Poly[[μ4-3,4,8,10,11,13-hexa­hydro-1H,6H-bis­([1,4]di­thio­cino)[6,7-b:6′,7′-e]pyrazine]di-μ-iodido-dicopper(I)]: a two-dimensional copper(I) coordination polymer

Assoumatine, T.; Stoeckli-Evans, H.

doi:10.1107/S2414314620004678

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 4| April 2020| x200467

https://doi.org/10.1107/S2414314620004678

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Poly[[μ₄-3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine]di-μ-iodido-dicopper(I)]: a two-dimensional copper(I) coordination polymer

Tokouré Assoumatine ^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 M. Weil, Vienna University of Technology, Austria (Received 30 March 2020; accepted 3 April 2020; online 7 April 2020)

The reaction of ligand 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine (L) with CuI led to the formation of a two-dimensional coordination polymer, incorporating a [Cu₂I₂] motif. These units are linked via the four S atoms of the ligand to form the title two-dimensional coordination polymer, poly[[μ₄-3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine]di-μ-iodido-dicopper(I)], [Cu₂I₂(C₁₂H₁₆N₂S₄)]_n, (I). The asymmetric unit is composed of a ligand molecule, two copper(I) atoms and two I⁻ ions. Both copper(I) atoms are fourfold S₂I₂ coordinate with almost regular trigonal-pyramidal environments. In the crystal, the layers, lying parallel to (102), are linked by C—H⋯I hydrogen bonds, forming a supramolecular framework.

Keywords: crystal structure; copper(I) iodide; pyrazine; pyrazinethiophane; two-dimensional coordination polymer; supramolecular framework.

CCDC reference: 1994655

Structure description

We have recently shown that the reaction of the title pyrazinethiophane ligand, 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine (L), with silver(I) nitrate leads to the formation of a two-dimensional coordination polymer, with the silver(I) atom coordinated by three S atoms of the ligand and an O atom of the nitrate anion (Assoumatine & Stoeckli-Evans, 2020 ). A series of pyrazinethiophanes, including ligand L, has been synthesized to study their coordination chemistry with transition metals (Assoumatine, 1999 ).

The reaction of L with CuI leads to the formation of a two-dimensional coordination polymer, poly[[μ₄-3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine]di-μ-iodido-dicopper(I)], incorporating a [Cu₂I₂] motif (Fig. 1). The asymmetric unit is composed of a ligand molecule, two copper(I) atoms and two I⁻ ions. The layers lie parallel to (102), and there are C—H⋯S and C—H⋯I intralayer hydrogen bonds present (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯S4	0.97	2.80	3.409 (6)	122
C9—H9A⋯I1	0.97	2.99	3.771 (6)	138
C6—H6A⋯I1ⁱ	0.97	2.89	3.702 (6)	142
Symmetry code: (i) -x+1, -y, -z.

Figure 1
A view of the asymmetric unit of complex I, expanded to show the coordination environments of the two copper(I) atoms. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) –x, –y, –z; (ii) –x, –y + 1, –z; (iii) x – 1, –y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iv) x + 1, –y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ].

Selected bond lengths and bond angles involving the copper(I) atoms in I are given in Table 2. In I, both copper(I) atoms are considered to be fourfold S₂I₂ coordinate. The fourfold index parameter τ₄ is 0.89 for atom Cu1 and 0.84 for atom Cu2 (τ₄ = 1 for a perfect tetrahedral environment, 0 for a perfect square-planar environment and 0.85 for a perfect trigonal–pyramidal environment; Yang et al., 2007 ). Hence, both metal atoms have similar trigonal–pyramidal coordination environments. The distance Cu1⋯Cu2 is 2.7759 (11) Å. The Cu—S and Cu—I bond lengths involving atom Cu1 are noticeably different to those involving atom Cu2 (Table 2). Bond lengths Cu1—S1 and Cu1—S4 [2.3955 (16) and 2.3187 (16) Å, respectively] are longer than bond lengths Cu2—S2 and Cu2—S3 [2.3030 (16) and 2.3039 (16) Å, respectively]. In contrast, it can be seen that bond lengths Cu1—I1 and Cu1—I2 [2.6190 (10) and 2.5915 (10) Å, respectively] are shorter than bond lengths Cu2—I1 and Cu2—I2 [2.7117 (10) and 2.6460 (9) Å, respectively]. As in the silver nitrate complex of L mentioned above, the pyrazine N atoms are not involved in coordination to the copper(I) atoms.

