4B	109.7
O4^vii—K1—O1W^viii	66.6 (6)	H4A—C4—H4B	108.2
O3^v—K1—O1W^viii	79.4 (6)	O2—C5—O1	126.8 (7)
O2—K1—O1W^viii	94.8 (6)	O2—C5—C4	115.7 (7)
O3^vi—K1—O1W^viii	166.2 (6)	O1—C5—C4	117.4 (7)
O2W^iv—K1—O3W^iv	24.4 (6)	O2—C5—K1	58.7 (4)
O4^vii—K1—O3W^iv	145.2 (5)	O1—C5—K1	84.4 (4)
O3^v—K1—O3W^iv	91.9 (4)	C4—C5—K1	132.6 (5)
O2—K1—O3W^iv	80.2 (4)	C2—C6—S2	105.7 (5)
O3^vi—K1—O3W^iv	98.4 (5)	C2—C6—H6A	110.6
O1W^viii—K1—O3W^iv	81.2 (8)	S2—C6—H6A	110.6
O2W^iv—K1—O4W^iv	54.0 (7)	C2—C6—H6B	110.6
O4^vii—K1—O4W^iv	115.6 (4)	S2—C6—H6B	110.6
O3^v—K1—O4W^iv	90.3 (5)	H6A—C6—H6B	108.7
O2—K1—O4W^iv	80.6 (5)	C8—C7—S2	117.4 (5)
O3^vi—K1—O4W^iv	128.4 (4)	C8—C7—H7A	108.0
O1W^viii—K1—O4W^iv	51.4 (7)	S2—C7—H7A	108.0
O3W^iv—K1—O4W^iv	30.2 (6)	C8—C7—H7B	108.0
O2W^iv—K1—C5	94.6 (6)	S2—C7—H7B	108.0
O4^vii—K1—C5	87.3 (2)	H7A—C7—H7B	107.2
O3^v—K1—C5	165.0 (2)	O4—C8—O3	124.6 (9)
O2—K1—C5	23.16 (17)	O4—C8—C7	120.7 (7)
O3^vi—K1—C5	79.11 (18)	O3—C8—C7	114.8 (7)
O1W^viii—K1—C5	114.7 (6)	O4—C8—K1^v	117.4 (5)
O3W^iv—K1—C5	95.1 (5)	O3—C8—K1^v	46.6 (4)
O4W^iv—K1—C5	102.4 (5)	C7—C8—K1^v	102.3 (4)
O2W^iv—K1—O5W^iv	16.3 (6)	O4—C8—K1^xiii	36.1 (4)
O4^vii—K1—O5W^iv	169.7 (4)	O3—C8—K1^xiii	92.8 (5)
O3^v—K1—O5W^iv	95.3 (4)	C7—C8—K1^xiii	147.2 (5)
O2—K1—O5W^iv	81.2 (5)	K1^v—C8—K1^xiii	83.44 (19)
O3^vi—K1—O5W^iv	61.4 (4)	O6W^iv—O1W—O5W^iv	50 (3)
