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Acta Cryst. (2007). E63, m2931    [ doi:10.1107/S1600536807054761 ]

[mu]-Glycine-[kappa]2O:O'-di-[mu]-sulfido-bis[(glycinato-[kappa]2N,O)oxidomolybdenum(V)]

Y. M. Li, Y. H. Li and C. P. Zhai

Abstract top

In the title compound, [Mo2(C2H4NO2)2O2S2(C2H5NO2)], the two MoV atoms are bridged by two [mu]2-S atoms and one glycine ligand in an O:O'-bidentate mode. In addition, each MoV atom is bonded to one terminal oxygen ligand and chelated by one N,O-bidentate glycinate ligand, resulting in a distorted octahedral coordination. A complex hydrogen-bonding network is constructed by intermolecular N-H...O hydrogen bonds.

Comment top

Dimolybdenum complexes containing [Mo2O2(µ-S)2] have attracted many chemists' attention, not only because the [Mo2O2(µ-S)2] unit has special stability but also because it may be employed as a starting material to react with many transition metals. Some [Mo2O2(µ-S)2] structural compounds based on amino-acid have been isolated and structurally characterized (Spivack & Dori, 1975; Li et al., 2005). The crystal structure of our new neutral dimolybdenum glycinato complex is similar to the compound [Mo2O4(C2H4NO2)2(C2H5NO2)] (Liu et al., 2000).

The title structure consists of the neutral Mo2O2(µ-S)2(C2H5NO2)(C2H4NO2)2 (Fig. 1). In the structure, the two molybdenum atoms are not crystallographically equivalent, which are linked by two µ2-S ligand and one glycine (+H3NCH2COO−) ligand in an O:O'-bidentate mode. Each MoV atom is also bonded to one terminal oxygen atom and chelated by one N,O-glycine (NH2CH2COO−) ligand, resulting in a distorted octahedral coordination. The Mo···Mo separation is 2.788 (2) Å, which is shorter than the Mo···Mo distance (2.848 (1) Å) in the histidinato complex (Spivack & Dori, 1975). The Mo—S, Mo—N, Mo—O and Mo═O bond lengths are 2.304 (5)—2.336 (4) Å, 2.195 (12)—2.225 (11) Å, 2.091 (11)—2.328 (9) Å and 1.668 (11)—1.696 (10) Å, respectively.

A three-dimensional network is constructed by six classic intermolecular N—H···O hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For related structure, see: Spivack & Dori (1975); Li et al. (2005); Liu et al. (2000); Lin et al. (1998).

Experimental top

The title compound was prepared by adding a solution of glycin (0.075 g, 1 mmol) in 5 ml H2O to a solution of (Et4N)2Mo2S2O2(edt)2 (0.366 g, 0.5 mmol) in 5 ml DMF. After stirring about 10 min, the solution was filtered. Orange block crystals of the title compound were obtained by slow evaporation of the orange filtrate for several weeks. (Et4N)2Mo2S2O2(edt)2 was synthesized by the literature (Lin et al.,1998).