Table 2
Selected geometric parameters (Å, °)

Cu1—S1	2.3955 (16)	Cu2—S2	2.3030 (16)
Cu1—S4	2.3187 (16)	Cu2—S3	2.3039 (16)
Cu1—I1	2.6190 (9)	Cu2—I1	2.7117 (10)
Cu1—I2	2.5915 (10)	Cu2—I2	2.6460 (9)
Cu1—Cu2	2.7759 (11)

S4—Cu1—S1	101.91 (6)	S2—Cu2—S3	129.92 (6)
S4—Cu1—I2	118.12 (5)	S2—Cu2—I2	108.76 (5)
S1—Cu1—I2	104.83 (5)	S3—Cu2—I2	106.63 (5)
S4—Cu1—I1	102.76 (5)	S2—Cu2—I1	90.49 (5)
S1—Cu1—I1	111.80 (5)	S3—Cu2—I1	107.95 (5)
I2—Cu1—I1	116.62 (3)	I2—Cu2—I1	111.68 (3)

In the complex, the ligand is step-shaped, as in the solid-state structure of the ligand itself (Assoumatine & Stoeckli-Evans, 2020). The conformation of the eight-membered rings fits best to the definition of a twist-boat-chair (Evans & Boeyens, 1988 ; Spek, 2020 ), with a pseudo-twofold rotation axis bisecting bonds C1—C2 and C6—C7 in one ring and bonds C3—C4 and C10—C11 in the second ring.

A search of the Cambridge Structural Database (CSD; Version 5.41, last update November 2019; Groom et al., 2016 ) for the benzene analogue of L, or complexes of this analogue, gave no hits. A search for the S₂CuI₂CuS₂ motif gave 34 hits for 33 structures (see file S1 in the supporting information). The Cu⋯Cu distances of the majority of these compounds vary from ca 2.580 to 3.087 Å (largest observed distance is 3.706 Å). For the majority of the compounds, the Cu—S bond lengths vary from 2.246 to 2.374 Å (largest observed distance is 2.531 Å), while the Cu—I bond lengths vary from 2.498 to 2.762 Å (largest observed bond length is 3.086 Å). It is evident from Table 2 that the bond lengths observed in complex I fall within these limits.

In the crystal of I, the layers lying parallel to plane (102) (Fig. 2) are linked by C—H⋯I hydrogen bonds forming a supramolecular framework (Fig. 3 and Table 1). There are no other significant intermolecular interactions present in the crystal.

Figure 2
A view, almost normal to plane (102), of the crystal packing of complex I.

Figure 3
A view along the b axis of the crystal packing of complex I. Hydrogen bonds are shown as dashed lines (Table 1

). For clarity, only the hydrogen atoms involved in these interactions have been included.

Synthesis and crystallization

The synthesis and crystal structure of the title ligand, 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine (L), have been reported (Assoumatine & Stoeckli-Evans, 2020).

Synthesis of complex I: A solution of L (20 mg, 0.06 mmol) in CHCl₃ (10 ml) was introduced into a 16 mm diameter glass tube and layered with MeCN (2 ml) as a buffer zone. Then a solution of CuI (11 mg, 0.06 mmol) in MeCN (5 ml) was added very gently to avoid possible mixing. The glass tube was sealed under an atmosphere of nitrogen and left in the dark at room temperature for at least 3 weeks, whereupon pale-yellow block-like crystals of complex I were isolated at the interface between the two solutions. Analysis for C₁₂H₁₆N₂S₄Cu₂I₂ (M_r = 697.46); calculated (%): C 20.66, H 2.32, N 4.02; found (%): C 20.90, H 2.31, N 3.93. The IR spectrum for I is shown in Fig. S1 of the supporting information.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The data were collected with a four-circle diffractometer at RT and only one equivalent of data were measured, hence R_int = 0.0. No suitable ψ scans could be found so the crystal was equated to a sphere and the ABSSphere absorption correction was applied (PLATON; Spek, 2020).

