cis-Di-μ-oxido-bis­[(N,N-diethyl­dithio­carbamato-κ2S,S′)oxidomolybdenum(V)](Mo—Mo) tetra­hydro­furan monosolvate

Fernandes, J.A.; Almeida Paz, F.A.; Romão, C.C.

doi:10.1107/S1600536811003187

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages m288-m289

doi:10.1107/S1600536811003187

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cis-Di-μ-oxido-bis[(N,N-diethyldithiocarbamato-κ²S,S′)oxidomolybdenum(V)](Mo—Mo) tetrahydrofuran monosolvate

José A. Fernandes,^a Filipe A. Almeida Paz ^a ^* and Carlos C. Romão ^b

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bInstituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, EAN, 2780-157 Oeiras, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 14 December 2010; accepted 24 January 2011; online 29 January 2011)

The title compound, [Mo₂(C₅H₁₀NS₂)₂O₄]·C₄H₈O, can be readily prepared in tetrahydrofuran (THF) by an oxidation reaction between the Mo^IV precursor [MoO(S₂CNEt₂)₂] with [ReMeO₃]. The compound is an axially symmetric Mo^V dimer (2 symmetry), in which the metal atoms exhibit a distorted square-pyramidal coordination environment. A THF molecule was found to be equally disordered over two symmetry-related sites (around a twofold rotation axis), trans-coordinated to the apical oxido group and weakly interacting with the Mo^V atoms [Mo—O = 2.6213 (19) Å]. In the crystal, some weak C—H⋯O interactions occur between the terminal oxido and neighbouring —CH₃ groups of an adjacent [Mo(μ-O)O(S₂CNEt₂)]₂ unit.

Related literature

For applications of dithiocarbamate compounds, see: Tiekink (2008 ); Zhao et al. (2005 ). For the synthesis of the Mo^IV precursor, [MoO(S₂CNEt₂)₂], see: Jowitt & Mitchell (1969 ). For the synthesis of unsolvated [Mo(μ-O)O(S₂CNEt₂)]₂, see: Ricard et al. (1975 ). For previous reports on dithiocarbamate compounds from our research groups, see: Drew et al. (1998 ); Romão & Royo (2002 ); Almeida Paz et al. (2003 ). For molybdenum dimers with long Mo—O_THF bonds, see: Cotton et al. (1978 , 1992 ); Cotton & Su (1995 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Mo₂(C₅H₁₀NS₂)₂O₄]·C₄H₈O
M_r = 624.50
Monoclinic, C 2/c
a = 12.8695 (7) Å
b = 12.6025 (7) Å
c = 14.4579 (8) Å
β = 94.184 (3)°
V = 2338.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 150 K
0.12 × 0.12 × 0.08 mm

Data collection

Bruker X8 KappaCCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.845, T_max = 0.893
48139 measured reflections
5649 independent reflections
4661 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.054
S = 1.03
5649 reflections
149 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.96 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—Mo1ⁱ	2.5591 (2)
Mo1—S1	2.4788 (4)
Mo1—S2	2.4680 (4)
Mo1—O1	1.9586 (9)
Mo1—O1ⁱ	1.9472 (9)
Mo1—O2	1.6826 (10)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O2ⁱⁱ	0.99	2.57	3.2687 (17)	127
C4—H4B⋯O2ⁱⁱⁱ	0.99	2.49	3.2443 (17)	133
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003187/pk2294sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003187/pk2294Isup2.hkl

checkCIF report

Comment top

Dithiocarbamates and their metal complexes have several applications in the treatment of some diseases (e.g., Wilson's disease and alcoholism) and industry processes (e.g., vulcanization of rubber and pesticides) (Tiekink, 2008). These molecules have already been used in the functionalization of gold nanoparticles (Zhao et al., 2005). Following our interest in the preparation of dithiocarbamate metal complexes (Drew et al., 1998; Romão et al., 2002; Almeida Paz et al., 2003), we attempted the preparation of a heterobimetallic compound from the reaction of [MoO(S₂CNEt₂)₂] and [ReMeO₃]. The sole product was an oxidation product whose structure we wish to report here: [Mo(µ-O)O(S₂CNEt₂)]₂^.THF. We note that the corresponding unsolvated compound, [Mo(µ-O)O(S₂CNEt₂)]₂, was previously reported by Ricard et al. (1975).

