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Acta Cryst. (2007). E63, m1877    [ doi:10.1107/S1600536807026384 ]

Di-[mu]-sulfido-bis[(2-aminoethanethiolato-[kappa]2N,S)oxidomolybdate(V)]

Y.-M. Li, J.-L. Zhang and X.-W. Zhao

Abstract top

The title compound, [Mo2O2S2(C2H6NS)2], was obtained by the reaction of sodium molybdate, H2S, sodium hydrosulfite and 2-aminoethanethiol. In the crystal structure, each MoV atom, in a square-pyramidal geometry, is coordinated by two [mu]-S atoms, one terminal O atom, one S atom and one N atom of the 2-aminoethanethiolate ligand. A three-dimensional hydrogen-bonding network is constructed by intermolecular N-H...O and N-H...S hydrogen bonds.

Comment top

Molybdenum chalcogenides have been extensively studied due to their applications in modelling of molybdoenzymes in biological systems. During the course of exploring polynuclear molybdenum clusters, dinuclear molybdenum complexes are always considered as excellent starting materials. Many compounds containing a [Mo2O2(µ-S)2] structural unit have been isolated and structurally characterized (Bunzey et al., 1977; Drew & Kay, 1971; Dulebohn et al., 1991; Howlader et al., 1984; Li et al., 2005; Llusar et al., 2005; Müller et al., 1982; Spivack & Dori,1970). Herein, we report the crystal structure of a new dinuclear molybdenum complex, (I).

In the structure of (I) (Fig. 1), the two Mo atoms are not crystallographically equivalent, which are linked by two µ-S atoms. Each Mo atom is chelated by one 2-aminoethanethiolate (aet) ligand in the equatorial plane. The two aet ligands are in a trans form. Each Mo atom is also bonded to one terminal O atom in the axial position, resulting in a five-coordinated square-pyramidal coordination geometry. In virtue of weak intermolecular N—H···O and N—H···S hydrogen bonds, a three-dimensional hydrogen-bonding network is constructed (Fig. 2).

Related literature top

For related structures, see: Bunzey et al. (1977); Drew & Kay (1971); Dulebohn et al. (1991); Howlader et al. (1984); Li et al. (2005); Llusar et al. (2005); Müller et al. (1982); Spivack & Dori (1970).

