Tetraethylammonium [1-methyl­imidazole-2(3H)-thione]copper(I)-di-μ-sulfido-dioxotungstate(VI)

Beheshti, A.; Brooks, N.R.; Clegg, W.; Khorrmdin, R.

doi:10.1107/S1600536804030132

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 12| December 2004| Pages m1923-m1926

https://doi.org/10.1107/S1600536804030132

Tetraethylammonium [1-methylimidazole-2(3H)-thione]copper(I)-di-μ-sulfido-dioxotungstate(VI)

Azizolla Beheshti,^a Neil R. Brooks,^b William Clegg ^b ^* and Rahman Khorrmdin ^a

^aDepartment of Chemistry, Faculty of Science, Shahid Chamran University, Ahvaz, Iran, and ^bSchool of Natural Sciences (Chemistry), University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, England
^*Correspondence e-mail: w.clegg@ncl.ac.uk

(Received 17 November 2004; accepted 18 November 2004; online 27 November 2004)

In the title complex, tetrethylammonium [1-methylimidazole-2(3H)-thione-2κS]dioxo-1κ²O-di-μ-sulfido-1:2κ⁴S:S-copper(I)tungstate(VI), (C₈H₂₀N)[WCuO₂S₂(Hmimt)], where Hmimt is 1-methylimidazole-2(3H)-thione (C₄H₆N₂S), the W and Cu atoms have tetrahedral and trigonal planar coordination, respectively. Two sulfide ligands bridge the two metal centres; tungsten is additionally coordinated by two terminal oxo ligands and copper by the exocyclic S atom of Hmimt. The bridged W⋯Cu distance is 2.670 (3) Å. Anions are linked into chains by N—H⋯O hydrogen bonds between Hmimt and oxo ligands.

Comment

Monovalent coinage metals are typical soft acids and their chemistry is largely based upon coordination by soft bases, such as sulfur donor ligands. Among the sulfur-containing ligands, heterocyclic thiones are of particular interest. Complexes of these ligands with transition metals are of interest in bioinorganic chemistry, because of the search for simple model compounds for metal proteins (Raper, 1996 ; Akrivos, 2001 ). In view of this, Cu^I (Dai et al., 2004 ; Aslanidis et al., 2004 ; Cox et al., 1999 ), Ag^I (Isab et al., 2002 ; Casas et al., 1996 ) and Au^I (Ahmad, 2004 ; Isab & Hussain, 1985 , 1986 ) complexes with thiones have been widely studied in recent years. We report here the synthesis and characterization of a copper(I) complex with Hmimt [1-methylimidazole-2(3H)-thione] and [WO₂S₂]²⁻ as a sulfur-donor ligands. The anion of the title compound, (I), is only the second example of copper coordination by the [WO₂S₂]²⁻ metalloligand to be verified by X-ray crystallography (Beheshti et al., 2001 ) and only the third example for any metal, the other being a palladium complex (Long et al., 1999 ).

A view of the structure is shown in Fig. 1 and selected geometric parameters are given in Table 1. The asymmetric unit consists of an (Et₄N)⁺ cation and an [O₂WS₂Cu(Hmimt)]⁻ anion. The geometry of the cation is unexceptional. The Cu atom, with trigonal–planar geometry, is coordinated by the exocyclic S atom of an Hmimt ligand and by two S atoms of the dithiotungstate group, similar to the arrangement in (PPh₄)[O₂WS₂Cu(PPh₃)]·Me₂CO (Beheshti et al., 2001), where triphenylphosphine replaces the Hmimt ligand. In the [O₂WS₂Cu(Hmimt)]⁻ anion, the three Cu—S bonds are slightly shorter than those in other compounds in which copper(I) is coordinated by three S atoms in a trigonal array involving bridging thiolates, including the clusters (Et₄N)[Cu₅(SBu)₆] (2.260–2.290 Å; Bowmaker et al., 1984 ) and (Me₄N)₂[Cu₄(SPh)₆]·EtOH (2.263–2.346 Å; Dance et al., 1983 ). The Cu—S1 bond is significantly shorter than Cu—S bonds (2.202–2.401 Å) in complexes in which copper(I) is coordinated in a trigonal array by a thiotungstate as a bidentate ligand. This observation can be rationalized as a delocalization of charge from Cu^I to W^VI when a π-donor ligand such as Hmimt and a π-acceptor ligand such as [WO₂S₂]²⁻ are bonded to a Cu^I atom. By the same reasoning, the Cu—S3 bond is shorter than that observed in (PPh₄)[O₂WS₂Cu(PPh3)]·Me₂CO (average 2.239 Å), in which copper(I) is coordinated by PPh₃ as a π-acceptor ligand (Beheshti et al., 2001).

