Dibromidobis(N,N-diethyl­dithio­carbamato-κ2S,S′)tetra-μ3-sulfido-dicopper(I)dimolybdenum(V) isopropanol disolvate

Zhang, Q.; Liu, M.

doi:10.1107/S1600536808035241

Dibromidobis(N,N-diethyldithiocarbamato-κ²S,S′)tetra-μ₃-sulfido-dicopper(I)dimolybdenum(V) isopropanol disolvate

The molecule of the title compound, [Cu₂Mo₂Br₂(C₇H₁₄NS₂)₂S₄]·2C₃H₇OH, comprises one [(i-C₃H₇)₂NCS₂]₂Mo₂S₄ unit and two CuBr units held together by six Cu—μ₃-S bonds, thus forming a cubane-like Mo₂S₄Cu₂ core. Intramolecular O—H

S hydrogen bonds may stabilize the structure. Two methyl groups of the two independent solvent molecules are disordered over two positions and were refined with occupancies of 0.733 (12) and 0.267 (12).

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808035241/hk2539sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808035241/hk2539Isup2.hkl Contains datablock I

CCDC reference: 712299

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.013 Å
Disorder in main residue
R factor = 0.055
wR factor = 0.121
Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mo2    --  S2      ..      15.95 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  S1      ..      26.93 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  S2      ..      27.93 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu2    --  S1      ..      20.67 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu2    --  S2      ..      29.46 su
PLAT420_ALERT_2_B D-H Without Acceptor       O1     -   H1D    ...          ?
PLAT432_ALERT_2_B Short Inter X...Y Contact  O2     ..  C16     ..       2.81 Ang.

Alert level C
            Value of measurement temperature given =   291.000
            Value of melting point given =     0.000
PLAT083_ALERT_2_C SHELXL Second Parameter in WGHT unusually Large.      12.00
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.96 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.33 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Cu1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Cu2
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C20
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C19A
PLAT301_ALERT_3_C Main Residue  Disorder .........................       3.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         13

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10

   0 ALERT level A = In general: serious problem
   7 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  13 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In the past decades, chemistry of the sulfido-bridged dinuclear complexes with an M₂S₄ core (M = Mo, W) and various transition metals has been intensively investigated. For example, precursors [(dtc)₂Mo₂S₂(µ-S)₂] (dtc = S₂CNEt₂) (Hidai et al., 1999; Lang et al., 2003) and [Cp^x₂Mo₂S₂(µ-S)₂] (Cp^x = pentamethyl-, pentaethyl- or pentabutyl-cyclopentadienyl) (Curtis et al., 1997; Stiefel et al., 1985) and [Et₄N]₂[(edt)₂Mo₂S₂(µ-S)₂] (edt = ethanedithiolate) (Wu et al., 1990) were shown to react with transition metals to form both incomplete [Mo₂MS₄] and complete [Mo₂M₂S₄] cubane-like clusters. We report herein the formation of a complete cubane-like [Mo₂Cu₂S₄] by using [(i-C₃H₇)₂NCS₂]₂Mo₂S₄ as the starting material to react with two equivalents of CuBr.

The title molecule contains one [(i-C₃H₇)₂NCS₂]₂Mo₂S₄ moiety and two CuBr units, which are assembled into a distorted Mo₂Cu₂S₄ cubane-like core (Fig. 1). The formal oxidation states for each Mo and Cu remain + 5 and + 1, respectively. Each Mo center is coordinated by three µ₃-S atoms, and the two S atoms of an [(i-C₃H₇)₂NCS₂] group, forming a distorted square pyramidal geometry, while each Cu atom is tetrahedrally coordinated by three µ₃-S atoms and a terminal bromide. The Mo-S bonds are in the range of 2.1621 (19)-2.4465 (18) Å, due to the different S atoms coordinated. The Cu-S(terminal) bonds [average value: 2.436 (2) Å] are longer than the other Cu-S bonds [average value: 2.211 (2) Å]. The Mo···Mo [2.7874 (10) Å] and Mo···Cu [average value: 2.8114 (15) Å] distances and the Cu-Br bonds [average value: 2.2812 (15) Å] have normal values. Intramolecular O-H···S hydrogen bonds (Table 1) may be effective in the stabilization of the structure.

Related literature top

For sulfido-bridged dinuclear complexes with an M₂S₄ core (M = Mo, W), see: Hidai et al. (1999); Lang et al. (2003); Curtis et al. (1997); Stiefel et al. (1985); Wu et al. (1990).

