Bis(acetonitrile-[kappa]N)bis­[hydrido­tris(3,5-dimethyl­pyrazol-1-yl-[kappa]N²)borato]di-[mu]₃-sulfido-tetra-[mu]₂-sulfido-di-[mu]₂-thio­cyanato-[kappa]²N:S;[kappa]²S:N-tetra­copper(I)ditungsten(VI)

Reactions of (Et₄N)[Tp*WS₃] [Tp* is hydridotris(3,5-di­methyl­pyrazol-1-yl)borate] with CuSCN in MeCN in the presence of melamine afforded the title neutral dimeric cluster [Cu₄W₂(C₁₅H₂₂BN₆)₂(NCS)₂S₆(C₂H₃N)₂] or [Tp*W([mu]₂-S)₂([mu]₃-S)Cu([mu]₂-SCN)(CuMeCN)]₂, which has two butterfly-shaped [Tp*WS₃Cu₂] cores bridged across a centre of inversion by two (CuSCN)^- anions. The S atoms of the bridging thio­cyanate ligands inter­act with the H atoms of the methyl groups of the Tp* units of a neighbouring dimer to form a C-H...S hydrogen-bonded chain. The N atoms of the thio­cyanate anions inter­act with the H atoms of the methyl groups of the Tp* units of neighbouring chains, affording a two-dimensional hydrogen-bonded network.

S1. Comment

In recent years, the chemistry of the Mo/W/Cu/S clusters derived from reactions of metal sulfide synthons {e.g. [MS₄]^2- (M = Mo, W) (Müller et al., 1981, 1989; Howard et al., 1986; Holm et al., 1995; Ansari et al., 1990; Hou et al., 1996; Wu et al., 2004; Niu et al., 2004; Zhang, Song, Ren et al., 2007 or Zhang, Song & Wang, 2007?); [Cp*MS₃]^- (Cp* = pentamethylcyclopentadienyl; M = Mo, W) (Kawaguchi et al., 1995, 1997; Lang, Kawaguchi, Ohnishi et al., 1997 or Lang, Kawaguchi & Tatsumi, 1997?; Lang et al., 1998, 1999); [Tp*MS₃]^- [Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate; M = Mo, W] (Seino et al., 2001, 2003; Wang et al., 2007; Wei et al., 2009)} with CuX (X = Cl, Br, I, SCN, CN) has been extensively investigated because of their structural variety, their potential applications in biological systems (Chan et al., 1995; Che et al., 2001; Eldredge et al., 1990; Stiefel et al., 1993, 1996; George et al., 2000, 2003; Dobbek et al., 2002; Ginda et al., 2003) and as opto-electronic materials (Shi et al., 1994, 1998; Zheng et al., 1997; Zhang et al., 2000; Che et al., 2001; Coe et al., 2004). Currently we are interested in using (Et₄N)[Tp*WS₃] (Seino et al., 2001, 2003) for the construction of new W/Cu/S clusters, because this synthon can generate more soluble W/Cu/S cluster precursors and some resulting clusters were [found to be] topologically unique in the chemistry of the tetrathiometallates and showed relatively good third-order nonlinear optical performances in solution (Lang, Kawaguchi, Ohnishi et al., 1997 or Lang, Kawaguchi & Tatsumi, 1997?; Lang et al., 1999, 2003; Xu et al., 2006; Zhang, Song, Ren et al., 2007 or Zhang, Song & Wang, 2007?). In our previous studies, stepwise addition reactions between (Et₄N)[Tp*WS₃] and CuSCN have been completed in the systems with different molar ratios, which led to the formation of the [1 + 1], [1 + 2], [1 + 3] and [1 + 4] addition products (Wei et al., 2009). As an extension of this study, we carried out reactions of (Et₄N)[Tp*WS₃] with CuSCN in the presence of melamine (MA) from which a hexanuclear W/Cu/S cluster [Tp*W(µ₂-S)₂(µ₃-S)Cu(µ₂-SCN)(CuMeCN)]_2, (I), was isolated. Herein we report the crystal structure of (I).