The title compound (see Scheme) is an axially symmetrical dimer of molybdenum(V) formed by way of two µ-oxido bridges, and with a short distance interaction with a tetrahydrofuran (THF) molecule, which was found to be disordered over two sites (symmetry-related by a twofold rotation axis). The asymmetric unit comprises one half of the molybdenum(V) dimer, and a half-occupied THF molecule (Figure 1). The coordination geometry around the metal centre can be envisaged as a highly distorted square pyramid (Table 1) with a terminal oxido ligand at the apex while the basal plane is occupied by two symmetry-equivalent µ-oxido bridges and a chelating dithiocarbamato ligand {MoO₃S₂}. The dimer also has a Mo—Mo direct bond with an intermetallic distance of 2.5591 (2) Å. A weakly-bonded THF molecule is trans to the apical oxido group.

The disordered THF molecule interacts weakly with the metal centre with the measured Mo···O distance being considerably longer [2.6213 (19) Å] than those typically found in related structures. Nevertheless, from a survey in the Cambridge Structural Database (Allen, 2002) we found 4 structures which have longer Mo—O_THF bonds than those of the title compound. These compounds correspond to isostructural dimers, each with four bridging carboxylates or dithiocarboxylates, very short Mo—Mo distances, and with THF acting as an axial ligand (Cotton et al., 1978, 1992, 1995).

Individual [Mo(µ-O)O(S₂CNEt₂)]₂^.THF complexes close pack in the solid state driven by the need to effectively fill the available space (Figure 2). Some weak C—H···O interactions are present connecting the terminal oxido and neighbouring —CH₃ groups of an adjacent [Mo(µ-O)O(S₂CNEt₂)]₂ entity (not shown; see Table 2 for geometrical details).

Related literature top

For applications of dithiocarbamate compounds, see: Tiekink (2008); Zhao et al. (2005). For the synthesis of the Mo^IV precursor, [MoO(S₂CNEt₂)₂], see: Jowitt & Mitchell (1969). For the synthesis of unsolvated [Mo(µ-O)O(S₂CNEt₂)]₂, see: Ricard et al. (1975). For previous reports on dithiocarbamate compounds from our research groups, see: Drew et al. (1998); Romão & Royo (2002); Almeida Paz et al. (2003). For molybdenum dimers with long Mo—O_THF bonds, see: Cotton et al. (1978, 1992, 1995). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The precursor [MoO(S₂CNEt₂)₂] (1) was prepared using a published method (Jowitt & Mitchell, 1969). [ReMeO₃] (MTO) was purchased from Sigma-Aldrich (71–76% of Re content), and used without any further purification. All manipulations were carried out by using standard Schlenk line and drybox techniques in an atmosphere of N₂. THF was distilled from Na/benzophenone.

A solution of MTO (0.18 g, 0.73 mmol) in THF (10 ml) was added to a solution of 1 (0.30 g, 0.73 mmol) in THF (15 ml). After stirring magnetically for 5 h at ambient temperature, a green solution and a green solid were obtained. The volume of the mixture was reduced to half by vacuum evaporation and further precipitation was forced by cooling to -30 °C. The solid product was dissolved in the minimum amount of hot THF and submitted to slow cooling to -30 °C. Yellow crystals of the title compound suitable for single-crystal X-ray diffraction were directly isolated and preserved in N₂ atmosphere prior to data collection.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular unit of the title compound showing all non-hydrogen atoms as thermal ellipsoids drawn at the 40% probability level and hydrogen atoms as small spheres with arbitrary radii. Atoms composing the asymmetric unit are highlighted by showing their respective label. The two possible locations for the disordered THF molecule are depicted with different colours for the bonds. For selected bond lengths see Table 1. Symmetry transformation used to generate equivalent atoms: (i) -x, y, 0.5 - z.