Experimental top

For the preparation of the title compound, [(i-C₃H₇)₂NCS₂]₂Mo₂S₄ (0.49 g, 0.5 mmol), and CuBr (0.144 g, 1.0 mmol) were added into CH₂Cl₂ solution (20 ml). The mixture was stirred at room temperature for 0.5 h, and the dark-red suspension gradually turned into dark red solution, and then filtered. The filtrate was layered with isopropyl alcohol (30 ml) to produce dark red crystals in 4 d.

Computing details top

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.

(I) top

Crystal data top

[Cu₂Mo₂Br₂(C₇H₁₄NS₂)₂S₄]·2C₃H₈O	Z = 2
M_r = 1079.91	F(000) = 1068
Triclinic, P1	D_x = 1.962 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.515 (3) Å	Cell parameters from 6125 reflections
b = 12.734 (3) Å	θ = 3.3–25.4°
c = 12.759 (3) Å	µ = 4.48 mm⁻¹
α = 107.76 (3)°	T = 291 K
β = 108.26 (3)°	Block, dark red
γ = 90.12 (3)°	0.30 × 0.29 × 0.20 mm
V = 1828.2 (9) Å³

Data collection top

Rigaku Mercury diffractometer	6703 independent reflections
Radiation source: fine-focus sealed tube	5814 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 25.4°, θ_min = 3.3°
Absorption correction: multi-scan (Jacobson, 1998)	h = −15→15
T_min = 0.284, T_max = 0.408	k = −15→15
17918 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0376P)² + 11.7921P] where P = (F_o² + 2F_c²)/3
6703 reflections	(Δ/σ)_max = 0.006
353 parameters	Δρ_max = 1.90 e Å⁻³
10 restraints	Δρ_min = −2.13 e Å⁻³

Crystal data top

[Cu₂Mo₂Br₂(C₇H₁₄NS₂)₂S₄]·2C₃H₈O	γ = 90.12 (3)°
M_r = 1079.91	V = 1828.2 (9) Å³
Triclinic, P1	Z = 2
a = 12.515 (3) Å	Mo Kα radiation
b = 12.734 (3) Å	µ = 4.48 mm⁻¹
c = 12.759 (3) Å	T = 291 K
α = 107.76 (3)°	0.30 × 0.29 × 0.20 mm
β = 108.26 (3)°

Data collection top

Rigaku Mercury diffractometer	6703 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	5814 reflections with I > 2σ(I)
T_min = 0.284, T_max = 0.408	R_int = 0.032
17918 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	10 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0376P)² + 11.7921P] where P = (F_o² + 2F_c²)/3
6703 reflections	Δρ_max = 1.90 e Å⁻³
353 parameters	Δρ_min = −2.13 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.