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₂I₂(C₁₂H₁₆N₂S₄)]
M_r	697.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.7612 (8), 13.1852 (13), 16.4458 (19)
β (°)	94.400 (9)
V (Å³)	1894.2 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.94
Crystal size (mm)	0.42 × 0.25 × 0.23

Data collection
Diffractometer	STOE–Siemens AED2, 4-circle
Absorption correction	For a sphere (ABSSphere; Spek, 2020)
T_min, T_max	0.281, 0.295
No. of measured, independent and observed [I > 2σ(I)] reflections	3481, 3481, 3032
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.084, 1.16
No. of reflections	3481
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.69
Computer programs: STADI4 and X-RED (Stoe & Cie, 1998 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 ), PLATON (Spek, 2020), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1994655

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314620004678/wm4128sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620004678/wm4128Isup2.hkl

Scheme for CSD search. DOI: https://doi.org/10.1107/S2414314620004678/wm4128sup3.tif

CSD Search. DOI: https://doi.org/10.1107/S2414314620004678/wm4128sup4.pdf

IR spectrum for complex I. DOI: https://doi.org/10.1107/S2414314620004678/wm4128sup5.tif

checkCIF report

Computing details top

Data collection: STADI4 (Stoe & Cie, 1998); cell refinement: STADI4 (Stoe & Cie, 1998); data reduction: X-RED (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

Poly[[µ₄-3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6',7'-e]pyrazine]di-µ-iodido-dicopper(I)] top

Crystal data top

[Cu₂I₂(C₁₂H₁₆N₂S₄)]	F(000) = 1320
M_r = 697.39	D_x = 2.445 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.7612 (8) Å	Cell parameters from 25 reflections
b = 13.1852 (13) Å	θ = 12.6–18.8°
c = 16.4458 (19) Å	µ = 5.94 mm⁻¹
β = 94.400 (9)°	T = 293 K
V = 1894.2 (3) Å³	Block, yellow
Z = 4	0.42 × 0.25 × 0.23 mm

Data collection top

STOE–Siemens AED2, 4-circle diffractometer	3032 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.0000
Plane graphite monochromator	θ_max = 25.5°, θ_min = 2.5°
ω/\2q scans	h = −10→10
Absorption correction: for a sphere (ABSSphere; Spek, 2020)	k = 0→15
T_min = 0.281, T_max = 0.295	l = 0→19
3481 measured reflections	3 standard reflections every 60 min
3481 independent reflections	intensity decay: 2.5%

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0312P)² + 6.7359P] where P = (F_o² + 2F_c²)/3
3481 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