Fig. 2. Crystal packing of the title compound viewed in perspective along the [001] direction of the unit cell. The two possible locations for the disordered THF molecule are depicted with different colours for the bonds (hydrogen atoms associated with these moieties have been omitted for clarity).

cis-Di-µ-oxido-bis[(N,N'-diethyldithiocarbamato- κ²S,S')oxidomolybdenum(V)] tetrahydrofuran monosolvate top

Crystal data top

[Mo₂(C₅H₁₀NS₂)₂O₄]·C₄H₈O	F(000) = 1256
M_r = 624.50	D_x = 1.774 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9063 reflections
a = 12.8695 (7) Å	θ = 2.6–35.3°
b = 12.6025 (7) Å	µ = 1.46 mm⁻¹
c = 14.4579 (8) Å	T = 150 K
β = 94.184 (3)°	Prism, yellow
V = 2338.6 (2) Å³	0.12 × 0.12 × 0.08 mm
Z = 4

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	5649 independent reflections
Radiation source: fine-focus sealed tube	4661 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω and ϕ scans	θ_max = 36.3°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −21→21
T_min = 0.845, T_max = 0.893	k = −20→20
48139 measured reflections	l = −23→24

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0219P)² + 2.1445P] where P = (F_o² + 2F_c²)/3
5649 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.74 e Å⁻³
5 restraints	Δρ_min = −0.96 e Å⁻³

Crystal data top

[Mo₂(C₅H₁₀NS₂)₂O₄]·C₄H₈O	V = 2338.6 (2) Å³
M_r = 624.50	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.8695 (7) Å	µ = 1.46 mm⁻¹
b = 12.6025 (7) Å	T = 150 K
c = 14.4579 (8) Å	0.12 × 0.12 × 0.08 mm
β = 94.184 (3)°