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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	1.00881 (5)	0.18736 (4)	0.39883 (5)	0.02348 (15)
Mo2	1.16712 (5)	0.20599 (5)	0.29120 (5)	0.02768 (16)
Cu1	1.12203 (10)	0.00501 (8)	0.33253 (10)	0.0544 (3)
Cu2	1.23373 (9)	0.24097 (8)	0.53604 (10)	0.0517 (3)
Br1	1.13513 (7)	−0.18080 (6)	0.29790 (7)	0.0441 (2)
Br2	1.37543 (7)	0.30267 (8)	0.71075 (7)	0.0535 (3)
S1	1.09552 (15)	0.10190 (15)	0.51854 (15)	0.0308 (4)
S2	1.29693 (17)	0.12006 (18)	0.3783 (2)	0.0473 (5)
S3	1.13192 (15)	0.34620 (14)	0.44228 (15)	0.0301 (4)
S4	1.00310 (14)	0.07858 (14)	0.21230 (14)	0.0281 (4)
S5	1.17527 (16)	0.15164 (14)	0.09288 (15)	0.0323 (4)
S6	1.28036 (15)	0.35219 (14)	0.27486 (15)	0.0311 (4)
S7	0.81395 (14)	0.10577 (14)	0.33380 (16)	0.0327 (4)
S8	0.90078 (15)	0.32398 (14)	0.48497 (16)	0.0325 (4)
O1	0.6199 (7)	0.1776 (6)	−0.1619 (6)	0.087 (2)
H1D	0.6271	0.1595	−0.2265	0.131*
O2	1.0055 (6)	0.3083 (5)	0.1913 (6)	0.0697 (19)
H2D	1.0646	0.2930	0.1781	0.104*
N1	0.6852 (5)	0.2439 (4)	0.4372 (5)	0.0284 (12)
N2	1.3096 (5)	0.3023 (5)	0.0653 (5)	0.0293 (13)
C1	0.5412 (6)	0.1342 (7)	0.2459 (6)	0.0413 (18)
H1A	0.5335	0.2023	0.2279	0.062*
H1B	0.4691	0.0901	0.2127	0.062*
H1C	0.5947	0.0940	0.2140	0.062*
C2	0.5971 (7)	0.0577 (6)	0.4167 (8)	0.046 (2)
H2A	0.6226	0.0806	0.5003	0.069*
H2B	0.6520	0.0160	0.3886	0.069*
H2C	0.5260	0.0122	0.3862	0.069*
C3	0.5824 (6)	0.1597 (6)	0.3769 (7)	0.0349 (16)
H3A	0.5220	0.1956	0.4033	0.042*
C4	0.6128 (7)	0.4224 (6)	0.4354 (7)	0.0429 (19)
H4A	0.6557	0.4262	0.3859	0.064*
H4B	0.6087	0.4959	0.4831	0.064*
H4C	0.5377	0.3876	0.3883	0.064*
C5	0.6097 (8)	0.3443 (7)	0.5956 (8)	0.050 (2)
H5A	0.6503	0.3014	0.6423	0.075*
H5B	0.5345	0.3081	0.5516	0.075*
H5C	0.6056	0.4169	0.6454	0.075*
C6	0.6703 (6)	0.3545 (6)	0.5132 (6)	0.0298 (15)
H6A	0.7460	0.3928	0.5609	0.036*
C7	0.7831 (6)	0.2252 (5)	0.4229 (6)	0.0287 (15)
C8	1.1642 (8)	0.2257 (9)	−0.1322 (7)	0.063 (3)
H8A	1.1360	0.2969	−0.1193	0.094*
H8B	1.1222	0.1780	−0.1100	0.094*
H8C	1.1559	0.1935	−0.2132	0.094*
C9	1.3407 (9)	0.1315 (7)	−0.0753 (8)	0.061 (3)
H9A	1.4192	0.1456	−0.0281	0.091*
H9B	1.3342	0.0982	−0.1557	0.091*
H9C	1.3022	0.0820	−0.0518	0.091*
C10	1.2881 (7)	0.2392 (6)	−0.0598 (6)	0.0401 (19)
H10A	1.3274	0.2847	−0.0889	0.048*