The asymmetric unit of compound (I) contains half of a [Tp*W(µ₂-S)₂(µ₃-S)Cu(µ₂-SCN)(CuMeCN)]₂ molecule. It contains two [Tp*W(µ₂-S)₂(µ₃-S)Cu(CuMeCN)]⁺ fragments, which are linked via a pair of NCS bridges (Fig. 1). A crystallographic center of symmetry is located at the middle of the W1—W1ⁱ bond [symmetry code: (i) -x, -y, -z]. The double butterfly-shaped hexanuclear structure of (I) is unprecedented in Mo(W)/Cu/S cluster chemistry. Each fragment may be viewed as a butterfly-shaped [Tp*WS₃Cu₂] core, which is similar to those found in [Tp*W(µ₃-S)(µ-S)₂Cu₂(MeCN)(µ-CN)]_∞ (Wang et al., 2007) and (Et₄N)[Tp*W(µ-S)₃(CuNCS)₂].ClCH₂CH₂Cl. The two Cu atoms in each fragment are not equivalent. Cu1 is coordinated by one N of the terminal MeCN molecule, two sulfur atoms and one N atom of the thiocyanate anion, forming a tetrahedral coordination geometry. Cu2 is coordinated by two sulfur atoms and one S atom of the thiocyanate anion, forming an approximately trigonal–planar geometry. Because of the different coordination geometries of the Cu atoms, the W···Cu separations are different. The trigonally coordinated W1···Cu2 [2.6354 (9) Å] contact (Table 1) is shorter than the corresponding ones in [Tp*W(µ₃-S)(µ-S)₂Cu₂(MeCN)(µ-CN)]_∞ [2.6560 (9) Å] and (Et₄N)[Tp*W(µ-S)₃(CuNCS)₂].ClCH₂CH₂Cl [2.6404 (11) Å] (Wei et al., 2009). The tetrahedrally coordinated W1···Cu1 [2.6737 (14) Å] contact is longer than those of the corresponding ones in [Tp*W(µ₃-S)(µ-S)₂Cu₂(MeCN)(µ-CN)]_∞ [2.6694 (10) Å]. The Cu—S bond lengths also reflect the different coordination modes of the copper atoms [on average 2.2086 (14) Å for a trigonal geometry and on average 2.2475 (14) Å for a tetrahedral environment]. The Cu—N(NCS) bond length [1.931 (4) Å] is almost the same as those of the copper(I) complexes containing bridging thiocyanates and coordinated MeCN in [Tp*W(µ₃-S)(µ-S)₂Cu₂(MeCN)(µ-CN)]_∞ [1.930 (7) Å]. The Cu—N(MeCN) bond length [2.213 (5) Å] is shorter than those of [Tp*W(µ₃-S)(µ-S)₂Cu₂(MeCN)(µ-CN)]_∞ [2.425 (7) Å]. It should be noted that the Cu1—µ₃-S2—Cu2 angle [78.26 (5)°] is 17.7° smaller than that of the cationic cluster [PPh₄][Cp*WS₃(CuCN)₂] (Lang et al., 2004) and slightly smaller than that in [Tp*W(µ₃-S)(µ-S)₂Cu₂(MeCN)(µ-CN)]_∞ [79.68 (6)°].

The S atoms of each cluster core in (I) interact with the hydrogen atoms of the methyl groups of the Tp* units to form four intramolecular C—H···S contacts (C5···S2, C5···S1, C10···S2, C15···S1) (Table 2). The S atoms of the bridged thiocyanate anion interact with the hydrogen atoms of the methyl groups of the Tp* units of the neighboring dimer to form one intermolecular hydrogen bond [C5···S4 (-1 + x, y, z)], forming a C—H···S-bonded chain. The N atoms of the thiocyanate anion interact with the hydrogen atoms of the methyl groups of the Tp* units of the neighboring chains to form one intermolecular contact [C8···N8 (2 - x, 1 - y, 1 - z)]. Together these interactions afford a two-dimensional hydrogen-bonded network extednded along the ab plane (Fig. 2).