Refinement top

All H atoms were positioned geometrically and treated as riding atoms (including free rotation about the C—NH3+ bond), with C—H = 0.97 Å and N—H = 0.89—0.90 Å, with Uiso(H) = 1.2 Ueq(C, N) (1.5 for —NH3+ groups). Rint value of 0.086 and R of 0.0869 indicate a low structure quality.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. A view of the crystal packing along the b axis. Hydrogen bonds are shown as dashed lines.
µ-Glycine-κ2O:O'-di-µ-sulfido- bis[(glycinato-κ2N,O)oxidomolybdenum(V)] top
Crystal data top
[Mo2(C2H4NO2)2O2S2(C2H5NO2)]F000 = 1000
Mr = 511.19Dx = 2.353 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 45 reflections
a = 13.1258 (13) Åθ = 2.5–25.0º
b = 10.8384 (10) ŵ = 2.07 mm−1
c = 10.5850 (10) ÅT = 295 K
β = 106.597 (2)ºBlock, orange
V = 1443.1 (2) Å30.20 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2519 independent reflections
Radiation source: fine-focus sealed tube1620 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.086
T = 295 Kθmax = 25.0º
phi and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→13
Tmin = 0.483, Tmax = 0.813k = −12→7
4358 measured reflectionsl = −7→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)] = 0.087H-atom parameters constrained
wR(F2) = 0.178  w = 1/[σ2(Fo2) + (0.0001P)2 + 52.2323P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2519 reflectionsΔρmax = 1.16 e Å−3
190 parametersΔρmin = −1.10 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mo2(C2H4NO2)2O2S2(C2H5NO2)]V = 1443.1 (2) Å3
Mr = 511.19Z = 4
Monoclinic, P21/cMo Kα
a = 13.1258 (13) ŵ = 2.07 mm−1
b = 10.8384 (10) ÅT = 295 K
c = 10.5850 (10) Å0.20 × 0.15 × 0.10 mm
β = 106.597 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2519 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1620 reflections with I > 2σ(I)
Tmin = 0.483, Tmax = 0.813Rint = 0.086
4358 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.087H-atom parameters constrained
wR(F2) = 0.178  w = 1/[σ2(Fo2) + (0.0001P)2 + 52.2323P]
where P = (Fo2 + 2Fc2)/3
S = 1.11Δρmax = 1.16 e Å−3
2519 reflectionsΔρmin = −1.10 e Å−3
190 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
xyzUiso*/Ueq
Mo10.72243 (11)0.35843 (13)0.32342 (13)0.0272 (4)
Mo20.64096 (11)0.59751 (13)0.30419 (13)0.0281 (4)
S10.7788 (4)0.5267 (4)0.2284 (5)0.0513 (13)
S20.5926 (3)0.4310 (4)0.4150 (4)0.0355 (10)
O11.0118 (9)0.1842 (12)0.4619 (12)0.051 (3)
O20.8716 (8)0.2768 (10)0.3310 (10)0.034 (3)
O30.6503 (8)0.2828 (10)0.1868 (10)0.036 (3)
O40.5367 (8)0.6025 (11)0.1700 (10)0.040 (3)
O50.7134 (10)0.9688 (11)0.3142 (13)0.051 (3)
O60.7004 (8)0.7698 (10)0.2716 (10)0.033 (3)
O70.7740 (7)0.6195 (10)0.5025 (10)0.030 (3)
O80.8358 (9)0.4270 (10)0.5171 (10)0.035 (3)
N10.7391 (10)0.1977 (10)0.4585 (12)0.027 (3)
H1A0.71190.21710.52500.032*