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	5649 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	4661 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.893	R_int = 0.033
48139 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	5 restraints
wR(F²) = 0.054	H-atom parameters constrained
S = 1.03	Δρ_max = 0.74 e Å⁻³
5649 reflections	Δρ_min = −0.96 e Å⁻³
149 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.081183 (8)	0.231212 (9)	0.203909 (7)	0.01717 (3)
S1	0.25495 (3)	0.31525 (3)	0.23038 (2)	0.02555 (7)
S2	0.11812 (3)	0.33069 (4)	0.06297 (2)	0.03297 (9)
O1	−0.06648 (7)	0.24910 (7)	0.16391 (6)	0.02023 (17)
O2	0.11161 (8)	0.10400 (8)	0.18310 (7)	0.0273 (2)
N1	0.30133 (9)	0.43361 (9)	0.08463 (7)	0.0222 (2)
C1	0.23528 (10)	0.36816 (11)	0.12027 (9)	0.0224 (2)
C2	0.40421 (10)	0.45692 (12)	0.13224 (9)	0.0250 (3)
H2A	0.3998	0.4513	0.2001	0.030*
H2B	0.4248	0.5304	0.1179	0.030*
C3	0.48586 (12)	0.38032 (14)	0.10190 (12)	0.0336 (3)
H3A	0.4671	0.3078	0.1187	0.050*
H3B	0.5538	0.3986	0.1328	0.050*
H3C	0.4895	0.3850	0.0345	0.050*
C4	0.27763 (12)	0.48736 (12)	−0.00497 (9)	0.0288 (3)
H4A	0.2232	0.4471	−0.0420	0.035*
H4B	0.3409	0.4887	−0.0400	0.035*
C5	0.24037 (16)	0.59952 (15)	0.00879 (12)	0.0423 (4)
H5A	0.1750	0.5980	0.0396	0.063*
H5B	0.2288	0.6345	−0.0516	0.063*
H5C	0.2931	0.6387	0.0473	0.063*
O3	0.02301 (17)	0.42667 (15)	0.23443 (16)	0.0298 (5)	0.50
C6	0.0064 (3)	0.5996 (3)	0.2983 (3)	0.0398 (8)	0.50
H6X	0.0481	0.6611	0.2799	0.048*	0.50
H6Y	−0.0215	0.6149	0.3589	0.048*	0.50
C7	0.0722 (3)	0.4986 (3)	0.3034 (3)	0.0370 (9)	0.50
H7X	0.1447	0.5143	0.2891	0.044*	0.50
H7Y	0.0732	0.4669	0.3661	0.044*	0.50
C8	−0.0831 (4)	0.5757 (3)	0.2237 (3)	0.0552 (11)	0.50
H8X	−0.1463	0.5508	0.2523	0.066*	0.50
H8Y	−0.1008	0.6391	0.1854	0.066*	0.50
C9	−0.0384 (3)	0.4905 (3)	0.1677 (3)	0.0346 (8)	0.50
H9X	−0.0943	0.4476	0.1353	0.042*	0.50
H9Y	0.0058	0.5209	0.1211	0.042*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01784 (5)	0.01611 (5)	0.01787 (5)	−0.00165 (3)	0.00340 (3)	0.00016 (3)
S1	0.02101 (13)	0.03126 (18)	0.02375 (14)	−0.00642 (12)	−0.00270 (11)	0.00826 (12)
S2	0.02936 (16)	0.0438 (2)	0.02449 (15)	−0.01877 (15)	−0.00690 (12)	0.01249 (14)
O1	0.0200 (4)	0.0193 (4)	0.0216 (4)	−0.0037 (3)	0.0031 (3)	−0.0016 (3)
O2	0.0301 (5)	0.0201 (5)	0.0334 (5)	−0.0007 (4)	0.0140 (4)	−0.0024 (4)
N1	0.0239 (5)	0.0239 (6)	0.0188 (4)	−0.0081 (4)	0.0026 (4)	−0.0002 (4)
C1	0.0219 (5)	0.0235 (6)	0.0216 (5)	−0.0054 (4)	0.0010 (4)	0.0027 (4)
C2	0.0239 (6)	0.0270 (7)	0.0243 (6)	−0.0102 (5)	0.0024 (4)	−0.0024 (5)
C3	0.0262 (6)	0.0337 (8)	0.0412 (8)	−0.0055 (6)	0.0034 (6)	−0.0031 (6)
C4	0.0357 (7)	0.0315 (8)	0.0192 (5)	−0.0125 (6)	0.0027 (5)	0.0032 (5)
C5	0.0556 (11)	0.0344 (9)	0.0356 (8)	−0.0022 (8)	−0.0049 (7)	0.0071 (7)
O3	0.0374 (15)	0.0189 (9)	0.0305 (13)	0.0046 (7)	−0.0149 (9)	−0.0052 (8)
C6	0.0471 (19)	0.0201 (14)	0.054 (2)	−0.0070 (13)	0.0157 (16)	−0.0181 (13)
C7	0.044 (2)	0.0296 (19)	0.036 (2)	−0.0117 (16)	−0.0057 (15)	−0.0132 (16)
C8	0.060 (3)	0.033 (2)	0.074 (3)	0.0083 (18)	0.005 (2)	0.0059 (19)
C9	0.039 (2)	0.0247 (16)	0.038 (2)	0.0112 (15)	−0.0093 (15)	0.0032 (15)

Geometric parameters (Å, º) top

Mo1—Mo1ⁱ	2.5591 (2)	C4—C5	1.510 (3)
Mo1—S1	2.4788 (4)	C4—H4A	0.9900
Mo1—S2	2.4680 (4)	C4—H4B	0.9900
Mo1—O1	1.9586 (9)	C5—H5A	0.9800
Mo1—O1ⁱ	1.9472 (9)	C5—H5B	0.9800
Mo1—O2	1.6826 (10)	C5—H5C	0.9800
Mo1—O3	2.6213 (19)	O3—C9	1.446 (4)
S1—C1	1.7276 (13)	O3—C7	1.457 (4)
S2—C1	1.7322 (13)	O3—Mo1ⁱ	2.972 (2)
O1—Mo1ⁱ	1.9472 (9)	C6—C7	1.527 (5)
O2—Mo1ⁱ	3.4621 (10)	C6—C8	1.549 (5)
N1—C1	1.3161 (16)	C6—H6X	0.9900
N1—C4	1.4739 (17)	C6—H6Y	0.9900
N1—C2	1.4766 (17)	C7—H7X	0.9900
C2—C3	1.515 (2)	C7—H7Y	0.9900
C2—H2A	0.9900	C8—C9	1.485 (5)
C2—H2B	0.9900	C8—H8X	0.9900
C3—H3A	0.9800	C8—H8Y	0.9900
C3—H3B	0.9800	C9—H9X	0.9900
C3—H3C	0.9800	C9—H9Y	0.9900