Related literature

For related literature, see: Ansari & Ibers (1990); Chan et al. (1995); Che et al. (2001); Coe (2004); Dobbek et al. (2002); Eldredge & Averill (1990); George et al. (2000, 2003); Ginda et al. (2003); Holm (1995); Hou et al. (1996); Howard et al. (1986); Kawaguchi & Tatsumi (1995); Kawaguchi et al. (1997); Lang & Tatsumi (1998); Lang et al. (1999, 2003, 2004); Lang, Kawaguchi & Tatsumi (1997); Lang, Kawaguchi, Ohnishi & Tatsumi (1997); Müller et al. (1981, 1989); Niu et al. (2004); Seino et al. (2001, 2003); Shi (1998); Shi et al. (1994); Stiefel & Matsumoto (1996); Stiefel et al. (1993); Wang et al. (2007); Wei et al. (2009); Wu (2004); Xu et al. (2006); Zhang et al. (2000); Zhang, Song & Wang (2007); Zhang, Song, Ren, Li, Li, Zhang & Lang (2007); Zheng et al. (1997).

S2. Experimental

To a red solution containing (Et₄N)[Tp*WS₃] (19 mg, 0.025 mmol) in MeCN (5 ml) was added CuNCS (6 mg, 0.050 mmol) and excess MA. The resulting mixture was stirred for 5 min to form a dark red solution and filtered. Diethyl ether (20 ml) was carefully layered onto the filtrate to form black block crystals, which were collected by filtration, washed with Et₂O, and dried in vacuo. Yield: 15 mg (75% based on W). Analysis calculated for C₃₆H₅₀B₂Cu₄N₁₆S₈W₂: C 26.91, H 3.14, N 13.95; found: C 23.78, H 3.25, N 13.82. IR (KBr disc): 2564 (w), 2122 (s), 2062 (m), 2090 (s), 1631 (w), 1546 (m), 1451 (m), 1439 (m), 1414 (m), 1347 (m), 1221 (m), 1072 (w), 1034 (w), 860 (w), 822 (w), 798 (w), 691 (w), 650 (w), 479 (w), 418 (w) cm^-1. ¹H NMR (400 MHz, DMSO-d₆): δ 2.04 (s, 6H, CH₃CN), 2.33 (s, 18H, CH₃ in Tp*), 2.72 (s, 18H, CH₃ in Tp*), 6.08 (s, 6H, CH in Tp*). The B—H proton was not located.

S3. Refinement

All H atoms were placed in geometrically idealized positions (C—H = 0.98 Å for methyl groups; C—H = 0.99 Å for methylene groups; C—H = 0.95 Å for phenyl groups) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C) for phenyl groups and U_iso(H) = 1.5U_eq(C) for methyl groups.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. View of the molecular structure of the title cluster, (I), with ellipsoids drawn at the 30% probability level. H atoms are drawn as spheres of arbitrary radii. [Symmetry code: (i) -x + 1, -y, -z + 1.]
	Fig. 2. View of the two-dimensional network of the title clusters. Dashed lines indicate C5—H5B···S4 interactions (green in the electronic version of the paper) and C8—H8···N8 interactions (blue).

Bis(acetonitrile-κN)bis[hydridotris(3,5-dimethylpyrazol-1-yl- κN²)borato]di-µ₃-sulfido-tetra-µ₂-sulfido-di-µ₂- thiocyanato-κ²N:S;κ²S:N- tetracopper(I)ditungsten(VI)

Crystal data

[Cu4W2(C15H22BN6)2(NCS)2S6(C2H3N)2]	Z = 1
Mr = 1606.88	F(000) = 780
Triclinic, P1	Dx = 2.006 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3349 (19) Å	Cell parameters from 6589 reflections
b = 9.954 (2) Å	θ = 3.3–27.5°
c = 15.547 (3) Å	µ = 6.24 mm^−1
α = 92.21 (3)°	T = 223 K
β = 93.73 (3)°	Block, black
γ = 112.33 (3)°	0.17 × 0.15 × 0.12 mm
V = 1330.3 (5) Å^3