Experimental top

The compound (I) was synthesized by bubbling H2S gas into a 20 ml aqueous solution of Na2MoO4·2H2O (4.84 g, 20 mmol). The solids of Na2S2O4 (0.469 g, 2.7 mmol) and 2-aminoethanethiol (2 g, 26 mmol) were added to the red solution with stirring for about 4 h at 358 K. After cooling to room temperature, the solution was filtered and the residue was dissolved in 10 ml DMF. Orange prism crystals of (I) were obtained by slow evaporation of the orange solution for several weeks.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.97 and N—H = 0.90 Å and Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Siemens, 1996); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of the crystal packing along the c axis. Hydrogen bonds are shown as dashed lines.
Di-µ-sulfido-bis[(2-aminoethanethiolato-κ2N,S)oxidomolybdate(V)](Mo—Mo) top
Crystal data top
[Mo2O2S2(C2H6NS)2]F000 = 856
Mr = 440.28Dx = 2.281 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 245 reflections
a = 10.2359 (9) Åθ = 2.1–25.1º
b = 12.5935 (11) ŵ = 2.59 mm−1
c = 10.2596 (9) ÅT = 293 (2) K
β = 104.166 (2)ºPrism, orange
V = 1282.30 (19) Å30.30 × 0.22 × 0.18 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer		2268 independent reflections
Radiation source: fine-focus sealed tube1753 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.073
T = 293(2) Kθmax = 25.1º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→12
Tmin = 0.492, Tmax = 0.633k = −14→15
6415 measured reflectionsl = −11→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0177P)2 + 11.6194P]
where P = (Fo2 + 2Fc2)/3
S = 1.18(Δ/σ)max < 0.001
2268 reflectionsΔρmax = 0.75 e Å−3
127 parametersΔρmin = −0.77 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mo2O2S2(C2H6NS)2]V = 1282.30 (19) Å3
Mr = 440.28Z = 4
Monoclinic, P21/cMo Kα
a = 10.2359 (9) ŵ = 2.59 mm−1
b = 12.5935 (11) ÅT = 293 (2) K
c = 10.2596 (9) Å0.30 × 0.22 × 0.18 mm
β = 104.166 (2)º
Data collection top
Siemens SMART CCD area-detector
diffractometer		2268 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1753 reflections with I > 2σ(I)
Tmin = 0.492, Tmax = 0.633Rint = 0.073
6415 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0177P)2 + 11.6194P]
where P = (Fo2 + 2Fc2)/3
S = 1.18Δρmax = 0.75 e Å−3
2268 reflectionsΔρmin = −0.77 e Å−3
127 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mo10.24088 (8)0.28563 (7)0.23707 (8)0.0308 (2)
Mo20.26812 (8)0.50741 (7)0.21672 (8)0.0314 (2)
S10.0614 (2)0.1740 (2)0.1200 (3)0.0390 (6)
S20.0689 (2)0.4136 (2)0.1873 (3)0.0398 (6)
S30.3706 (3)0.5979 (2)0.0634 (3)0.0428 (6)
S40.4155 (2)0.3758 (2)0.1811 (3)0.0446 (7)
O10.2747 (8)0.2657 (6)0.4035 (7)0.057 (2)
O20.3266 (8)0.5483 (6)0.3766 (7)0.0517 (19)
N10.3497 (7)0.1462 (6)0.1863 (8)0.0345 (18)
H1C0.35880.15350.10170.041*