H1B0.70180.13360.41430.032*
N20.5774 (10)0.7223 (11)0.4264 (12)0.030 (3)
H2A0.50610.71540.40280.036*
H2B0.60230.69920.51130.036*
N30.9018 (10)0.6917 (13)0.7315 (12)0.035 (3)
H3A0.94750.70590.81010.053*
H3B0.83580.70470.73550.053*
H3E0.91560.74230.67220.053*
C10.9187 (14)0.2111 (16)0.4302 (18)0.040 (4)
C20.8498 (12)0.1619 (18)0.5123 (16)0.043 (5)
H2C0.85470.07260.51580.052*
H2D0.87630.19290.60160.052*
C30.6054 (14)0.8498 (15)0.4143 (17)0.040 (4)
H3C0.63940.88230.50160.047*
H3D0.54090.89680.37750.047*
C40.6778 (13)0.8681 (16)0.3302 (14)0.034 (4)
C50.9124 (13)0.5617 (16)0.6923 (17)0.042 (4)
H5A0.98430.54680.68840.050*
H5B0.89800.50610.75690.050*
C60.8361 (12)0.5390 (16)0.5617 (14)0.029 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.0314 (8)0.0282 (8)0.0244 (7)−0.0040 (6)0.0116 (6)−0.0006 (6)
Mo20.0289 (8)0.0300 (8)0.0281 (7)0.0000 (6)0.0128 (6)0.0005 (6)
S10.062 (3)0.035 (3)0.061 (3)0.000 (2)0.024 (3)−0.004 (2)
S20.039 (3)0.035 (3)0.038 (2)−0.0018 (19)0.019 (2)0.0015 (19)
O10.032 (7)0.057 (9)0.062 (9)0.005 (6)0.010 (6)0.015 (7)
O20.026 (6)0.046 (7)0.035 (6)0.002 (5)0.017 (5)0.003 (6)
O30.037 (7)0.039 (7)0.032 (6)−0.012 (5)0.012 (5)−0.001 (5)
O40.035 (7)0.052 (8)0.037 (6)0.004 (6)0.016 (5)0.007 (6)
O50.058 (9)0.030 (7)0.078 (10)−0.009 (6)0.038 (8)−0.005 (7)
O60.038 (7)0.025 (6)0.043 (7)0.005 (5)0.023 (6)0.006 (5)
O70.015 (5)0.038 (7)0.030 (6)−0.004 (5)−0.004 (4)−0.006 (5)
O80.046 (7)0.033 (7)0.028 (6)−0.004 (5)0.012 (5)0.002 (5)
N10.044 (8)0.007 (6)0.037 (7)−0.003 (6)0.023 (6)−0.002 (5)
N20.032 (8)0.031 (8)0.030 (7)0.001 (6)0.012 (6)0.001 (6)
N30.031 (8)0.053 (10)0.024 (7)−0.003 (7)0.011 (6)−0.007 (6)
C10.033 (11)0.037 (11)0.053 (12)0.010 (8)0.015 (9)0.002 (9)
C20.028 (10)0.067 (14)0.033 (10)−0.012 (9)0.004 (8)0.000 (9)
C30.047 (11)0.030 (10)0.050 (11)0.000 (8)0.028 (9)−0.005 (8)
C40.035 (9)0.040 (11)0.021 (8)−0.003 (8)−0.003 (7)0.003 (8)
C50.034 (10)0.045 (11)0.047 (11)0.007 (8)0.012 (8)−0.011 (9)
C60.017 (8)0.049 (11)0.021 (8)0.012 (8)0.003 (7)0.004 (8)
Geometric parameters (Å, °) top
Mo1—O31.696 (10)N1—C21.454 (19)
Mo1—O22.129 (10)N1—H1A0.9000
Mo1—N12.225 (11)N1—H1B0.9000
Mo1—O82.286 (11)N2—C31.44 (2)
Mo1—S12.304 (5)N2—H2A0.9000
Mo1—S22.325 (4)N2—H2B0.9000
Mo1—Mo22.788 (2)N3—C51.49 (2)
Mo2—O41.668 (11)N3—H3A0.8900
Mo2—O62.091 (11)N3—H3B0.8900
Mo2—N22.195 (12)N3—H3E0.8900
Mo2—S12.310 (5)C1—C21.52 (2)
Mo2—O72.328 (9)C2—H2C0.9700
Mo2—S22.336 (4)C2—H2D0.9700
O1—C11.206 (19)C3—C41.49 (2)
O2—C11.274 (19)C3—H3C0.9700
O5—C41.219 (19)C3—H3D0.9700
O6—C41.308 (19)C5—C61.48 (2)
O7—C61.235 (17)C5—H5A0.9700
O8—C61.303 (19)C5—H5B0.9700
O3—Mo1—O296.6 (5)C6—O8—Mo1124.2 (9)
O3—Mo1—N195.6 (5)C2—N1—Mo1111.4 (9)
O2—Mo1—N174.3 (4)C2—N1—H1A109.3
O3—Mo1—O8169.5 (5)Mo1—N1—H1A109.3
O2—Mo1—O875.2 (4)C2—N1—H1B109.3