The Cu1—S1—C1 angle is essentially the same as those obtained for the terminal Hmimt ligand in [Cu(Hmim)₃](NO₃) (average 107.3°; Atkinson et al., 1985 ). The bending at the thione S atom introduces an asymmetry in the anion which is also apparent in the dimensions of the WS₂CuS core. In particular, the S3—Cu—S1 angle on the same side of the anion as the Hmimt ligand is significantly greater than the other two bond angles at the Cu atom. This deviation from ideal trigonal–planar angles of 120° is attributed to steric effects and the bonding requirements of the Hmimt ligand.

The C2—C3 bond length in the Hmimt ligand is clearly consistent with a localized double bond and the thione C=S bond is weakened and lengthened on coordination relative to that of the uncoordinated Hmimt molecule (1.676 Å; Raper et al., 1983 ), due to a reduction in the π-bond character of the thione linkage accompanying metal–thione coordination. The ¹H NMR signals of Hmimt are shifted downfield from those for the uncoordinated molecule, indicating that the ligand remains attached to Cu in solution in dimethyl sulfoxide. The ¹³C NMR signals, compared with their positions in the spectrum of the uncomplexed ligand, support the coordination through S, leading to a weakening of the C=S bond and some partial double bond character for C—N (Popovic et al., 2000 ; Bierbach et al., 1998 ).

Tungsten has only slightly distorted tetrahedral coordination. The double sulfide bridges generate a short W⋯Cu distance of 2.670 (3) Å, which is not interpreted as a significant direct metal–metal bond.

The NH group of Hmimt forms a hydrogen bond with an oxo ligand attached to tungsten in a neighbouring anion, with an N⋯O distance of 2.70 (3) Å and an N—H⋯O angle of 177°. Repetition of this hydrogen bond by a screw axis generates a chain of anions along the b axis (Fig. 2). The tautomeric form of Hmimt is also confirmed by characteristic bands in the FT—IR spectrum, with an N—H but no S—H stretching vibration, and by the presence of a ¹H NMR signal for H bonded to N. There are no other significant interactions among the components apart from normal coulombic and van der Waals forces; the packing is shown in Fig. 3.

The FT–IR spectrum of the complex exhibits strong features at 902 and 837 cm⁻¹ characteristic of the symmetric and asymmetric stretching vibrations of the W=O bonds in the coordinated [WO₂S₂]²⁻ anion, respectively. The band at 437 cm⁻¹ is assigned to the bridging W—S bonds.

Figure 1
The molecular structure, with atom labels and 50% probability ellipsoids for non-H atoms.

Figure 2
The chain of anions generated by N—H⋯O hydrogen bonding (shown as dashed lines).

Figure 3
The crystal packing, viewed down the a axis.