H1D0.43290.14450.24160.041*
N20.1333 (8)0.6454 (6)0.1567 (8)0.041 (2)
H2C0.07760.63320.07550.050*
H2D0.08260.65440.21620.050*
C10.1444 (9)0.0480 (8)0.1021 (10)0.038 (2)
H1A0.0911−0.01050.12240.046*
H1B0.15220.04000.01030.046*
C20.2825 (9)0.0463 (8)0.1971 (10)0.042 (2)
H2A0.27470.03620.28860.050*
H2B0.3347−0.01210.17430.050*
C30.2878 (11)0.7277 (9)0.0442 (10)0.049 (3)
H3A0.35480.78330.05160.059*
H3B0.22620.7327−0.04410.059*
C40.2115 (12)0.7426 (8)0.1509 (11)0.048 (3)
H4A0.27370.75530.23730.058*
H4B0.15150.80310.12930.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.0347 (5)0.0266 (5)0.0306 (4)0.0024 (4)0.0070 (3)0.0003 (4)
Mo20.0363 (4)0.0267 (5)0.0305 (4)−0.0013 (4)0.0068 (3)−0.0026 (3)
S10.0306 (12)0.0306 (14)0.0560 (16)−0.0003 (10)0.0108 (11)0.0003 (12)
S20.0340 (13)0.0301 (14)0.0586 (16)0.0021 (11)0.0176 (12)0.0041 (12)
S30.0438 (14)0.0433 (16)0.0441 (15)−0.0091 (12)0.0159 (12)−0.0018 (12)
S40.0309 (13)0.0344 (16)0.0696 (18)−0.0044 (11)0.0142 (12)−0.0091 (13)
O10.083 (5)0.054 (5)0.036 (4)0.014 (4)0.016 (4)0.001 (4)
O20.076 (5)0.040 (5)0.037 (4)0.000 (4)0.008 (4)−0.005 (3)
N10.029 (4)0.025 (4)0.047 (5)0.004 (3)0.005 (3)−0.001 (4)
N20.050 (5)0.034 (5)0.043 (5)0.004 (4)0.017 (4)0.001 (4)
C10.043 (6)0.025 (5)0.050 (6)−0.001 (4)0.015 (5)−0.003 (5)
C20.041 (6)0.036 (6)0.046 (6)−0.002 (5)0.008 (5)0.005 (5)
C30.054 (6)0.046 (7)0.050 (6)−0.005 (5)0.015 (5)0.011 (5)
C40.073 (7)0.018 (5)0.050 (6)0.000 (5)0.007 (6)0.002 (4)
Geometric parameters (Å, °) top
Mo1—O11.676 (7)N1—H1D0.9000
Mo1—N12.209 (7)N2—C41.471 (12)
Mo1—S42.306 (3)N2—H2C0.9000
Mo1—S22.349 (3)N2—H2D0.9000
Mo1—S12.391 (3)C1—C21.508 (13)
Mo1—Mo22.8197 (12)C1—H1A0.9700
Mo2—O21.683 (7)C1—H1B0.9700
Mo2—N22.211 (8)C2—H2A0.9700
Mo2—S22.312 (3)C2—H2B0.9700
Mo2—S42.329 (3)C3—C41.505 (14)
Mo2—S32.383 (3)C3—H3A0.9700
S1—C11.829 (10)C3—H3B0.9700
S3—C31.830 (11)C4—H4A0.9700
N1—C21.451 (12)C4—H4B0.9700
N1—H1C0.9000
O1—Mo1—N197.5 (3)C2—N1—H1C108.9
O1—Mo1—S4110.4 (3)Mo1—N1—H1C108.9
N1—Mo1—S482.3 (2)C2—N1—H1D108.9
O1—Mo1—S2106.4 (3)Mo1—N1—H1D108.9
N1—Mo1—S2152.7 (2)H1C—N1—H1D107.7
S4—Mo1—S2101.13 (10)C4—N2—Mo2110.9 (6)
O1—Mo1—S1111.4 (3)C4—N2—H2C109.5
N1—Mo1—S177.5 (2)Mo2—N2—H2C109.5
S4—Mo1—S1135.38 (10)C4—N2—H2D109.5
S2—Mo1—S181.46 (9)Mo2—N2—H2D109.5
O1—Mo1—Mo2103.0 (3)H2C—N2—H2D108.1
N1—Mo1—Mo2134.8 (2)C2—C1—S1109.5 (7)
S4—Mo1—Mo252.90 (7)C2—C1—H1A109.8
S2—Mo1—Mo252.17 (6)S1—C1—H1A109.8
S1—Mo1—Mo2128.55 (7)C2—C1—H1B109.8
O2—Mo2—N294.6 (3)S1—C1—H1B109.8
O2—Mo2—S2112.1 (3)H1A—C1—H1B108.2
N2—Mo2—S284.0 (2)N1—C2—C1109.0 (8)
O2—Mo2—S4106.3 (3)N1—C2—H2A109.9
N2—Mo2—S4154.1 (2)C1—C2—H2A109.9
S2—Mo2—S4101.55 (9)N1—C2—H2B109.9
O2—Mo2—S3112.8 (3)C1—C2—H2B109.9
N2—Mo2—S377.6 (2)H2A—C2—H2B108.3
S2—Mo2—S3132.44 (10)C4—C3—S3110.0 (7)
S4—Mo2—S380.21 (10)C4—C3—H3A109.7