Data collection

Rigaku Mercury diffractometer	5976 independent reflections
Radiation source: fine-focus sealed tube	5024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −10→12
Tmin = 0.417, Tmax = 0.522	k = −12→12
12835 measured reflections	l = −19→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0328P)^2] where P = (Fo^2 + 2Fc^2)/3
5976 reflections	(Δ/σ)max = 0.001
318 parameters	Δρmax = 0.96 e Å^−3
0 restraints	Δρmin = −1.14 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
W1	0.69500 (2)	0.341798 (19)	0.751384 (11)	0.01945 (7)
Cu1	0.49365 (8)	0.11341 (6)	0.65306 (4)	0.03033 (15)
Cu2	0.81606 (7)	0.22955 (6)	0.63367 (4)	0.02770 (14)
S1	0.49778 (16)	0.15630 (12)	0.79559 (8)	0.0282 (3)
S2	0.64272 (14)	0.32686 (12)	0.60211 (7)	0.0233 (2)
S3	0.89767 (16)	0.27450 (14)	0.77082 (8)	0.0292 (3)
S4	0.94078 (16)	0.14121 (15)	0.54485 (8)	0.0338 (3)
B1	0.7508 (7)	0.6627 (6)	0.8632 (3)	0.0244 (11)
H1B1	0.767 (6)	0.773 (5)	0.898 (3)	0.028 (13)*
N1	0.5431 (5)	0.4753 (4)	0.7617 (2)	0.0222 (8)
N2	0.5961 (5)	0.6092 (4)	0.8086 (2)	0.0229 (8)
N3	0.8691 (5)	0.5764 (4)	0.7409 (2)	0.0224 (8)
N4	0.8801 (5)	0.6858 (4)	0.8018 (2)	0.0235 (8)
N5	0.7507 (5)	0.4171 (4)	0.8935 (2)	0.0239 (9)
N6	0.7521 (5)	0.5493 (4)	0.9246 (2)	0.0233 (8)
N7	0.5807 (6)	−0.0635 (5)	0.6375 (3)	0.0444 (12)
N8	0.6949 (5)	−0.0077 (4)	0.4198 (3)	0.0328 (10)
C1	0.5110 (8)	0.8110 (6)	0.8469 (4)	0.0428 (14)
H1A	0.5317	0.8074	0.9086	0.064*
H1B	0.4181	0.8318	0.8363	0.064*
H1C	0.5985	0.8870	0.8251	0.064*
C2	0.4872 (6)	0.6681 (5)	0.8022 (3)	0.0263 (11)
C3	0.3635 (7)	0.5735 (6)	0.7505 (3)	0.0327 (12)
H3	0.2710	0.5864	0.7342	0.039*
C4	0.3990 (6)	0.4550 (5)	0.7263 (3)	0.0253 (10)
C5	0.2937 (6)	0.3242 (6)	0.6717 (3)	0.0366 (13)
H5A	0.3382	0.3194	0.6176	0.055*
H5B	0.1932	0.3306	0.6602	0.055*