Experimental

(NH₄)₂[WO₂S₂] (0.316 g, 1.0 mmol) was dissolved in dimethylformamide (5 ml) and solid (Et₄N)Br (0.441 g, 2.1 mmol) was added. The mixture was stirred at room temperature for 5 min. CuCl (0.1 g, 1.01 mmol) was added and the mixture was stirred for another 5 min and then filtered. 2-Propanol (10 ml) and diethyl ether (20 ml) were added to the filtrate. After stirring for 5 min, the precipitate was collected by filtration. It was washed with 2-propanol (3 ml) and diethyl ether (5 ml) and dried in vacuo to give a hygroscopic orange powder of (Et₄N)[O₂WS₂CuCl] (yield 59%). (Et₄N)₂[O₂WS₂CuCl] (0.128 g, 0.2 mmol) was dissolved in acetonitrile (5 ml). Hmimt (0.049 g, 0.43 mmol) was added and the mixture was stirred at room temperature for 30 min and then filtered. Dry diethyl ether was added to the filtrate until a cloudiness persisted throughout the solution. Upon leaving the solution to stand in a sealed flask at 278 K overnight, pale-orange crystals of (Et₄N)[O₂WS₂Cu(Hmimt) were obtained. ¹H NMR (DMSO-d₆): δ 12.62 (s, NH), 7.23 (s, CH), 7.06 (s, CH), 3.53 (s, NCH₃), together with characteristic signals for the cation; ¹³C NMR (DMSO-d₆): δ 155.64 (C1), 121.87 (C3), 116.34 (C2), 34.96 (NCH₃), and cation signals, using the numbering scheme of Fig. 1.

Crystal data

(C₈H₂₀N)[WCuO₂S₂(C₄H₆N₂S)]
M_r = 587.93
Orthorhombic, P2₁2₁2₁
a = 7.1985 (5) Å
b = 16.3720 (14) Å
c = 17.244 (2) Å
V = 2032.3 (3) Å³
Z = 4
D_x = 1.922 Mg m⁻³
Mo Kα radiation
Cell parameters from 17595 reflections
θ = 2.5–26.0°
μ = 7.02 mm⁻¹
T = 150 (2) K
Block, pale orange
0.34 × 0.16 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.190, T_max = 0.570
17533 measured reflections
3557 independent reflections
3369 reflections with I > 2σ(I)
R_int = 0.035
θ_max = 25.0°
h = −8 → 6
k = −19 → 19
l = −20 → 20

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.092
wR(F²) = 0.233
S = 1.24
3557 reflections
201 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + 149.3501P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.043
Δρ_max = 3.68 e Å⁻³
Δρ_min = −3.79 e Å⁻³
Extinction correction: SHELXTL
Extinction coefficient: 0.0029 (6)
Absolute structure: Flack (1983 ), 1506 Friedel pairs
Flack parameter = 0.35 (5)

Table 1
Selected geometric parameters (Å, °)

W—S2	2.288 (7)
W—S3	2.228 (10)
W—O1	1.77 (2)
W—O2	1.75 (2)
Cu—S1	2.189 (7)
Cu—S2	2.340 (9)
Cu—S3	2.168 (9)
S1—C1	1.75 (3)
N1—C1	1.37 (3)
N1—C2	1.36 (4)
N1—C4	1.40 (3)
N2—C1	1.34 (3)
N2—C3	1.37 (4)
C2—C3	1.33 (4)

S2—W—S3	107.0 (3)
S2—W—O1	107.8 (12)
S2—W—O2	106.3 (8)
S3—W—O1	114.2 (13)
S3—W—O2	112.2 (9)
O1—W—O2	108.9 (12)
S1—Cu—S2	121.7 (3)
S1—Cu—S3	130.9 (4)
S2—Cu—S3	107.2 (4)
Cu—S1—C1	106.5 (10)
W—S2—Cu	70.4 (2)
W—S3—Cu	74.8 (3)
C1—N1—C2	106 (2)
C1—N1—C4	121 (2)
C2—N1—C4	132 (2)
C1—N2—C3	109 (2)
S1—C1—N1	130 (2)
S1—C1—N2	122 (2)
N1—C1—N2	108 (2)
N1—C2—C3	110 (3)
N2—C3—C2	106 (3)