O1ⁱ—Mo1—O1	96.59 (4)	C5—C4—H4A	109.4
O1—Mo1—O3	70.04 (6)	N1—C4—H4B	109.4
O1ⁱ—Mo1—O3	71.13 (6)	C5—C4—H4B	109.4
O1—Mo1—S1	147.29 (3)	H4A—C4—H4B	108.0
O1ⁱ—Mo1—S1	87.14 (3)	C4—C5—H5A	109.5
O1—Mo1—S2	86.50 (3)	C4—C5—H5B	109.5
O1ⁱ—Mo1—S2	142.17 (3)	H5A—C5—H5B	109.5
O2—Mo1—O1	106.88 (5)	C4—C5—H5C	109.5
O2—Mo1—O1ⁱ	109.05 (5)	H5A—C5—H5C	109.5
O2—Mo1—O3	176.86 (6)	H5B—C5—H5C	109.5
O2—Mo1—S1	102.45 (4)	C9—O3—C7	107.4 (2)
O2—Mo1—S2	105.96 (4)	C9—O3—Mo1	124.0 (2)
S1—Mo1—O3	80.68 (5)	C7—O3—Mo1	125.8 (2)
S2—Mo1—O3	74.70 (5)	C9—O3—Mo1ⁱ	115.1 (2)
S2—Mo1—S1	71.612 (11)	C7—O3—Mo1ⁱ	119.6 (2)
O2—Mo1—Mo1ⁱ	107.62 (3)	Mo1—O3—Mo1ⁱ	54.01 (4)
O1ⁱ—Mo1—Mo1ⁱ	49.26 (3)	C7—C6—C8	104.6 (3)
O1—Mo1—Mo1ⁱ	48.87 (3)	C7—C6—H6X	110.8
S2—Mo1—Mo1ⁱ	130.072 (11)	C8—C6—H6X	110.8
S1—Mo1—Mo1ⁱ	132.947 (10)	C7—C6—H6Y	110.8
Mo1ⁱ—Mo1—O3	70.02 (5)	C8—C6—H6Y	110.8
C1—S1—Mo1	87.29 (4)	H6X—C6—H6Y	108.9
C1—S2—Mo1	87.53 (4)	O3—C7—C6	105.9 (3)
Mo1ⁱ—O1—Mo1	81.87 (4)	C6—C7—Mo1	141.2 (2)
C1—N1—C4	122.27 (11)	O3—C7—H7X	110.6
C1—N1—C2	121.66 (11)	C6—C7—H7X	110.6
C4—N1—C2	116.06 (11)	Mo1—C7—H7X	92.6
N1—C1—S1	123.18 (10)	O3—C7—H7Y	110.6
N1—C1—S2	123.24 (10)	C6—C7—H7Y	110.6
S1—C1—S2	113.54 (7)	Mo1—C7—H7Y	89.4
N1—C1—Mo1	176.95 (11)	H7X—C7—H7Y	108.7
S1—C1—Mo1	56.96 (4)	C9—C8—C6	102.8 (3)
S2—C1—Mo1	56.60 (4)	C9—C8—H8X	111.2
N1—C2—C3	110.82 (11)	C6—C8—H8X	111.2
N1—C2—H2A	109.5	C9—C8—H8Y	111.2
C3—C2—H2A	109.5	C6—C8—H8Y	111.2
N1—C2—H2B	109.5	H8X—C8—H8Y	109.1
C3—C2—H2B	109.5	O3—C9—C8	104.7 (3)
H2A—C2—H2B	108.1	C8—C9—Mo1	138.4 (3)
C2—C3—H3A	109.5	O3—C9—H9X	110.8
C2—C3—H3B	109.5	C8—C9—H9X	110.8
H3A—C3—H3B	109.5	Mo1—C9—H9X	82.1
C2—C3—H3C	109.5	O3—C9—H9Y	110.8
H3A—C3—H3C	109.5	C8—C9—H9Y	110.8
H3B—C3—H3C	109.5	Mo1—C9—H9Y	100.8
N1—C4—C5	111.21 (12)	H9X—C9—H9Y	108.9
N1—C4—H4A	109.4