H5C	0.2810	0.2374	0.7019	0.055*
C6	1.0411 (7)	0.9492 (5)	0.8421 (4)	0.0426 (14)
H6A	0.9635	0.9897	0.8283	0.064*
H6B	1.1422	1.0171	0.8290	0.064*
H6C	1.0439	0.9319	0.9030	0.064*
C7	1.0002 (6)	0.8080 (5)	0.7893 (3)	0.0287 (11)
C8	1.0739 (6)	0.7789 (5)	0.7216 (3)	0.0311 (11)
H8	1.1641	0.8435	0.6996	0.037*
C9	0.9890 (6)	0.6355 (5)	0.6924 (3)	0.0261 (10)
C10	1.0235 (6)	0.5602 (6)	0.6156 (3)	0.0325 (12)
H10A	1.0329	0.4708	0.6323	0.049*
H10B	1.1202	0.6235	0.5945	0.049*
H10C	0.9397	0.5376	0.5703	0.049*
C11	0.7690 (8)	0.6862 (6)	1.0651 (3)	0.0473 (16)
H11A	0.8511	0.7745	1.0503	0.071*
H11B	0.7853	0.6719	1.1258	0.071*
H11C	0.6693	0.6945	1.0542	0.071*
C12	0.7709 (6)	0.5599 (5)	1.0117 (3)	0.0303 (11)
C13	0.7831 (7)	0.4334 (6)	1.0377 (3)	0.0364 (13)
H13	0.7983	0.4106	1.0948	0.044*
C14	0.7685 (6)	0.3467 (5)	0.9633 (3)	0.0312 (12)
C15	0.7720 (8)	0.1978 (6)	0.9619 (3)	0.0457 (16)
H15A	0.6990	0.1363	0.9157	0.069*
H15B	0.7435	0.1566	1.0168	0.069*
H15C	0.8760	0.2040	0.9524	0.069*
C16	0.7941 (6)	0.0550 (5)	0.4710 (3)	0.0283 (11)
C17	0.6692 (9)	−0.2715 (7)	0.5941 (4)	0.0512 (17)
H17A	0.6018	−0.3301	0.5451	0.077*
H17B	0.6641	−0.3323	0.6420	0.077*
H17C	0.7753	−0.2297	0.5783	0.077*
C18	0.6190 (7)	−0.1559 (6)	0.6194 (3)	0.0344 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.02163 (11)	0.01687 (9)	0.01946 (10)	0.00761 (7)	0.00064 (7)	−0.00379 (6)
Cu1	0.0277 (4)	0.0265 (3)	0.0287 (3)	0.0025 (3)	−0.0001 (3)	−0.0061 (2)
Cu2	0.0279 (4)	0.0304 (3)	0.0264 (3)	0.0141 (3)	0.0012 (3)	−0.0078 (2)
S1	0.0312 (7)	0.0202 (5)	0.0288 (6)	0.0045 (5)	0.0079 (5)	−0.0014 (5)
S2	0.0245 (7)	0.0237 (6)	0.0209 (5)	0.0090 (5)	−0.0008 (5)	−0.0023 (4)
S3	0.0311 (8)	0.0351 (7)	0.0258 (6)	0.0189 (6)	−0.0027 (5)	−0.0042 (5)
S4	0.0247 (7)	0.0395 (7)	0.0359 (7)	0.0132 (6)	−0.0015 (6)	−0.0173 (6)