C11	1.3276 (8)	0.4937 (7)	0.0623 (9)	0.056 (2)
H11A	1.2572	0.5032	0.0775	0.084*
H11B	1.3132	0.4691	−0.0203	0.084*
H11C	1.3750	0.5630	0.0975	0.084*
C12	1.4996 (7)	0.3893 (7)	0.0935 (7)	0.046 (2)
H12A	1.5341	0.3352	0.1281	0.069*
H12B	1.5484	0.4578	0.1287	0.069*
H12C	1.4879	0.3629	0.0113	0.069*
C13	1.3864 (6)	0.4082 (6)	0.1130 (6)	0.0337 (16)
H13A	1.4011	0.4361	0.1974	0.040*
C14	1.2634 (6)	0.2720 (5)	0.1317 (6)	0.0281 (15)
C15	0.7206 (16)	0.1461 (12)	0.0386 (12)	0.041 (3)*	0.733 (12)
H15A	0.7706	0.0973	0.0688	0.061*	0.733 (12)
H15B	0.6436	0.1170	0.0193	0.061*	0.733 (12)
H15C	0.7353	0.2182	0.0964	0.061*	0.733 (12)
C15A	0.722 (4)	0.186 (5)	0.057 (3)	0.041 (3)*	0.267 (12)
H15D	0.7931	0.2152	0.1172	0.061*	0.267 (12)
H15E	0.6914	0.1219	0.0661	0.061*	0.267 (12)
H15F	0.6700	0.2418	0.0613	0.061*	0.267 (12)
C16	0.8461 (8)	0.2073 (9)	−0.0314 (8)	0.039 (3)	0.733 (12)
H16A	0.8528	0.2791	0.0251	0.058*	0.733 (12)
H16B	0.8590	0.2158	−0.0989	0.058*	0.733 (12)
H16C	0.9012	0.1639	0.0017	0.058*	0.733 (12)
C16A	0.750 (3)	0.181 (5)	0.0666 (18)	0.039 (3)	0.267 (12)
H16D	0.8166	0.1527	0.1055	0.058*	0.267 (12)
H16E	0.6846	0.1478	0.0724	0.058*	0.267 (12)
H16F	0.7567	0.2603	0.1025	0.058*	0.267 (12)
C17	0.7390 (11)	0.1546 (12)	−0.0634 (10)	0.092 (4)
H17	0.7484	0.0778	−0.1029	0.111*
C18	0.8873 (8)	0.4760 (11)	0.2435 (8)	0.080 (4)
H18A	0.8899	0.5548	0.2593	0.120*
H18B	0.8831	0.4585	0.3103	0.120*
H18C	0.8218	0.4401	0.1775	0.120*
C19	1.0116 (11)	0.4568 (14)	0.1142 (12)	0.059 (4)	0.733 (12)
H19A	1.0792	0.4282	0.1019	0.088*	0.733 (12)
H19B	1.0174	0.5354	0.1280	0.088*	0.733 (12)
H19C	0.9474	0.4214	0.0464	0.088*	0.733 (12)
C19A	0.991 (3)	0.388 (4)	0.100 (4)	0.059 (4)	0.267 (12)
H19D	0.9542	0.4360	0.0569	0.088*	0.267 (12)
H19E	0.9475	0.3167	0.0671	0.088*	0.267 (12)
H19F	1.0654	0.3808	0.0950	0.088*	0.267 (12)
C20	0.9974 (10)	0.4343 (10)	0.2164 (10)	0.083 (3)
H20	1.0628	0.4732	0.2846	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0218 (3)	0.0244 (3)	0.0245 (3)	−0.0001 (2)	0.0092 (2)	0.0066 (2)
Mo2	0.0320 (3)	0.0283 (3)	0.0232 (3)	−0.0066 (2)	0.0126 (2)	0.0052 (2)
Cu1	0.0570 (7)	0.0372 (6)	0.0485 (6)	0.0155 (5)	−0.0029 (5)	0.0061 (5)
Cu2	0.0422 (6)	0.0401 (6)	0.0523 (6)	−0.0043 (4)	−0.0116 (5)	0.0145 (5)
Br1	0.0499 (5)	0.0361 (4)	0.0474 (5)	0.0070 (4)	0.0162 (4)	0.0146 (4)