O1W^viii—K1—O5W^iv	118.5 (7)	O6W^iv—O1W—K1^xiv	112 (4)
O3W^iv—K1—O5W^iv	37.5 (6)	O5W^iv—O1W—K1^xiv	155 (2)
O4W^iv—K1—O5W^iv	67.6 (5)	O5W—O2W—O3W	119 (3)
C5—K1—O5W^iv	82.5 (4)	O5W—O2W—O6W	27 (2)
O2W^iv—K1—O1	112.9 (6)	O3W—O2W—O6W	143 (2)
O4^vii—K1—O1	71.53 (16)	O5W—O2W—K1^xv	126.2 (17)
O3^v—K1—O1	146.36 (18)	O3W—O2W—K1^xv	96.4 (16)
O2—K1—O1	42.72 (15)	O6W—O2W—K1^xv	117.0 (16)
O3^vi—K1—O1	73.37 (15)	O2W—O3W—O4W	138 (2)
O1W^viii—K1—O1	119.2 (6)	O2W—O3W—K1^xv	59.1 (13)
O3W^iv—K1—O1	117.2 (5)	O4W—O3W—K1^xv	82.0 (11)
O4W^iv—K1—O1	123.3 (5)	O3W—O4W—K1^xv	67.8 (10)
C5—K1—O1	22.47 (17)	O6W—O5W—O2W	121 (4)
O5W^iv—K1—O1	98.4 (4)	O6W—O5W—O1W^xv	49 (3)
O2W^iv—K1—O6W^ix	95.0 (8)	O2W—O5W—O1W^xv	131 (2)
O4^vii—K1—O6W^ix	76.0 (7)	O6W—O5W—O7W^x	111 (4)
O3^v—K1—O6W^ix	66.1 (7)	O2W—O5W—O7W^x	122 (3)
O2—K1—O6W^ix	107.3 (7)	O1W^xv—O5W—O7W^x	101 (3)
O3^vi—K1—O6W^ix	151.6 (7)	O6W—O5W—K1^xv	107 (3)
O1W^viii—K1—O6W^ix	15.1 (8)	O2W—O5W—K1^xv	37.5 (13)
O3W^iv—K1—O6W^ix	75.6 (9)	O1W^xv—O5W—K1^xv	95.3 (16)
O4W^iv—K1—O6W^ix	48.4 (8)	O7W^x—O5W—K1^xv	140 (2)
C5—K1—O6W^ix	128.6 (7)	O1W^xv—O6W—O5W	82 (4)
O5W^iv—K1—O6W^ix	111.1 (7)	O1W^xv—O6W—O2W	98 (4)
O1—K1—O6W^ix	134.3 (7)	O5W—O6W—O2W	32 (2)
C3—S1—C4	99.7 (3)	O1W^xv—O6W—K1^xvi	53 (3)
C3—S1—Ag1ⁱ	97.3 (2)	O5W—O6W—K1^xvi	131 (4)
C4—S1—Ag1ⁱ	110.7 (2)	O2W—O6W—K1^xvi	151 (2)
C3—S1—Ag1	92.9 (2)	O7W^xi—O7W—O5W^x	96 (3)
C4—S1—Ag1	116.3 (3)

