cis-Di-μ-oxido-bis-[(N,N-diethyl-dithio-carbamato-κS,S')oxidomolybdenum(V)](Mo-Mo) tetra-hydro-furan monosolvate.

The title compound, [Mo(2)(C(5)H(10)NS(2))(2)O(4)]·C(4)H(8)O, can be readily prepared in tetra-hydro-furan (THF) by an oxidation reaction between the Mo(IV) precursor [MoO(S(2)CNEt(2))(2)] with [ReMeO(3)]. 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 mol-ecule 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 inter-acting with the Mo(V) atoms [Mo-O = 2.6213 (19) Å]. In the crystal, some weak C-H⋯O inter-actions occur between the terminal oxido and neighbouring -CH(3) groups of an adjacent [Mo(μ-O)O(S(2)CNEt(2))](2) unit.

Related literature

For applications of dithio­carbamate compounds, see: Tiekink (2008 ▶); Zhao et al. (2005 ▶). For the synthesis of the MoIV 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—OTHF 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 = 624.50

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.054

S = 1.03

5649 reflections

149 parameters

5 restraints

H-atom parameters constrained

Δρmax = 0.74 e Å−3

Δρmin = −0.96 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mo2(C5H10NS2)2O4]·C4H8O	F(000) = 1256
Mr = 624.50	Dx = 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

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

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(Fo2) + (0.0219P)2 + 2.1445P] where P = (Fo2 + 2Fc2)/3
5649 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 0.74 e Å−3
5 restraints	Δρmin = −0.96 e Å−3

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.

	x	y	z	Uiso*/Ueq	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

	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)

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)

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

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) .

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) ; (iii) .