Br2	0.0384 (5)	0.0843 (7)	0.0297 (4)	−0.0176 (4)	0.0042 (3)	0.0146 (4)
S1	0.0307 (9)	0.0365 (9)	0.0284 (9)	−0.0022 (7)	0.0110 (7)	0.0139 (8)
S2	0.0355 (11)	0.0513 (12)	0.0539 (13)	−0.0013 (9)	0.0220 (10)	0.0076 (10)
S3	0.0314 (9)	0.0260 (9)	0.0325 (9)	−0.0032 (7)	0.0133 (8)	0.0061 (7)
S4	0.0302 (9)	0.0285 (9)	0.0240 (8)	−0.0036 (7)	0.0095 (7)	0.0057 (7)
S5	0.0387 (10)	0.0319 (9)	0.0249 (9)	−0.0102 (7)	0.0161 (8)	0.0017 (7)
S6	0.0368 (10)	0.0311 (9)	0.0244 (8)	−0.0107 (7)	0.0157 (7)	0.0019 (7)
S7	0.0233 (9)	0.0280 (9)	0.0390 (10)	−0.0016 (7)	0.0123 (8)	−0.0022 (8)
S8	0.0265 (9)	0.0267 (9)	0.0405 (10)	−0.0028 (7)	0.0152 (8)	0.0015 (8)
O1	0.117 (7)	0.081 (5)	0.064 (5)	−0.019 (5)	0.042 (5)	0.010 (4)
O2	0.081 (5)	0.060 (4)	0.067 (4)	0.012 (4)	0.020 (4)	0.024 (4)
N1	0.026 (3)	0.026 (3)	0.029 (3)	−0.002 (2)	0.008 (2)	0.003 (2)
N2	0.033 (3)	0.033 (3)	0.023 (3)	−0.002 (2)	0.016 (2)	0.004 (2)
C1	0.033 (4)	0.042 (4)	0.039 (4)	0.000 (3)	0.004 (3)	0.007 (4)
C2	0.039 (5)	0.041 (4)	0.057 (5)	−0.007 (4)	0.011 (4)	0.021 (4)
C3	0.022 (4)	0.035 (4)	0.043 (4)	0.000 (3)	0.012 (3)	0.004 (3)
C4	0.046 (5)	0.037 (4)	0.044 (5)	0.011 (4)	0.014 (4)	0.012 (4)
C5	0.060 (6)	0.044 (5)	0.057 (5)	0.005 (4)	0.037 (5)	0.011 (4)
C6	0.027 (4)	0.032 (4)	0.028 (4)	0.004 (3)	0.012 (3)	0.001 (3)
C7	0.033 (4)	0.026 (3)	0.028 (4)	0.003 (3)	0.014 (3)	0.006 (3)
C8	0.057 (6)	0.090 (7)	0.031 (5)	−0.026 (5)	−0.002 (4)	0.022 (5)
C9	0.077 (7)	0.053 (5)	0.049 (5)	−0.005 (5)	0.041 (5)	−0.010 (4)
C10	0.053 (5)	0.045 (4)	0.020 (4)	−0.012 (4)	0.016 (3)	0.002 (3)
C11	0.064 (6)	0.043 (5)	0.074 (6)	0.002 (4)	0.032 (5)	0.026 (5)
C12	0.045 (5)	0.044 (5)	0.051 (5)	−0.007 (4)	0.022 (4)	0.014 (4)
C13	0.040 (4)	0.032 (4)	0.031 (4)	−0.012 (3)	0.016 (3)	0.008 (3)
C14	0.029 (4)	0.028 (4)	0.027 (4)	−0.002 (3)	0.010 (3)	0.007 (3)
C16	0.020 (5)	0.068 (7)	0.018 (4)	−0.017 (5)	0.002 (4)	0.005 (4)
C16A	0.020 (5)	0.068 (7)	0.018 (4)	−0.017 (5)	0.002 (4)	0.005 (4)
C17	0.089 (9)	0.125 (11)	0.087 (9)	0.027 (8)	0.045 (7)	0.051 (8)
C18	0.056 (6)	0.154 (11)	0.031 (5)	−0.012 (7)	0.010 (4)	0.034 (6)
C19	0.047 (7)	0.092 (12)	0.072 (8)	0.031 (8)	0.028 (6)	0.065 (10)
C19A	0.047 (7)	0.092 (12)	0.072 (8)	0.031 (8)	0.028 (6)	0.065 (10)
C20	0.093 (9)	0.084 (8)	0.054 (6)	0.015 (7)	0.010 (6)	0.011 (6)