S2—Cu—S1—C1	157.1 (9)
S3—Cu—S1—C1	−18.0 (11)
Cu—S1—C1—N1	65 (3)
Cu—S1—C1—N2	−121 (2)

H atoms were positioned geometrically and refined with a riding model, and with U_iso values constrained to be 1.2 (1.5 for methyl groups) times U_eq of the carrier atom. Large and highly anisotropic displacement ellipsoids for the atoms of the cation indicate probable disorder, but no simple disorder model could be resolved; refinement was assisted by restraints on geometry and displacement parameters, and the overall precision of the structure is relatively low as a result. The cation and anion are both achiral, but the compound crystallizes in a non-centrosymmetric space group; the refined Flack (1983) parameter of 0.35 (5) indicates partial inversion twinning of the structure. The maximum and minimum final difference electron density features both lie almost 1 Å from the W atom.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: EvalCCD (Duisenberg et al., 2003 ); data reduction: EvalCCD; program(s) used to solve structure: SHELXTL (Sheldrick, 1997 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536804030132/lh6320sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804030132/lh6320Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

[1-methylimidazole-2(3H)-thione-2κS]dioxo-1κ²O-di-µ-sulfido-1:2κ⁴S:S- copper(I)tungstate(VI) top

Crystal data top

(C₈H₂₀N)[WCuO₂S₂(C₄H₆N₂S)]	F(000) = 1144
M_r = 587.93	D_x = 1.922 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 17595 reflections
a = 7.1985 (5) Å	θ = 2.5–26.0°
b = 16.3720 (14) Å	µ = 7.02 mm⁻¹
c = 17.244 (2) Å	T = 150 K
V = 2032.3 (3) Å³	Block, pale orange
Z = 4	0.34 × 0.16 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	3557 independent reflections
Radiation source: sealed tube	3369 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 25.0°, θ_min = 4.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −8→6
T_min = 0.190, T_max = 0.570	k = −19→19
17533 measured reflections	l = −20→20

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.092	w = 1/[σ²(F_o²) + 149.3501P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.233	(Δ/σ)_max = 0.043
S = 1.24	Δρ_max = 3.68 e Å⁻³
3557 reflections	Δρ_min = −3.79 e Å⁻³
201 parameters	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
127 restraints	Extinction coefficient: 0.0029 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1483 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.35 (5)