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
Cu1	0.25837 (9)	0.05716 (6)	−0.12025 (5)	0.03502 (19)
Cu2	0.12846 (9)	0.24930 (6)	−0.12571 (5)	0.03483 (19)
I1	0.29009 (5)	0.17469 (3)	0.00833 (2)	0.03617 (12)
I2	0.04113 (5)	0.10364 (3)	−0.22976 (3)	0.03942 (13)
S1	0.48581 (17)	0.05318 (11)	−0.19226 (9)	0.0303 (3)
S2	0.34612 (17)	0.32435 (11)	−0.16802 (9)	0.0279 (3)
S3	−0.09175 (18)	0.32212 (11)	−0.08436 (10)	0.0321 (3)
S4	0.25769 (18)	−0.10386 (11)	−0.06361 (10)	0.0312 (3)
N1	0.3515 (6)	−0.3124 (4)	−0.1619 (3)	0.0293 (11)
N2	−0.2450 (5)	0.4626 (3)	0.0627 (3)	0.0269 (10)
C1	0.5775 (7)	0.0972 (4)	−0.3460 (3)	0.0283 (13)
C2	0.3672 (6)	0.5213 (4)	−0.1047 (3)	0.0250 (12)
C3	−0.1754 (6)	0.3721 (4)	0.0703 (3)	0.0241 (12)
C4	0.2279 (6)	−0.2971 (4)	−0.1210 (4)	0.0285 (13)
C5	0.4370 (7)	0.0879 (5)	−0.2977 (4)	0.0312 (13)
H5A	0.368915	0.036971	−0.322989	0.037*
H5B	0.382704	0.152044	−0.299458	0.037*
C6	0.5233 (7)	−0.0809 (4)	−0.2035 (4)	0.0304 (13)
H6A	0.519170	−0.113186	−0.150759	0.036*
H6B	0.442255	−0.109868	−0.239791	0.036*
C7	0.3230 (7)	0.3938 (5)	−0.2633 (4)	0.0295 (13)
H7A	0.262393	0.353567	−0.303239	0.035*
H7B	0.267680	0.456170	−0.254845	0.035*
C8	0.4350 (6)	0.4182 (4)	−0.0976 (4)	0.0276 (12)
H8A	0.427790	0.394136	−0.042326	0.033*
H8B	0.542830	0.422877	−0.106818	0.033*
C9	−0.0402 (7)	0.3558 (4)	0.0216 (4)	0.0308 (13)
H9A	0.022699	0.302154	0.046841	0.037*
H9B	0.020761	0.417228	0.023067	0.037*
C10	−0.2260 (7)	0.2176 (5)	−0.0786 (4)	0.0327 (13)
H10A	−0.315614	0.243139	−0.054062	0.039*
H10B	−0.258726	0.197287	−0.133864	0.039*
C11	0.1717 (7)	−0.1229 (4)	0.0318 (4)	0.0290 (13)
H11A	0.193515	−0.064180	0.066213	0.035*
H11B	0.061486	−0.126864	0.020645	0.035*
C12	0.1564 (7)	−0.1940 (4)	−0.1323 (4)	0.0325 (13)
H12A	0.049539	−0.197057	−0.120952	0.039*
H12B	0.161706	−0.172085	−0.188363	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0399 (4)	0.0265 (4)	0.0396 (4)	0.0031 (3)	0.0092 (3)	0.0012 (3)
Cu2	0.0321 (4)	0.0366 (4)	0.0377 (4)	−0.0002 (3)	0.0149 (3)	−0.0002 (3)
I1	0.0411 (2)	0.0373 (2)	0.0302 (2)	0.00574 (18)	0.00281 (17)	0.00025 (17)
I2	0.0331 (2)	0.0469 (3)	0.0380 (2)	0.00192 (19)	0.00058 (17)	−0.00704 (19)
S1	0.0302 (8)	0.0294 (8)	0.0332 (8)	0.0000 (6)	0.0142 (6)	−0.0026 (6)
S2	0.0321 (7)	0.0208 (7)	0.0325 (8)	−0.0023 (6)	0.0140 (6)	−0.0019 (6)
S3	0.0345 (8)	0.0267 (8)	0.0371 (8)	0.0040 (6)	0.0165 (6)	0.0062 (6)
S4	0.0356 (8)	0.0218 (7)	0.0382 (8)	−0.0004 (6)	0.0153 (7)	0.0020 (6)
N1	0.032 (3)	0.025 (3)	0.033 (3)	−0.001 (2)	0.014 (2)	−0.003 (2)
N2	0.031 (3)	0.022 (2)	0.030 (3)	−0.002 (2)	0.013 (2)	−0.006 (2)
C1	0.034 (3)	0.025 (3)	0.028 (3)	0.002 (3)	0.014 (2)	0.007 (2)
C2	0.026 (3)	0.022 (3)	0.028 (3)	−0.003 (2)	0.008 (2)	−0.006 (2)
C3	0.023 (3)	0.022 (3)	0.027 (3)	−0.005 (2)	0.006 (2)	−0.002 (2)
C4	0.027 (3)	0.026 (3)	0.033 (3)	0.000 (2)	0.011 (2)	−0.009 (2)
C5	0.024 (3)	0.035 (3)	0.037 (3)	0.005 (3)	0.015 (3)	0.010 (3)
C6	0.034 (3)	0.028 (3)	0.032 (3)	0.005 (3)	0.013 (3)	0.005 (3)
C7	0.030 (3)	0.031 (3)	0.028 (3)	−0.005 (3)	0.005 (2)	−0.005 (3)
C8	0.026 (3)	0.030 (3)	0.027 (3)	0.001 (2)	0.007 (2)	0.000 (2)
C9	0.031 (3)	0.022 (3)	0.041 (4)	−0.001 (2)	0.017 (3)	−0.003 (3)
C10	0.033 (3)	0.033 (3)	0.033 (3)	−0.001 (3)	0.009 (3)	0.003 (3)
C11	0.030 (3)	0.027 (3)	0.032 (3)	−0.002 (2)	0.011 (2)	0.000 (2)
C12	0.035 (3)	0.031 (3)	0.032 (3)	0.005 (3)	0.007 (3)	−0.003 (3)