Geometric parameters (Å, º) top

Mo1—Mo2	2.7874 (10)	C8—H8B	0.9600
Mo1—Cu1	2.7715 (14)	C8—H8C	0.9600
Mo1—Cu2	2.7618 (16)	C9—C10	1.508 (12)
Mo1—S1	2.1621 (19)	C9—H9A	0.9600
Mo1—S3	2.3535 (19)	C9—H9B	0.9600
Mo1—S4	2.3386 (19)	C9—H9C	0.9600
Mo1—S7	2.4310 (19)	C10—N2	1.486 (8)
Mo1—S8	2.4160 (19)	C10—H10A	0.9800
Mo2—Cu1	2.8547 (14)	C11—C13	1.510 (11)
Mo2—Cu2	2.8582 (15)	C11—H11A	0.9600
Mo2—S2	2.166 (2)	C11—H11B	0.9600
Mo2—S3	2.352 (2)	C11—H11C	0.9600
Mo2—S4	2.356 (2)	C12—C13	1.522 (10)
Mo2—S5	2.4465 (18)	C12—H12A	0.9600
Mo2—S6	2.4349 (18)	C12—H12B	0.9600
Cu1—Br1	2.2867 (14)	C12—H12C	0.9600
Cu1—S1	2.444 (2)	C13—N2	1.497 (8)
Cu1—S2	2.437 (2)	C13—H13A	0.9800
Cu1—S4	2.213 (2)	C14—N2	1.306 (8)
Cu2—Br2	2.2756 (16)	C15—H15A	0.9600
Cu2—S1	2.383 (2)	C15—H15B	0.9600
Cu2—S2	2.481 (3)	C15—H15C	0.9600
Cu2—S3	2.209 (2)	C15A—H15D	0.9600
S5—C14	1.731 (7)	C15A—H15E	0.9600
S6—C14	1.744 (7)	C15A—H15F	0.9600
S7—C7	1.726 (7)	C16—H16A	0.9600
S8—C7	1.741 (7)	C16—H16B	0.9600
O1—H1D	0.8200	C16—H16C	0.9600
O2—H2D	0.8200	C16A—H16D	0.9600
C1—C3	1.515 (10)	C16A—H16E	0.9600
C1—H1A	0.9600	C16A—H16F	0.9600
C1—H1B	0.9600	C17—C16	1.378 (15)
C1—H1C	0.9600	C17—C15	1.425 (17)
C2—C3	1.525 (10)	C17—C15A	1.544 (19)
C2—H2A	0.9600	C17—C16A	1.547 (18)
C2—H2B	0.9600	C17—O1	1.715 (15)
C2—H2C	0.9600	C17—H17	0.9800
C3—N1	1.505 (8)	C18—H18A	0.9600
C3—H3A	0.9800	C18—H18B	0.9600
C4—C6	1.526 (10)	C18—H18C	0.9600
C4—H4A	0.9600	C19—H19A	0.9600
C4—H4B	0.9600	C19—H19B	0.9600
C4—H4C	0.9600	C19—H19C	0.9600
C5—C6	1.510 (10)	C19A—H19D	0.9600
C5—H5A	0.9600	C19A—H19E	0.9600
C5—H5B	0.9600	C19A—H19F	0.9600
C5—H5C	0.9600	C20—C19A	1.40 (4)
C6—N1	1.497 (8)	C20—C19	1.479 (17)
C6—H6A	0.9800	C20—O2	1.546 (13)
C7—N1	1.306 (8)	C20—C18	1.579 (12)
C8—C10	1.513 (12)	C20—H20	0.9800
C8—H8A	0.9600