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

	x	y	z	U_iso*/U_eq
W	0.58610 (18)	0.94048 (7)	0.62415 (7)	0.0437 (4)
Cu	0.6062 (5)	1.10332 (18)	0.6250 (2)	0.0378 (7)
S1	0.6003 (11)	1.2370 (4)	0.6215 (5)	0.0446 (15)
S2	0.3362 (11)	1.0254 (5)	0.6095 (5)	0.055 (2)
S3	0.8309 (10)	1.0192 (7)	0.6499 (6)	0.072 (3)
O1	0.608 (6)	0.8821 (14)	0.5385 (15)	0.091 (8)
O2	0.532 (3)	0.8752 (14)	0.7011 (14)	0.061 (6)
N1	0.983 (3)	1.2608 (15)	0.6551 (14)	0.037 (5)
N2	0.784 (3)	1.3187 (13)	0.7341 (13)	0.037 (5)
H2	0.6796	1.3353	0.7554	0.044*
C1	0.797 (4)	1.2705 (18)	0.6717 (15)	0.033 (5)
C2	1.077 (5)	1.3000 (18)	0.7126 (19)	0.051 (7)
H2A	1.2083	1.300	0.7182	0.061*
C3	0.959 (4)	1.3381 (19)	0.760 (2)	0.053 (8)
H3	0.9901	1.3719	0.8026	0.064*
C4	1.042 (4)	1.2144 (18)	0.5914 (17)	0.043 (6)
H4A	0.9340	1.1954	0.5621	0.064*
H4B	1.1135	1.1672	0.6098	0.064*
H4C	1.1209	1.2481	0.5579	0.064*
N3	0.584 (3)	0.5761 (17)	0.6088 (11)	0.071 (6)
C5	0.460 (5)	0.612 (4)	0.671 (2)	0.114 (15)
H5A	0.5352	0.6467	0.7058	0.137*
H5B	0.4049	0.5675	0.7019	0.137*
C6	0.302 (5)	0.664 (4)	0.634 (4)	0.15 (2)
H6A	0.2162	0.6821	0.6751	0.223*
H6B	0.2343	0.6315	0.5961	0.223*
H6C	0.3556	0.7123	0.6088	0.223*
C7	0.480 (5)	0.520 (2)	0.5540 (18)	0.065 (8)
H7A	0.5691	0.4988	0.5154	0.078*
H7B	0.3869	0.5534	0.5255	0.078*
C8	0.379 (5)	0.447 (2)	0.593 (3)	0.089 (12)
H8A	0.3165	0.4145	0.5529	0.133*
H8B	0.2863	0.4677	0.6297	0.133*
H8C	0.4694	0.4132	0.6202	0.133*
C9	0.734 (4)	0.537 (3)	0.658 (2)	0.101 (13)
H9A	0.6744	0.5029	0.6986	0.121*
H9B	0.8051	0.5806	0.6847	0.121*
C10	0.869 (5)	0.483 (3)	0.610 (2)	0.093 (13)
H10A	0.9599	0.4577	0.6443	0.140*
H10B	0.9342	0.5177	0.5718	0.140*
H10C	0.7987	0.4410	0.5824	0.140*
C11	0.671 (6)	0.643 (2)	0.560 (3)	0.091 (11)
H11A	0.5732	0.6731	0.5325	0.109*
H11B	0.7546	0.6176	0.5212	0.109*
C12	0.785 (12)	0.702 (3)	0.612 (5)	0.20 (3)
H12A	0.8427	0.7443	0.5796	0.297*
H12B	0.8811	0.6721	0.6401	0.297*
H12C	0.7013	0.7286	0.6496	0.297*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W	0.0549 (7)	0.0380 (6)	0.0381 (6)	0.0110 (5)	0.0246 (6)	0.0077 (6)
Cu	0.0451 (18)	0.0381 (15)	0.0304 (14)	0.0067 (14)	0.0083 (17)	−0.0095 (15)
S1	0.044 (4)	0.040 (3)	0.049 (4)	0.001 (3)	0.001 (4)	−0.013 (3)
S2	0.039 (3)	0.056 (4)	0.071 (6)	0.017 (3)	−0.022 (4)	−0.013 (4)
S3	0.016 (3)	0.090 (6)	0.109 (8)	0.011 (3)	0.008 (4)	0.029 (6)
O1	0.16 (2)	0.049 (11)	0.069 (11)	0.031 (14)	0.040 (17)	−0.016 (9)
O2	0.062 (15)	0.059 (10)	0.061 (11)	0.004 (8)	0.022 (11)	0.021 (9)
N1	0.014 (7)	0.047 (13)	0.049 (12)	0.014 (8)	0.004 (7)	0.006 (8)
N2	0.035 (9)	0.035 (12)	0.040 (11)	−0.015 (9)	0.018 (8)	−0.009 (8)
C1	0.026 (8)	0.045 (12)	0.028 (11)	0.000 (9)	0.007 (8)	−0.001 (9)
C2	0.032 (9)	0.054 (18)	0.067 (17)	−0.025 (13)	0.014 (11)	0.001 (12)
C3	0.042 (14)	0.042 (17)	0.08 (2)	−0.025 (13)	0.009 (12)	−0.018 (13)
C4	0.027 (14)	0.050 (17)	0.051 (14)	0.008 (11)	0.010 (11)	0.006 (10)
N3	0.067 (16)	0.12 (2)	0.027 (12)	0.022 (12)	−0.015 (9)	−0.019 (10)
C5	0.05 (2)	0.20 (5)	0.09 (3)	0.02 (2)	0.003 (17)	−0.07 (2)
C6	0.012 (15)	0.27 (6)	0.16 (5)	0.04 (2)	−0.02 (3)	−0.09 (4)
C7	0.07 (2)	0.070 (18)	0.052 (17)	0.019 (14)	−0.028 (14)	0.005 (12)
C8	0.05 (2)	0.10 (2)	0.12 (3)	0.028 (15)	0.006 (18)	0.03 (2)
C9	0.014 (13)	0.21 (4)	0.08 (2)	0.005 (17)	−0.012 (12)	0.018 (19)
C10	0.06 (2)	0.15 (4)	0.08 (2)	0.021 (19)	−0.005 (18)	0.06 (2)
C11	0.05 (2)	0.09 (2)	0.13 (3)	0.014 (16)	0.00 (2)	−0.014 (17)
C12	0.25 (7)	0.07 (3)	0.27 (7)	−0.01 (3)	−0.12 (6)	−0.02 (4)