O2—Mo1—S1—C1	103.85 (6)	O1ⁱ—Mo1—O3—C7	50.7 (3)
O1ⁱ—Mo1—S1—C1	−147.26 (6)	O1—Mo1—O3—C7	155.4 (3)
O1—Mo1—S1—C1	−49.51 (7)	S2—Mo1—O3—C7	−112.8 (3)
S2—Mo1—S1—C1	0.95 (5)	S1—Mo1—O3—C7	−39.4 (3)
Mo1ⁱ—Mo1—S1—C1	−127.18 (5)	Mo1ⁱ—Mo1—O3—C7	103.2 (3)
O3—Mo1—S1—C1	−75.92 (7)	O1ⁱ—Mo1—O3—Mo1ⁱ	−52.44 (3)
O2—Mo1—S2—C1	−99.06 (6)	O1—Mo1—O3—Mo1ⁱ	52.22 (3)
O1ⁱ—Mo1—S2—C1	58.14 (7)	S2—Mo1—O3—Mo1ⁱ	144.06 (3)
O1—Mo1—S2—C1	154.38 (6)	S1—Mo1—O3—Mo1ⁱ	−142.59 (3)
S1—Mo1—S2—C1	−0.94 (5)	C9—O3—C7—C6	21.9 (3)
Mo1ⁱ—Mo1—S2—C1	130.25 (5)	Mo1—O3—C7—C6	−176.6 (2)
O3—Mo1—S2—C1	84.12 (7)	Mo1ⁱ—O3—C7—C6	−111.7 (3)
O2—Mo1—O1—Mo1ⁱ	98.92 (4)	C9—O3—C7—Mo1	−161.5 (3)
O1ⁱ—Mo1—O1—Mo1ⁱ	−13.32 (5)	Mo1ⁱ—O3—C7—Mo1	64.91 (18)
S2—Mo1—O1—Mo1ⁱ	−155.46 (3)	C8—C6—C7—O3	1.4 (4)
S1—Mo1—O1—Mo1ⁱ	−108.31 (4)	C8—C6—C7—Mo1	−1.7 (6)
O3—Mo1—O1—Mo1ⁱ	−80.47 (6)	O2—Mo1—C7—O3	−173.53 (19)
O1ⁱ—Mo1—O2—Mo1ⁱ	52.06 (3)	O1ⁱ—Mo1—C7—O3	−122.3 (3)
O1—Mo1—O2—Mo1ⁱ	−51.33 (3)	O1—Mo1—C7—O3	−23.1 (3)
S2—Mo1—O2—Mo1ⁱ	−142.50 (2)	S2—Mo1—C7—O3	63.8 (3)
S1—Mo1—O2—Mo1ⁱ	143.34 (2)	S1—Mo1—C7—O3	136.9 (3)
C4—N1—C1—S1	−172.85 (11)	Mo1ⁱ—Mo1—C7—O3	−71.1 (3)
C2—N1—C1—S1	7.5 (2)	O2—Mo1—C7—C6	−168.3 (3)
C4—N1—C1—S2	4.7 (2)	O1ⁱ—Mo1—C7—C6	−117.0 (5)
C2—N1—C1—S2	−174.93 (10)	O1—Mo1—C7—C6	−17.8 (4)
Mo1—S1—C1—N1	176.36 (12)	S2—Mo1—C7—C6	69.0 (4)
Mo1—S1—C1—S2	−1.40 (7)	S1—Mo1—C7—C6	142.1 (5)
Mo1—S2—C1—N1	−176.35 (12)	Mo1ⁱ—Mo1—C7—C6	−65.9 (4)
Mo1—S2—C1—S1	1.40 (7)	O3—Mo1—C7—C6	5.2 (3)
O2—Mo1—C1—S1	−86.15 (6)	C7—C6—C8—C9	−23.1 (5)
O1ⁱ—Mo1—C1—S1	37.22 (6)	C7—O3—C9—C8	−37.5 (4)
O1—Mo1—C1—S1	152.10 (4)	Mo1—O3—C9—C8	160.5 (2)
S2—Mo1—C1—S1	−178.47 (8)	Mo1ⁱ—O3—C9—C8	98.3 (3)
Mo1ⁱ—Mo1—C1—S1	93.83 (5)	C7—O3—C9—Mo1	161.9 (3)
O3—Mo1—C1—S1	95.97 (7)	Mo1ⁱ—O3—C9—Mo1	−62.18 (15)
O2—Mo1—C1—S2	92.31 (6)	C6—C8—C9—O3	36.8 (4)
O1ⁱ—Mo1—C1—S2	−144.31 (4)	C6—C8—C9—Mo1	54.3 (6)
O1—Mo1—C1—S2	−29.43 (6)	O2—Mo1—C9—O3	172.71 (17)
S1—Mo1—C1—S2	178.47 (8)	O1ⁱ—Mo1—C9—O3	27.7 (3)
Mo1ⁱ—Mo1—C1—S2	−87.70 (6)	O1—Mo1—C9—O3	126.7 (3)
O3—Mo1—C1—S2	−85.56 (7)	S2—Mo1—C9—O3	−128.3 (3)
C1—N1—C2—C3	90.63 (16)	S1—Mo1—C9—O3	−59.5 (3)
C4—N1—C2—C3	−89.02 (15)	Mo1ⁱ—Mo1—C9—O3	75.6 (3)
C1—N1—C4—C5	98.86 (16)	O2—Mo1—C9—C8	143.6 (4)
C2—N1—C4—C5	−81.49 (16)	O1ⁱ—Mo1—C9—C8	−1.4 (4)
O1ⁱ—Mo1—O3—C9	−150.6 (3)	O1—Mo1—C9—C8	97.6 (5)
O1—Mo1—O3—C9	−46.0 (3)	S2—Mo1—C9—C8	−157.4 (5)
S2—Mo1—O3—C9	45.9 (3)	S1—Mo1—C9—C8	−88.6 (5)
S1—Mo1—O3—C9	119.2 (3)	Mo1ⁱ—Mo1—C9—C8	46.5 (4)
Mo1ⁱ—Mo1—O3—C9	−98.2 (3)	O3—Mo1—C9—C8	−29.1 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱⁱ	0.99	2.57	3.2687 (17)	127
C4—H4B···O2ⁱⁱⁱ	0.99	2.49	3.2443 (17)	133