C2ⁱⁱ—N1—C1—C2	0.9 (10)	K1^xii—O3—C8—C7	70.3 (8)
Ag1—N1—C1—C2	−153.3 (5)	K1^xii—O3—C8—K1^v	153.8 (8)
C2ⁱⁱ—N1—C1—C3	−175.4 (6)	K1^v—O3—C8—K1^xiii	78.2 (4)
Ag1—N1—C1—C3	30.4 (7)	K1^xii—O3—C8—K1^xiii	−128.0 (4)
N1—C1—C2—N1ⁱⁱ	−0.9 (10)	S2—C7—C8—O4	1.5 (10)
C3—C1—C2—N1ⁱⁱ	175.2 (6)	S2—C7—C8—O3	−178.3 (5)
N1—C1—C2—C6	−177.5 (6)	S2—C7—C8—K1^v	134.0 (4)
C3—C1—C2—C6	−1.4 (10)	S2—C7—C8—K1^xiii	37.0 (11)
N1—C1—C3—S1	−61.4 (7)	O5W—O2W—O3W—O4W	162 (3)
C2—C1—C3—S1	122.3 (6)	O6W—O2W—O3W—O4W	179 (3)
C4—S1—C3—C1	−66.2 (6)	K1^xv—O2W—O3W—O4W	24 (3)
Ag1ⁱ—S1—C3—C1	−178.7 (5)	O5W—O2W—O3W—K1^xv	138 (3)
Ag1—S1—C3—C1	51.1 (5)	O6W—O2W—O3W—K1^xv	155 (4)
C3—S1—C4—C5	165.4 (5)	O2W—O3W—O4W—K1^xv	−21 (3)
Ag1ⁱ—S1—C4—C5	−93.0 (5)	O3W—O2W—O5W—O6W	157 (4)
Ag1—S1—C4—C5	67.3 (5)	K1^xv—O2W—O5W—O6W	−78 (4)
K1—O2—C5—O1	53.3 (8)	O3W—O2W—O5W—O1W^xv	−143 (3)
K1—O2—C5—C4	−125.8 (5)	O6W—O2W—O5W—O1W^xv	60 (4)
Ag1ⁱⁱⁱ—O1—C5—O2	33.0 (11)	K1^xv—O2W—O5W—O1W^xv	−18 (5)
K1—O1—C5—O2	−43.5 (7)	O3W—O2W—O5W—O7W^x	7 (4)
Ag1ⁱⁱⁱ—O1—C5—C4	−147.9 (5)	O6W—O2W—O5W—O7W^x	−150 (6)
K1—O1—C5—C4	135.6 (6)	K1^xv—O2W—O5W—O7W^x	132 (3)
Ag1ⁱⁱⁱ—O1—C5—K1	76.5 (5)	O3W—O2W—O5W—K1^xv	−125 (4)
S1—C4—C5—O2	−159.1 (5)	O6W—O2W—O5W—K1^xv	78 (4)
S1—C4—C5—O1	21.6 (8)	O2W—O5W—O6W—O1W^xv	120 (4)
S1—C4—C5—K1	130.8 (5)	O7W^x—O5W—O6W—O1W^xv	−87 (4)
N1ⁱⁱ—C2—C6—S2	−70.4 (7)	K1^xv—O5W—O6W—O1W^xv	81 (4)
C1—C2—C6—S2	106.2 (6)	O1W^xv—O5W—O6W—O2W	−120 (4)
C7—S2—C6—C2	165.8 (5)	O7W^x—O5W—O6W—O2W	153 (5)
Ag1ⁱⁱ—S2—C6—C2	68.0 (4)	K1^xv—O5W—O6W—O2W	−39 (2)
C6—S2—C7—C8	−69.2 (6)	O2W—O5W—O6W—K1^xvi	142 (3)
Ag1ⁱⁱ—S2—C7—C8	18.9 (6)	O1W^xv—O5W—O6W—K1^xvi	22 (2)
Ag1ⁱⁱ—O4—C8—O3	150.8 (6)	O7W^x—O5W—O6W—K1^xvi	−65 (5)
K1^xiii—O4—C8—O3	−32.5 (10)	K1^xv—O5W—O6W—K1^xvi	103 (4)
Ag1ⁱⁱ—O4—C8—C7	−29.0 (9)	O5W—O2W—O6W—O1W^xv	−60 (5)
K1^xiii—O4—C8—C7	147.7 (6)	O3W—O2W—O6W—O1W^xv	−94 (5)
Ag1ⁱⁱ—O4—C8—K1^v	−154.8 (3)	K1^xv—O2W—O6W—O1W^xv	58 (5)
K1^xiii—O4—C8—K1^v	21.9 (8)	O3W—O2W—O6W—O5W	−34 (6)
Ag1ⁱⁱ—O4—C8—K1^xiii	−176.7 (9)	K1^xv—O2W—O6W—O5W	118 (4)
K1^v—O3—C8—O4	96.7 (8)	O5W—O2W—O6W—K1^xvi	−72 (5)
K1^xii—O3—C8—O4	−109.5 (8)	O3W—O2W—O6W—K1^xvi	−106 (5)
K1^v—O3—C8—C7	−83.5 (7)	K1^xv—O2W—O6W—K1^xvi	45 (5)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) x, −y+3/2, z−1/2; (vii) x, −y+1/2, z−1/2; (viii) x, y−1, z; (ix) −x+1, y−3/2, −z+1/2; (x) −x+1, −y+1, −z; (xi) −x+1, −y, −z; (xii) x, −y+3/2, z+1/2; (xiii) x, −y+1/2, z+1/2; (xiv) x, y+1, z; (xv) −x+1, y+1/2, −z+1/2; (xvi) −x+1, y+3/2, −z+1/2.

Acknowledgements

HSE is grateful to the University of Neuchâtel for their support over the years.

Funding information

Funding for this research was provided by: Swiss National Science Foundation; University of Neuchatel.

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