B1	0.026 (3)	0.021 (2)	0.024 (3)	0.008 (2)	0.000 (2)	−0.004 (2)
N1	0.023 (2)	0.0179 (18)	0.0257 (19)	0.0075 (17)	0.0024 (16)	−0.0040 (15)
N2	0.025 (2)	0.0158 (17)	0.025 (2)	0.0056 (17)	0.0048 (17)	−0.0058 (15)
N3	0.023 (2)	0.0164 (18)	0.0259 (19)	0.0061 (16)	0.0005 (16)	−0.0012 (15)
N4	0.027 (2)	0.0192 (18)	0.0229 (19)	0.0075 (17)	0.0032 (17)	−0.0031 (15)
N5	0.029 (2)	0.0216 (19)	0.0203 (19)	0.0101 (18)	−0.0019 (17)	−0.0028 (15)
N6	0.024 (2)	0.0208 (19)	0.0205 (19)	0.0043 (17)	0.0015 (16)	−0.0067 (15)
N7	0.058 (4)	0.033 (3)	0.045 (3)	0.021 (3)	0.011 (2)	0.001 (2)
N8	0.033 (3)	0.028 (2)	0.030 (2)	0.004 (2)	0.002 (2)	−0.0079 (18)
C1	0.050 (4)	0.031 (3)	0.053 (3)	0.022 (3)	0.001 (3)	−0.012 (3)
C2	0.031 (3)	0.025 (2)	0.029 (2)	0.017 (2)	0.005 (2)	0.0001 (19)
C3	0.033 (3)	0.039 (3)	0.033 (3)	0.024 (3)	0.000 (2)	−0.003 (2)
C4	0.024 (3)	0.029 (2)	0.026 (2)	0.014 (2)	0.001 (2)	−0.0014 (19)
C5	0.024 (3)	0.042 (3)	0.043 (3)	0.015 (2)	−0.011 (2)	−0.016 (2)
C6	0.040 (4)	0.025 (3)	0.053 (3)	0.002 (2)	0.007 (3)	−0.011 (2)
C7	0.028 (3)	0.021 (2)	0.033 (3)	0.005 (2)	0.000 (2)	0.001 (2)
C8	0.029 (3)	0.022 (2)	0.037 (3)	0.003 (2)	0.007 (2)	0.005 (2)
C9	0.021 (3)	0.025 (2)	0.027 (2)	0.004 (2)	0.004 (2)	−0.0004 (19)
C10	0.028 (3)	0.034 (3)	0.032 (3)	0.007 (2)	0.008 (2)	−0.005 (2)
C11	0.070 (5)	0.040 (3)	0.028 (3)	0.018 (3)	0.005 (3)	−0.011 (2)
C12	0.033 (3)	0.032 (3)	0.021 (2)	0.008 (2)	0.002 (2)	−0.007 (2)
C13	0.047 (4)	0.040 (3)	0.019 (2)	0.014 (3)	0.001 (2)	−0.002 (2)
C14	0.036 (3)	0.031 (3)	0.027 (2)	0.013 (2)	0.004 (2)	−0.002 (2)
C15	0.074 (5)	0.042 (3)	0.030 (3)	0.033 (3)	0.007 (3)	0.005 (2)
C16	0.028 (3)	0.024 (2)	0.029 (2)	0.005 (2)	0.008 (2)	−0.006 (2)
C17	0.069 (5)	0.052 (4)	0.050 (4)	0.042 (4)	0.010 (3)	0.003 (3)
C18	0.044 (4)	0.030 (3)	0.027 (3)	0.012 (3)	0.005 (2)	0.005 (2)