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

Experimental details

Crystal data
Chemical formula	[Mo₂(C₅H₁₀NS₂)₂O₄]·C₄H₈O
M_r	624.50
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	12.8695 (7), 12.6025 (7), 14.4579 (8)
β (°)	94.184 (3)
V (Å³)	2338.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.46
Crystal size (mm)	0.12 × 0.12 × 0.08

Data collection
Diffractometer	Bruker X8 KappaCCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.845, 0.893
No. of measured, independent and observed [I > 2σ(I)] reflections	48139, 5649, 4661
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.833

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.054, 1.03
No. of reflections	5649
No. of parameters	149
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.96

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected bond lengths (Å) top

Mo1—Mo1ⁱ	2.5591 (2)	Mo1—O1ⁱ	1.9472 (9)
Mo1—S1	2.4788 (4)	Mo1—O2	1.6826 (10)
Mo1—S2	2.4680 (4)	Mo1—O3	2.6213 (19)
Mo1—O1	1.9586 (9)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱⁱ	0.99	2.57	3.2687 (17)	127
C4—H4B···O2ⁱⁱⁱ	0.99	2.49	3.2443 (17)	133

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

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support, for the post-doctoral research grants Nos. SFRH/BPD/23461/2005 and SFRH/BPD/63736/2009 (to JAF) and for specific funding toward the purchase of the single-crystal diffractometer.

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