Geometric parameters (Å, º) top

Cu1—S1	2.3955 (16)	C2—C8	1.485 (8)
Cu1—S4	2.3187 (16)	C3—C4ⁱⁱⁱ	1.395 (8)
Cu1—I1	2.6190 (9)	C3—C9	1.495 (7)
Cu1—I2	2.5915 (10)	C4—C12	1.502 (8)
Cu1—Cu2	2.7759 (11)	C5—H5A	0.9700
Cu2—S2	2.3030 (16)	C5—H5B	0.9700
Cu2—S3	2.3039 (16)	C6—C7ⁱ	1.529 (8)
Cu2—I1	2.7117 (10)	C6—H6A	0.9700
Cu2—I2	2.6460 (9)	C6—H6B	0.9700
S1—C6	1.810 (6)	C7—H7A	0.9700
S1—C5	1.812 (6)	C7—H7B	0.9700
S2—C7	1.812 (6)	C8—H8A	0.9700
S2—C8	1.827 (6)	C8—H8B	0.9700
S3—C10	1.819 (6)	C9—H9A	0.9700
S3—C9	1.821 (6)	C9—H9B	0.9700
S4—C11	1.809 (6)	C10—C11ⁱⁱⁱ	1.524 (8)
S4—C12	1.823 (6)	C10—H10A	0.9700
N1—C4	1.333 (7)	C10—H10B	0.9700
N1—C1ⁱ	1.346 (8)	C11—H11A	0.9700
N2—C2ⁱⁱ	1.334 (7)	C11—H11B	0.9700
N2—C3	1.341 (7)	C12—H12A	0.9700
C1—C2ⁱ	1.399 (8)	C12—H12B	0.9700
C1—C5	1.520 (7)

S4—Cu1—S1	101.91 (6)	C1—C5—S1	112.3 (4)
S4—Cu1—I2	118.12 (5)	C1—C5—H5A	109.2
S1—Cu1—I2	104.83 (5)	S1—C5—H5A	109.2
S4—Cu1—I1	102.76 (5)	C1—C5—H5B	109.2
S1—Cu1—I1	111.80 (5)	S1—C5—H5B	109.1
I2—Cu1—I1	116.62 (3)	H5A—C5—H5B	107.9
S4—Cu1—Cu2	146.61 (5)	C7ⁱ—C6—S1	115.0 (4)
S1—Cu1—Cu2	111.01 (5)	C7ⁱ—C6—H6A	108.5
I2—Cu1—Cu2	58.95 (3)	S1—C6—H6A	108.5
I1—Cu1—Cu2	60.27 (3)	C7ⁱ—C6—H6B	108.5
S2—Cu2—S3	129.92 (6)	S1—C6—H6B	108.5
S2—Cu2—I2	108.76 (5)	H6A—C6—H6B	107.5
S3—Cu2—I2	106.63 (5)	C6^iv—C7—S2	112.1 (4)
S2—Cu2—I1	90.49 (5)	C6^iv—C7—H7A	109.2
S3—Cu2—I1	107.95 (5)	S2—C7—H7A	109.2
I2—Cu2—I1	111.68 (3)	C6^iv—C7—H7B	109.2
S2—Cu2—Cu1	93.15 (5)	S2—C7—H7B	109.2
S3—Cu2—Cu1	136.16 (5)	H7A—C7—H7B	107.9
I2—Cu2—Cu1	57.04 (3)	C2—C8—S2	115.0 (4)
I1—Cu2—Cu1	57.00 (2)	C2—C8—H8A	108.5
Cu1—I1—Cu2	62.73 (3)	S2—C8—H8A	108.5
Cu1—I2—Cu2	64.00 (3)	C2—C8—H8B	108.5
C6—S1—C5	100.4 (3)	S2—C8—H8B	108.5
C6—S1—Cu1	103.67 (19)	H8A—C8—H8B	107.5
C5—S1—Cu1	108.86 (19)	C3—C9—S3	113.5 (4)
C7—S2—C8	102.7 (3)	C3—C9—H9A	108.9
C7—S2—Cu2	116.0 (2)	S3—C9—H9A	108.9
C8—S2—Cu2	114.97 (19)	C3—C9—H9B	108.9
C10—S3—C9	104.4 (3)	S3—C9—H9B	108.9
C10—S3—Cu2	105.0 (2)	H9A—C9—H9B	107.7
C9—S3—Cu2	103.4 (2)	C11ⁱⁱⁱ—C10—S3	118.0 (4)
C11—S4—C12	103.4 (3)	C11ⁱⁱⁱ—C10—H10A	107.8
C11—S4—Cu1	119.3 (2)	S3—C10—H10A	107.8
C12—S4—Cu1	111.3 (2)	C11ⁱⁱⁱ—C10—H10B	107.8
C4—N1—C1ⁱ	118.2 (5)	S3—C10—H10B	107.8
C2ⁱⁱ—N2—C3	118.1 (5)	H10A—C10—H10B	107.2
N1^iv—C1—C2ⁱ	120.8 (5)	C10ⁱⁱⁱ—C11—S4	114.7 (4)
N1^iv—C1—C5	114.1 (5)	C10ⁱⁱⁱ—C11—H11A	108.6
C2ⁱ—C1—C5	125.1 (5)	S4—C11—H11A	108.6
N2ⁱⁱ—C2—C1^iv	120.9 (5)	C10ⁱⁱⁱ—C11—H11B	108.6
N2ⁱⁱ—C2—C8	116.0 (5)	S4—C11—H11B	108.6
C1^iv—C2—C8	123.1 (5)	H11A—C11—H11B	107.6
N2—C3—C4ⁱⁱⁱ	121.2 (5)	C4—C12—S4	109.5 (4)
N2—C3—C9	116.9 (5)	C4—C12—H12A	109.8
C4ⁱⁱⁱ—C3—C9	121.9 (5)	S4—C12—H12A	109.8
N1—C4—C3ⁱⁱⁱ	120.8 (5)	C4—C12—H12B	109.8
N1—C4—C12	114.9 (5)	S4—C12—H12B	109.8
C3ⁱⁱⁱ—C4—C12	124.3 (5)	H12A—C12—H12B	108.2