S1—Mo1—S4	107.30 (7)	C10—C8—H8B	109.5
S1—Mo1—S3	105.60 (7)	H8A—C8—H8B	109.5
S4—Mo1—S3	104.32 (7)	C10—C8—H8C	109.5
S1—Mo1—S8	110.87 (7)	H8A—C8—H8C	109.5
S4—Mo1—S8	137.84 (7)	H8B—C8—H8C	109.5
S3—Mo1—S8	82.15 (6)	C6—C5—H5A	109.5
S1—Mo1—S7	102.40 (7)	C6—C5—H5B	109.5
S4—Mo1—S7	83.56 (7)	H5A—C5—H5B	109.5
S3—Mo1—S7	146.89 (7)	C6—C5—H5C	109.5
S8—Mo1—S7	71.52 (6)	H5A—C5—H5C	109.5
S1—Mo1—Cu2	56.33 (6)	H5B—C5—H5C	109.5
S4—Mo1—Cu2	107.39 (6)	C3—C2—H2A	109.5
S3—Mo1—Cu2	50.40 (6)	C3—C2—H2B	109.5
S8—Mo1—Cu2	108.24 (6)	H2A—C2—H2B	109.5
S7—Mo1—Cu2	157.85 (6)	C3—C2—H2C	109.5
S1—Mo1—Cu1	57.82 (6)	H2A—C2—H2C	109.5
S4—Mo1—Cu1	50.46 (5)	H2B—C2—H2C	109.5
S3—Mo1—Cu1	106.97 (6)	C3—C1—H1A	109.5
S8—Mo1—Cu1	166.67 (6)	C3—C1—H1B	109.5
S7—Mo1—Cu1	102.73 (6)	H1A—C1—H1B	109.5
Cu2—Mo1—Cu1	72.36 (5)	C3—C1—H1C	109.5
S1—Mo1—Mo2	101.97 (5)	H1A—C1—H1C	109.5
S4—Mo1—Mo2	53.87 (5)	H1B—C1—H1C	109.5
S3—Mo1—Mo2	53.66 (5)	C6—C4—H4A	109.5
S8—Mo1—Mo2	130.76 (5)	C6—C4—H4B	109.5
S7—Mo1—Mo2	135.61 (5)	H4A—C4—H4B	109.5
Cu2—Mo1—Mo2	62.00 (4)	C6—C4—H4C	109.5
Cu1—Mo1—Mo2	61.80 (4)	H4A—C4—H4C	109.5
S2—Mo2—S3	105.05 (8)	H4B—C4—H4C	109.5
S2—Mo2—S4	104.02 (8)	N2—C13—C11	109.8 (6)
S3—Mo2—S4	103.81 (7)	N2—C13—C12	111.4 (6)
S2—Mo2—S6	101.58 (8)	C11—C13—C12	112.6 (6)
S3—Mo2—S6	85.72 (6)	N2—C13—H13A	107.6
S4—Mo2—S6	149.13 (7)	C11—C13—H13A	107.6
S2—Mo2—S5	103.59 (8)	C12—C13—H13A	107.6
S3—Mo2—S5	146.24 (7)	N1—C7—S7	126.4 (5)
S4—Mo2—S5	86.05 (7)	N1—C7—S8	123.9 (5)
S6—Mo2—S5	71.31 (7)	S7—C7—S8	109.6 (4)
S2—Mo2—Mo1	98.63 (6)	N2—C10—C9	111.9 (6)
S3—Mo2—Mo1	53.70 (5)	N2—C10—C8	112.6 (7)
S4—Mo2—Mo1	53.29 (5)	C9—C10—C8	113.5 (7)
S6—Mo2—Mo1	138.23 (5)	N2—C10—H10A	106.1
S5—Mo2—Mo1	137.45 (5)	C9—C10—H10A	106.1
S2—Mo2—Cu1	56.09 (6)	C8—C10—H10A	106.1
S3—Mo2—Cu1	104.42 (5)	N1—C6—C5	112.3 (6)
S4—Mo2—Cu1	49.13 (5)	N1—C6—C4	108.4 (6)
S6—Mo2—Cu1	156.98 (6)	C5—C6—C4	113.6 (6)
S5—Mo2—Cu1	106.21 (6)	N1—C6—H6A	107.4
Mo1—Mo2—Cu1	58.83 (4)	C5—C6—H6A	107.4
S2—Mo2—Cu2	57.22 (7)	C4—C6—H6A	107.4
S3—Mo2—Cu2	49.00 (5)	N1—C3—C1	112.6 (6)
S4—Mo2—Cu2	103.90 (6)	N1—C3—C2	112.3 (6)
S6—Mo2—Cu2	104.35 (6)	C1—C3—C2	114.5 (6)
S5—Mo2—Cu2	159.79 (6)	N1—C3—H3A	105.5
Mo1—Mo2—Cu2	58.56 (4)	C1—C3—H3A	105.5
Cu1—Mo2—Cu2	69.75 (5)	C2—C3—H3A	105.5
S4—Cu1—Br1	124.95 (7)	N2—C14—S5	126.6 (5)
S4—Cu1—S2	100.02 (9)	N2—C14—S6	123.5 (5)
Br1—Cu1—S2	116.22 (8)	S5—C14—S6	109.9 (4)
S4—Cu1—S1	102.17 (8)	C16—C17—C15	108.4 (12)
Br1—Cu1—S1	114.44 (7)	C16—C17—C15A	100 (2)
S2—Cu1—S1	93.70 (8)	C16—C17—C16A	90.1 (16)
S4—Cu1—Mo1	54.58 (5)	C16—C17—O1	125.5 (10)
Br1—Cu1—Mo1	148.85 (6)	C15—C17—O1	113.2 (11)
S2—Cu1—Mo1	92.75 (7)	C15A—C17—O1	108.3 (18)
S1—Cu1—Mo1	48.48 (5)	C16A—C17—O1	121 (2)
S4—Cu1—Mo2	53.62 (6)	C16—C17—H17	102.0
Br1—Cu1—Mo2	150.08 (6)	C15—C17—H17	102.0
S2—Cu1—Mo2	47.51 (6)	C15A—C17—H17	120.4
S1—Cu1—Mo2	93.37 (6)	C16A—C17—H17	115.2
Mo1—Cu1—Mo2	59.37 (3)	O1—C17—H17	102.0
S3—Cu2—Br2	125.87 (7)	C19A—C20—O2	72.2 (18)