O2—Mo2—Mo1104.4 (3)S3—C3—H3A109.7
N2—Mo2—Mo1137.1 (2)C4—C3—H3B109.7
S2—Mo2—Mo153.37 (7)S3—C3—H3B109.7
S4—Mo2—Mo152.15 (7)H3A—C3—H3B108.2
S3—Mo2—Mo1126.15 (8)N2—C4—C3108.1 (8)
C1—S1—Mo1104.0 (3)N2—C4—H4A110.1
Mo2—S2—Mo174.46 (8)C3—C4—H4A110.1
C3—S3—Mo2103.4 (3)N2—C4—H4B110.1
Mo1—S4—Mo274.95 (8)C3—C4—H4B110.1
C2—N1—Mo1113.3 (6)H4A—C4—H4B108.4
O1—Mo1—Mo2—O26.2 (4)N1—Mo1—S2—Mo2−116.2 (4)
N1—Mo1—Mo2—O2−108.5 (4)S4—Mo1—S2—Mo2−21.39 (10)
S4—Mo1—Mo2—O2−99.7 (3)S1—Mo1—S2—Mo2−156.15 (9)
S2—Mo1—Mo2—O2107.0 (3)O2—Mo2—S3—C3−76.3 (5)
S1—Mo1—Mo2—O2137.7 (3)N2—Mo2—S3—C313.5 (4)
O1—Mo1—Mo2—N2−107.2 (4)S2—Mo2—S3—C383.3 (4)
N1—Mo1—Mo2—N2138.1 (4)S4—Mo2—S3—C3−180.0 (4)
S4—Mo1—Mo2—N2146.9 (3)Mo1—Mo2—S3—C3153.8 (4)
S2—Mo1—Mo2—N2−6.5 (3)O1—Mo1—S4—Mo2−91.1 (3)
S1—Mo1—Mo2—N224.3 (3)N1—Mo1—S4—Mo2173.7 (2)
O1—Mo1—Mo2—S2−100.8 (3)S2—Mo1—S4—Mo221.17 (10)
N1—Mo1—Mo2—S2144.5 (3)S1—Mo1—S4—Mo2110.25 (12)
S4—Mo1—Mo2—S2153.34 (13)O2—Mo2—S4—Mo195.8 (3)
S1—Mo1—Mo2—S230.75 (12)N2—Mo2—S4—Mo1−121.7 (5)
O1—Mo1—Mo2—S4105.9 (3)S2—Mo2—S4—Mo1−21.56 (10)
N1—Mo1—Mo2—S4−8.8 (3)S3—Mo2—S4—Mo1−153.14 (10)
S2—Mo1—Mo2—S4−153.34 (13)O1—Mo1—N1—C272.4 (7)
S1—Mo1—Mo2—S4−122.59 (13)S4—Mo1—N1—C2−177.9 (6)
O1—Mo1—Mo2—S3139.3 (3)S2—Mo1—N1—C2−78.5 (8)
N1—Mo1—Mo2—S324.6 (3)S1—Mo1—N1—C2−38.0 (6)
S4—Mo1—Mo2—S333.46 (12)Mo2—Mo1—N1—C2−170.9 (5)
S2—Mo1—Mo2—S3−119.88 (12)O2—Mo2—N2—C470.5 (7)
S1—Mo1—Mo2—S3−89.13 (12)S2—Mo2—N2—C4−177.7 (6)
O1—Mo1—S1—C1−83.6 (4)S4—Mo2—N2—C4−73.7 (9)
N1—Mo1—S1—C19.7 (4)S3—Mo2—N2—C4−41.9 (6)
S4—Mo1—S1—C174.9 (4)Mo1—Mo2—N2—C4−172.5 (5)
S2—Mo1—S1—C1172.2 (3)Mo1—S1—C1—C215.9 (7)
Mo2—Mo1—S1—C1148.0 (3)Mo1—N1—C2—C159.9 (9)
O2—Mo2—S2—Mo1−91.9 (3)S1—C1—C2—N1−46.7 (9)
N2—Mo2—S2—Mo1175.6 (2)Mo2—S3—C3—C413.0 (8)
S4—Mo2—S2—Mo121.20 (10)Mo2—N2—C4—C362.8 (9)
S3—Mo2—S2—Mo1108.43 (12)S3—C3—C4—N2−46.8 (11)
O1—Mo1—S2—Mo293.9 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O1i0.902.253.025 (11)144
N1—H1D···S3ii0.902.533.400 (8)161
N2—H2C···S2iii0.902.813.704 (9)173
N2—H2D···S1iv0.902.503.403 (8)178
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, −y+1, −z; (iv) −x, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Mo1—O11.676 (7)Mo2—O21.683 (7)
Mo1—N12.209 (7)Mo2—N22.211 (8)
Mo1—S42.306 (3)Mo2—S22.312 (3)
Mo1—S22.349 (3)Mo2—S42.329 (3)
Mo1—S12.391 (3)Mo2—S32.383 (3)
Mo1—Mo22.8197 (12)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O1i0.902.253.025 (11)144
N1—H1D···S3ii0.902.533.400 (8)161
N2—H2C···S2iii0.902.813.704 (9)173
N2—H2D···S1iv0.902.503.403 (8)178
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, −y+1, −z; (iv) −x, y+1/2, −z+1/2.
Acknowledgements top

The authors thank Henan University for financial support and Professors X.-T. Wu and T.-L. Sheng for their help.

references
References top

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