C2ⁱⁱ—N2—C3—C4ⁱⁱⁱ	−0.6 (8)	C7—S2—C8—C2	43.6 (5)
C2ⁱⁱ—N2—C3—C9	179.1 (5)	Cu2—S2—C8—C2	−83.2 (4)
C1ⁱ—N1—C4—C3ⁱⁱⁱ	1.2 (9)	N2—C3—C9—S3	−80.9 (6)
C1ⁱ—N1—C4—C12	179.4 (5)	C4ⁱⁱⁱ—C3—C9—S3	98.9 (6)
N1^iv—C1—C5—S1	−83.4 (6)	C10—S3—C9—C3	−50.9 (5)
C2ⁱ—C1—C5—S1	96.8 (7)	Cu2—S3—C9—C3	−160.6 (4)
C6—S1—C5—C1	−77.1 (5)	C9—S3—C10—C11ⁱⁱⁱ	−58.6 (5)
Cu1—S1—C5—C1	174.4 (4)	Cu2—S3—C10—C11ⁱⁱⁱ	49.8 (5)
C5—S1—C6—C7ⁱ	76.2 (5)	C12—S4—C11—C10ⁱⁱⁱ	77.0 (5)
Cu1—S1—C6—C7ⁱ	−171.3 (4)	Cu1—S4—C11—C10ⁱⁱⁱ	−158.8 (4)
C8—S2—C7—C6^iv	67.3 (5)	N1—C4—C12—S4	−83.0 (6)
Cu2—S2—C7—C6^iv	−166.5 (3)	C3ⁱⁱⁱ—C4—C12—S4	95.2 (6)
N2ⁱⁱ—C2—C8—S2	85.1 (6)	C11—S4—C12—C4	−82.9 (5)
C1^iv—C2—C8—S2	−92.7 (6)	Cu1—S4—C12—C4	147.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···S4	0.97	2.80	3.409 (6)	122
C9—H9A···I1	0.97	2.99	3.771 (6)	138
C6—H6A···I1^v	0.97	2.89	3.702 (6)	142

Symmetry code: (v) −x+1, −y, −z.

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 and the University of Neuchâtel .

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