Geometric parameters (Å, º) top

W—S2	2.288 (7)	C5—H5A	0.99
W—S3	2.228 (10)	C5—H5B	0.99
W—O1	1.77 (2)	C5—C6	1.56 (3)
W—O2	1.75 (2)	C6—H6A	0.98
Cu—S1	2.189 (7)	C6—H6B	0.98
Cu—S2	2.340 (9)	C6—H6C	0.98
Cu—S3	2.168 (9)	C7—H7A	0.99
S1—C1	1.75 (3)	C7—H7B	0.99
N1—C1	1.37 (3)	C7—C8	1.55 (3)
N1—C2	1.36 (4)	C8—H8A	0.98
N1—C4	1.40 (3)	C8—H8B	0.98
N2—H2	0.88	C8—H8C	0.98
N2—C1	1.34 (3)	C9—H9A	0.99
N2—C3	1.37 (4)	C9—H9B	0.99
C2—H2A	0.95	C9—C10	1.56 (3)
C2—C3	1.33 (4)	C10—H10A	0.98
C3—H3	0.95	C10—H10B	0.98
C4—H4A	0.98	C10—H10C	0.98
C4—H4B	0.98	C11—H11A	0.99
C4—H4C	0.98	C11—H11B	0.99
N3—C5	1.51 (2)	C11—C12	1.56 (3)
N3—C7	1.51 (2)	C12—H12A	0.98
N3—C9	1.51 (2)	C12—H12B	0.98
N3—C11	1.51 (2)	C12—H12C	0.98