S3—Cu2—S1	103.11 (8)	C19—C20—O2	104.5 (10)
Br2—Cu2—S1	115.75 (7)	C19A—C20—C18	118.1 (18)
S3—Cu2—S2	99.62 (9)	C19—C20—C18	113.8 (9)
Br2—Cu2—S2	112.85 (8)	O2—C20—C18	115.1 (10)
S1—Cu2—S2	94.10 (8)	C19A—C20—H20	129.3
S3—Cu2—Mo1	55.17 (5)	C19—C20—H20	107.7
Br2—Cu2—Mo1	153.00 (6)	O2—C20—H20	107.7
S1—Cu2—Mo1	49.02 (5)	C18—C20—H20	107.7
S2—Cu2—Mo1	92.04 (7)	C20—C18—H18A	109.5
S3—Cu2—Mo2	53.47 (6)	C20—C18—H18B	109.5
Br2—Cu2—Mo2	146.41 (6)	H18A—C18—H18B	109.5
S1—Cu2—Mo2	94.60 (6)	C20—C18—H18C	109.5
S2—Cu2—Mo2	47.21 (6)	H18A—C18—H18C	109.5
Mo1—Cu2—Mo2	59.44 (4)	H18B—C18—H18C	109.5
Cu1—S4—Mo1	74.96 (6)	C7—N1—C6	120.0 (5)
Cu1—S4—Mo2	77.26 (7)	C7—N1—C3	123.1 (6)
Mo1—S4—Mo2	72.84 (6)	C6—N1—C3	116.9 (5)
C14—S6—Mo2	89.4 (2)	C14—N2—C10	124.0 (6)
C7—S7—Mo1	89.2 (2)	C14—N2—C13	120.0 (5)
C7—S8—Mo1	89.3 (2)	C10—N2—C13	116.0 (5)
Mo2—S2—Cu1	76.40 (7)	C17—O1—H1D	109.5
Mo2—S2—Cu2	75.57 (7)	C20—O2—H2D	109.5
Cu1—S2—Cu2	83.22 (8)	C17—C15—H15A	109.5
Mo1—S1—Cu2	74.65 (6)	C17—C15—H15B	109.5
Mo1—S1—Cu1	73.70 (6)	C17—C15—H15C	109.5
Cu2—S1—Cu1	85.16 (7)	C20—C19—H19A	109.5
C14—S5—Mo2	89.3 (2)	C20—C19—H19B	109.5
Cu2—S3—Mo2	77.53 (7)	H19A—C19—H19B	109.5
Cu2—S3—Mo1	74.43 (6)	C20—C19—H19C	109.5
Mo2—S3—Mo1	72.65 (6)	H19A—C19—H19C	109.5
C10—C9—H9A	109.5	H19B—C19—H19C	109.5
C10—C9—H9B	109.5	C17—C16—H16A	109.5
H9A—C9—H9B	109.5	C17—C16—H16B	109.5
C10—C9—H9C	109.5	C17—C16—H16C	109.5
H9A—C9—H9C	109.5	C20—C19A—H19D	109.5
H9B—C9—H9C	109.5	C20—C19A—H19E	109.5
C13—C12—H12A	109.5	H19D—C19A—H19E	109.5
C13—C12—H12B	109.5	C20—C19A—H19F	109.5
H12A—C12—H12B	109.5	H19D—C19A—H19F	109.5
C13—C12—H12C	109.5	H19E—C19A—H19F	109.5
H12A—C12—H12C	109.5	C17—C15A—H15D	109.5
H12B—C12—H12C	109.5	C17—C15A—H15E	109.5
C13—C11—H11A	109.5	H15D—C15A—H15E	109.5
C13—C11—H11B	109.5	C17—C15A—H15F	109.5
H11A—C11—H11B	109.5	H15D—C15A—H15F	109.5
C13—C11—H11C	109.5	H15E—C15A—H15F	109.5
H11A—C11—H11C	109.5	C17—C16A—H16D	109.5
H11B—C11—H11C	109.5	C17—C16A—H16E	109.5
C10—C8—H8A	109.5	C17—C16A—H16F	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2D···S5	0.82	2.47	3.199 (8)	149
O2—H2D···S6	0.82	2.59	3.258 (8)	139

Experimental details

Crystal data
Chemical formula	[Cu₂Mo₂Br₂(C₇H₁₄NS₂)₂S₄]·2C₃H₈O
M_r	1079.91
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	12.515 (3), 12.734 (3), 12.759 (3)
α, β, γ (°)	107.76 (3), 108.26 (3), 90.12 (3)
V (Å³)	1828.2 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.48
Crystal size (mm)	0.30 × 0.29 × 0.20

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.284, 0.408
No. of measured, independent and observed [I > 2σ(I)] reflections	17918, 6703, 5814
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.121, 1.12
No. of reflections	6703
No. of parameters	353
No. of restraints	10
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0376P)² + 11.7921P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.90, −2.13

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).