N1—Mo1—O876.0 (4)Mo1—N1—H1B109.3
O3—Mo1—S1100.4 (4)H1A—N1—H1B108.0
O2—Mo1—S186.5 (3)C3—N2—Mo2112.8 (9)
N1—Mo1—S1156.3 (4)C3—N2—H2A109.0
O8—Mo1—S185.8 (3)Mo2—N2—H2A109.0
O3—Mo1—S2102.8 (4)C3—N2—H2B109.0
O2—Mo1—S2154.2 (3)Mo2—N2—H2B109.0
N1—Mo1—S286.9 (3)H2A—N2—H2B107.8
O8—Mo1—S283.3 (3)C5—N3—H3A109.5
S1—Mo1—S2106.19 (17)C5—N3—H3B109.5
O3—Mo1—Mo2106.1 (4)H3A—N3—H3B109.5
O2—Mo1—Mo2135.9 (3)C5—N3—H3E109.5
N1—Mo1—Mo2137.7 (3)H3A—N3—H3E109.5
O8—Mo1—Mo284.3 (3)H3B—N3—H3E109.5
S1—Mo1—Mo252.90 (13)O1—C1—O2125.3 (16)
S2—Mo1—Mo253.45 (11)O1—C1—C2118.6 (16)
O4—Mo2—O694.9 (5)O2—C1—C2116.1 (14)
O4—Mo2—N297.1 (5)N1—C2—C1112.0 (14)
O6—Mo2—N276.7 (4)N1—C2—H2C109.2
O4—Mo2—S1104.4 (4)C1—C2—H2C109.2
O6—Mo2—S182.7 (3)N1—C2—H2D109.2
N2—Mo2—S1151.3 (4)C1—C2—H2D109.2
O4—Mo2—O7170.5 (5)H2C—C2—H2D107.9
O6—Mo2—O780.7 (4)N2—C3—C4113.7 (13)
N2—Mo2—O773.7 (4)N2—C3—H3C108.8
S1—Mo2—O783.5 (3)C4—C3—H3C108.8
O4—Mo2—S2100.2 (4)N2—C3—H3D108.8
O6—Mo2—S2160.1 (3)C4—C3—H3D108.8
N2—Mo2—S288.7 (3)H3C—C3—H3D107.7
S1—Mo2—S2105.66 (17)O5—C4—O6121.1 (15)
O7—Mo2—S282.4 (3)O5—C4—C3122.5 (16)
O4—Mo2—Mo1107.2 (4)O6—C4—C3116.4 (14)
O6—Mo2—Mo1133.5 (3)C6—C5—N3109.0 (14)
N2—Mo2—Mo1137.1 (3)C6—C5—H5A109.9
S1—Mo2—Mo152.73 (13)N3—C5—H5A109.9
O7—Mo2—Mo181.7 (3)C6—C5—H5B109.9
S2—Mo2—Mo153.08 (11)N3—C5—H5B109.9
Mo1—S1—Mo274.36 (16)H5A—C5—H5B108.3
Mo1—S2—Mo273.47 (13)O7—C6—O8122.7 (14)
C1—O2—Mo1119.2 (10)O7—C6—C5122.0 (15)
C4—O6—Mo2120.2 (10)O8—C6—C5115.2 (14)
C6—O7—Mo2127.0 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.092.975 (16)167
N1—H1B···O5ii0.902.102.882 (16)144
N2—H2A···O3iii0.902.132.958 (16)153
N3—H3A···O1iv0.892.333.119 (17)148
N3—H3B···O6v0.891.942.825 (16)172
N3—H3E···O1vi0.892.082.934 (17)160
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+2, y+1/2, −z+3/2; (v) x, −y+3/2, z+1/2; (vi) −x+2, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.092.975 (16)167
N1—H1B···O5ii0.902.102.882 (16)144
N2—H2A···O3iii0.902.132.958 (16)153
N3—H3A···O1iv0.892.333.119 (17)148
N3—H3B···O6v0.891.942.825 (16)172
N3—H3E···O1vi0.892.082.934 (17)160
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+2, y+1/2, −z+3/2; (v) x, −y+3/2, z+1/2; (vi) −x+2, −y+1, −z+1.
Acknowledgements top

The authors thank Henan University for financial support.

references
References top

Li, D.-M., Xing, Y.-H., Li, Z.-C., Xu, J.-Q., Song, W.-B., Wang, T.-G., Yang, G.-D., Hu, N.-H., Jia, H.-Q. & Zhang, H.-M. (2005). J. Inorg. Biochem. 99, 1602–1610.

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Liu, G., Liu, J., Wei, Y.-G., Liu, Q. & Zhang, S.-W. (2000). Acta Cryst. C56, 822–823.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Siemens (1996). SAINT, SMART and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Spivack, B. & Dori, Z. (1975). J. Chem. Soc. Dalton Trans. pp. 1077–1080.