Geometric parameters (Å, º)

W1—S1	2.2250 (15)	C1—H1B	0.9700
W1—S3	2.2414 (13)	C1—H1C	0.9700
W1—N5	2.268 (4)	C2—C3	1.364 (7)
W1—N1	2.290 (4)	C3—C4	1.386 (6)
W1—N3	2.303 (4)	C3—H3	0.9400
W1—S2	2.3274 (12)	C4—C5	1.489 (7)
W1—Cu2	2.6354 (9)	C5—H5A	0.9700
W1—Cu1	2.6737 (14)	C5—H5B	0.9700
Cu1—N8^i	1.931 (4)	C5—H5C	0.9700
Cu1—N7	2.213 (5)	C6—C7	1.502 (6)
Cu1—S1	2.2356 (13)	C6—H6A	0.9700
Cu1—S2	2.2594 (16)	C6—H6B	0.9700
Cu1—Cu2	2.8260 (12)	C6—H6C	0.9700
Cu2—S3	2.1870 (14)	C7—C8	1.374 (7)
Cu2—S2	2.2185 (14)	C8—C9	1.384 (7)
Cu2—S4	2.2202 (14)	C8—H8	0.9400
S4—C16	1.660 (5)	C9—C10	1.502 (6)
B1—N6	1.510 (7)	C10—H10A	0.9700
B1—N2	1.520 (7)	C10—H10B	0.9700
B1—N4	1.542 (7)	C10—H10C	0.9700
B1—H1B1	1.16 (5)	C11—C12	1.487 (7)
N1—C4	1.357 (6)	C11—H11A	0.9700
N1—N2	1.389 (5)	C11—H11B	0.9700
N2—C2	1.353 (6)	C11—H11C	0.9700
N3—C9	1.346 (6)	C12—C13	1.379 (7)
N3—N4	1.384 (5)	C13—C14	1.384 (7)
N4—C7	1.335 (6)	C13—H13	0.9400
N5—C14	1.349 (6)	C14—C15	1.494 (7)
N5—N6	1.379 (5)	C15—H15A	0.9700
N6—C12	1.348 (6)	C15—H15B	0.9700
N7—C18	1.139 (6)	C15—H15C	0.9700
N8—C16	1.144 (6)	C17—C18	1.448 (7)
N8—Cu1^i	1.931 (4)	C17—H17A	0.9700
C1—C2	1.490 (6)	C17—H17B	0.9700
C1—H1A	0.9700	C17—H17C	0.9700
S1—W1—S3	103.79 (5)	C14—N5—W1	131.2 (3)
S1—W1—N5	84.93 (11)	N6—N5—W1	121.9 (3)
S3—W1—N5	84.25 (11)	C12—N6—N5	109.8 (4)
S1—W1—N1	87.06 (10)	C12—N6—B1	129.5 (4)
S3—W1—N1	160.63 (10)	N5—N6—B1	120.3 (3)
N5—W1—N1	80.74 (13)	C18—N7—Cu1	171.8 (4)
S1—W1—N3	159.82 (10)	C16—N8—Cu1^i	171.1 (4)
S3—W1—N3	88.29 (11)	C2—C1—H1A	109.5
N5—W1—N3	80.20 (14)	C2—C1—H1B	109.5
N1—W1—N3	77.17 (14)	H1A—C1—H1B	109.5
S1—W1—S2	104.38 (6)	C2—C1—H1C	109.5
S3—W1—S2	104.49 (5)	H1A—C1—H1C	109.5
N5—W1—S2	164.95 (9)	H1B—C1—H1C	109.5
N1—W1—S2	87.86 (10)	N2—C2—C3	107.3 (4)
N3—W1—S2	87.75 (10)	N2—C2—C1	122.3 (5)
S1—W1—Cu2	106.18 (4)	C3—C2—C1	130.4 (5)
S3—W1—Cu2	52.54 (4)	C2—C3—C4	107.5 (4)
N5—W1—Cu2	136.68 (10)	C2—C3—H3	126.2
N1—W1—Cu2	140.13 (9)	C4—C3—H3	126.2
N3—W1—Cu2	94.00 (10)	N1—C4—C3	109.5 (4)
S2—W1—Cu2	52.66 (4)	N1—C4—C5	125.3 (4)
S1—W1—Cu1	53.35 (4)	C3—C4—C5	125.2 (5)
S3—W1—Cu1	100.84 (4)	C4—C5—H5A	109.5
N5—W1—Cu1	138.13 (11)	C4—C5—H5B	109.5
N1—W1—Cu1	98.51 (10)	H5A—C5—H5B	109.5
N3—W1—Cu1	140.91 (9)	C4—C5—H5C	109.5
S2—W1—Cu1	53.17 (4)	H5A—C5—H5C	109.5
Cu2—W1—Cu1	64.32 (3)	H5B—C5—H5C	109.5
N8^i—Cu1—N7	92.82 (19)	C7—C6—H6A	109.5