S2—W—S3	107.0 (3)	H5B—C5—C6	109.4
S2—W—O1	107.8 (12)	C5—C6—H6A	109.5
S2—W—O2	106.3 (8)	C5—C6—H6B	109.5
S3—W—O1	114.2 (13)	C5—C6—H6C	109.4
S3—W—O2	112.2 (9)	H6A—C6—H6B	109.5
O1—W—O2	108.9 (12)	H6A—C6—H6C	109.5
S1—Cu—S2	121.7 (3)	H6B—C6—H6C	109.5
S1—Cu—S3	130.9 (4)	N3—C7—H7A	108.4
S2—Cu—S3	107.2 (4)	N3—C7—H7B	108.5
Cu—S1—C1	106.5 (10)	N3—C7—C8	115 (3)
W—S2—Cu	70.4 (2)	H7A—C7—H7B	107.5
W—S3—Cu	74.8 (3)	H7A—C7—C8	108.5
C1—N1—C2	106 (2)	H7B—C7—C8	108.4
C1—N1—C4	121 (2)	C7—C8—H8A	109.5
C2—N1—C4	132 (2)	C7—C8—H8B	109.5
H2—N2—C1	125.4	C7—C8—H8C	109.5
H2—N2—C3	125.4	H8A—C8—H8B	109.5
C1—N2—C3	109 (2)	H8A—C8—H8C	109.5
S1—C1—N1	130 (2)	H8B—C8—H8C	109.5
S1—C1—N2	122 (2)	N3—C9—H9A	109.1
N1—C1—N2	108 (2)	N3—C9—H9B	109.1
N1—C2—H2A	124.8	N3—C9—C10	112 (3)
N1—C2—C3	110 (3)	H9A—C9—H9B	107.8
H2A—C2—C3	124.8	H9A—C9—C10	109.1
N2—C3—C2	106 (3)	H9B—C9—C10	109.1
N2—C3—H3	126.9	C9—C10—H10A	109.5
C2—C3—H3	126.9	C9—C10—H10B	109.5
N1—C4—H4A	109.5	C9—C10—H10C	109.5
N1—C4—H4B	109.5	H10A—C10—H10B	109.5
N1—C4—H4C	109.5	H10A—C10—H10C	109.5
H4A—C4—H4B	109.5	H10B—C10—H10C	109.5
H4A—C4—H4C	109.5	N3—C11—H11A	109.5
H4B—C4—H4C	109.5	N3—C11—H11B	109.5
C5—N3—C7	113 (3)	N3—C11—C12	111 (4)
C5—N3—C9	101 (2)	H11A—C11—H11B	108.1
C5—N3—C11	111 (4)	H11A—C11—C12	109.5
C7—N3—C9	117 (3)	H11B—C11—C12	109.5
C7—N3—C11	107 (3)	C11—C12—H12A	109.5
C9—N3—C11	108 (3)	C11—C12—H12B	109.5
N3—C5—H5A	109.4	C11—C12—H12C	109.5
N3—C5—H5B	109.4	H12A—C12—H12B	109.5
N3—C5—C6	111 (3)	H12A—C12—H12C	109.5
H5A—C5—H5B	108.0	H12B—C12—H12C	109.5
H5A—C5—C6	109.4

S2—Cu—S1—C1	157.1 (9)	Cu—S1—C1—N1	65 (3)
S3—Cu—S1—C1	−18.0 (11)	Cu—S1—C1—N2	−121 (2)
S3—W—S2—Cu	5.3 (4)	C1—N1—C2—C3	−5 (4)
O1—W—S2—Cu	−117.9 (11)	C4—N1—C2—C3	179 (3)
O2—W—S2—Cu	125.5 (9)	N1—C2—C3—N2	4 (4)
S1—Cu—S2—W	178.4 (3)	C1—N2—C3—C2	−1 (4)
S3—Cu—S2—W	−5.5 (4)	C7—N3—C5—C6	−61 (5)
S1—Cu—S3—W	−178.9 (4)	C9—N3—C5—C6	174 (4)
S2—Cu—S3—W	5.5 (4)	C11—N3—C5—C6	59 (5)
S2—W—S3—Cu	−5.6 (4)	C5—N3—C7—C8	−58 (4)
O1—W—S3—Cu	113.6 (11)	C9—N3—C7—C8	58 (4)
O2—W—S3—Cu	−121.9 (9)	C11—N3—C7—C8	180 (3)
C3—N2—C1—S1	−178 (2)	C5—N3—C9—C10	172 (4)
C3—N2—C1—N1	−2 (3)	C7—N3—C9—C10	49 (5)
C2—N1—C1—S1	179 (2)	C11—N3—C9—C10	−72 (4)
C2—N1—C1—N2	4 (3)	C5—N3—C11—C12	57 (5)
C4—N1—C1—S1	−4 (4)	C7—N3—C11—C12	−179 (4)
C4—N1—C1—N2	−179 (2)	C9—N3—C11—C12	−52 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.88	1.82	2.70 (3)	177

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

We thank the EPSRC (UK) and Shahid Chamran University for financial support.

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