N8^i—Cu1—S1	123.14 (14)	C7—C6—H6B	109.5
N7—Cu1—S1	105.52 (13)	H6A—C6—H6B	109.5
N8^i—Cu1—S2	113.49 (13)	C7—C6—H6C	109.5
N7—Cu1—S2	115.02 (14)	H6A—C6—H6C	109.5
S1—Cu1—S2	106.31 (6)	H6B—C6—H6C	109.5
N8^i—Cu1—W1	155.15 (13)	N4—C7—C8	107.8 (4)
N7—Cu1—W1	111.99 (14)	N4—C7—C6	123.9 (5)
S1—Cu1—W1	52.99 (4)	C8—C7—C6	128.3 (5)
S2—Cu1—W1	55.54 (4)	C7—C8—C9	106.4 (5)
N8^i—Cu1—Cu2	136.69 (13)	C7—C8—H8	126.8
N7—Cu1—Cu2	69.48 (14)	C9—C8—H8	126.8
S1—Cu1—Cu2	99.94 (6)	N3—C9—C8	110.0 (4)
S2—Cu1—Cu2	50.23 (4)	N3—C9—C10	125.5 (4)
W1—Cu1—Cu2	57.18 (3)	C8—C9—C10	124.5 (5)
S3—Cu2—S2	110.17 (5)	C9—C10—H10A	109.5
S3—Cu2—S4	119.50 (6)	C9—C10—H10B	109.5
S2—Cu2—S4	129.01 (5)	H10A—C10—H10B	109.5
S3—Cu2—W1	54.43 (4)	C9—C10—H10C	109.5
S2—Cu2—W1	56.52 (4)	H10A—C10—H10C	109.5
S4—Cu2—W1	173.70 (4)	H10B—C10—H10C	109.5
S3—Cu2—Cu1	97.71 (5)	C12—C11—H11A	109.5
S2—Cu2—Cu1	51.51 (4)	C12—C11—H11B	109.5
S4—Cu2—Cu1	126.62 (5)	H11A—C11—H11B	109.5
W1—Cu2—Cu1	58.50 (3)	C12—C11—H11C	109.5
W1—S1—Cu1	73.66 (5)	H11A—C11—H11C	109.5
Cu2—S2—Cu1	78.26 (5)	H11B—C11—H11C	109.5
Cu2—S2—W1	70.82 (4)	N6—C12—C13	107.7 (4)
Cu1—S2—W1	71.29 (5)	N6—C12—C11	123.1 (5)
Cu2—S3—W1	73.03 (5)	C13—C12—C11	129.2 (4)
C16—S4—Cu2	98.52 (17)	C12—C13—C14	106.6 (4)
N6—B1—N2	109.6 (4)	C12—C13—H13	126.7
N6—B1—N4	109.2 (4)	C14—C13—H13	126.7
N2—B1—N4	107.9 (4)	N5—C14—C13	109.6 (4)
N6—B1—H1B1	113 (2)	N5—C14—C15	126.0 (4)
N2—B1—H1B1	108 (3)	C13—C14—C15	124.4 (4)
N4—B1—H1B1	109 (3)	C14—C15—H15A	109.5
C4—N1—N2	105.4 (4)	C14—C15—H15B	109.5
C4—N1—W1	132.9 (3)	H15A—C15—H15B	109.5
N2—N1—W1	121.7 (3)	C14—C15—H15C	109.5
C2—N2—N1	110.3 (4)	H15A—C15—H15C	109.5
C2—N2—B1	129.5 (4)	H15B—C15—H15C	109.5
N1—N2—B1	120.0 (4)	N8—C16—S4	177.9 (5)
C9—N3—N4	105.5 (4)	C18—C17—H17A	109.5
C9—N3—W1	133.2 (3)	C18—C17—H17B	109.5
N4—N3—W1	120.4 (3)	H17A—C17—H17B	109.5
C7—N4—N3	110.3 (4)	C18—C17—H17C	109.5
C7—N4—B1	128.9 (4)	H17A—C17—H17C	109.5
N3—N4—B1	120.2 (4)	H17B—C17—H17C	109.5
C14—N5—N6	106.3 (3)	N7—C18—C17	178.4 (6)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···S4^ii	0.97	2.85	3.518 (5)	127
C8—H8···N8^iii	0.94	2.60	3.456 (7)	152
C5—H5A···S2	0.97	2.84	3.491 (6)	125
C5—H5C···S1	0.97	2.80	3.510 (6)	131
C10—H10C···S2	0.97	2.86	3.415 (6)	117
C15—H15A···S1	0.97	2.63	3.415 (6)	138

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