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Acta Cryst. (2007). E63, m3034    [ doi:10.1107/S160053680705756X ]

Bis(pyridine-2-methanol-[kappa]2N,O]bis(thiocyanato-[kappa]N)cobalt(II)

Y.-P. Pan, D.-C. Li and D.-Q. Wang

Abstract top

The CoII ion in the title complex, [Co(NCS)2(C6H7NO)2], lies on a crystallographic twofold axis and is in a slightly distorted octahedral coordination environment. In the crystal structure, intermolecular O-H...S hydrogen bonds link molecules to form a two-dimensional network perpendicular to the c axis.

Comment top

In recent years there has been considerable interest in metal complexes of hydroxymethyl-pyridine due to the ligands versatile coordination modes and bridging function (Yoo et al., 2000; Yang et al., 2003). As an extension of this work on the structural characterization of hydroxymethyl-pyridine derivatives, we have synthesized here title compound, (I), and report herein its crystal structure.

The complex (Fig. 1) consists of two L2−(L=(hydroxymethyl)(pyridine) ligands, one CoII ion and two thiocyanato ligands. The coordination geometry around the Co center is slightly distorted octahedral with a CoN4O2 ligand set (see table of geometric parameters). Atom N2 of a thiocyanato ligand and atom O1 of an hydroxymethylpyridine ligand occupy the axial sites. In the crystal structure, intermolecular O—H···S hydrogen bonds link molecules to form a two-dimensional network perpendicular to the c axis (see hydrogen-bond geometry table).

Related literature top

For related literature, see: Yang et al. (2003); Yoo et al. (2000).

Experimental top

2-hydroxymethylpyridine (0.546 g, 5 mmol) and Et4NOH with 20% aqueous solution (0.736 g, 1 mmol) were added to a mixture(30 ml) of methanol and acetonitrile (V1: V2=2:1) containing cobaltous chlorine hexahydrate(0.476 g, 2 mmol)·After the solution was stirred at room temperature for 0.5 h. Potassium thiocyanato(0,486 g, 5 mmol) in 5 ml of methanol was added to the above solution and then further stirred for 2 h. The resulting clear solution was filtered and left to stand at room temperature. Red crystal suitable for X-ray diffraction were obtained by slow evaporation of the solvents within 2 weeks. (m.p.=458 K-459 K). Elemental analysis calculated for C14H14N4O2CoS2: C 42.75, H 3.59, N 14.24%; found: C 42.80, H 3.54, N 14.30%.

Refinement top

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H 0.93(pyridine), C—H 0.97 (methylene) Å [Uiso(H) = 1.2Ueq(C)] and O—H 0.82 Å (hydroxyl) [Uiso(H) = 1.5Ueq(O)].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecule structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Atoms labelled with the suffix A are generated by the symmetry operation (−x + 1, y, −z + 1/2). H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.
Bis(pyridine-2-methanol-κ2N,O]bis(thiocyanato-κN)cobalt(II) top
Crystal data top
[Co(NCS)2(C6H7NO)2]F000 = 804
Mr = 393.34Dx = 1.565 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 2060 reflections
a = 11.371 (10) Åθ = 2.9–24.0º
b = 8.255 (8) ŵ = 1.29 mm−1
c = 17.779 (16) ÅT = 298 (2) K
V = 1669 (3) Å3Block, red
Z = 40.45 × 0.37 × 0.30 mm
Data collection top
Bruker SMART CCD
diffractometer		1463 independent reflections
Radiation source: fine-focus sealed tube1079 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.088
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→13
Tmin = 0.594, Tmax = 0.698k = −8→9
6193 measured reflectionsl = −18→20
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)] = 0.055H-atom parameters constrained
wR(F2) = 0.170  w = 1/[σ2(Fo2) + (0.0972P)2 + 2.6034P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1463 reflectionsΔρmax = 0.90 e Å−3
105 parametersΔρmin = −0.80 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Co(NCS)2(C6H7NO)2]V = 1669 (3) Å3
Mr = 393.34Z = 4
Orthorhombic, PbcnMo Kα
a = 11.371 (10) ŵ = 1.29 mm−1
b = 8.255 (8) ÅT = 298 (2) K
c = 17.779 (16) Å0.45 × 0.37 × 0.30 mm
Data collection top
Bruker SMART CCD
diffractometer		1463 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1079 reflections with I > 2σ(I)
Tmin = 0.594, Tmax = 0.698Rint = 0.088
6193 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055105 parameters
wR(F2) = 0.170H-atom parameters constrained
S = 1.00Δρmax = 0.90 e Å−3
1463 reflectionsΔρmin = −0.80 e Å−3
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
Co10.50000.21568 (11)0.25000.0366 (4)
N10.6485 (4)0.2744 (5)0.1860 (2)0.0415 (10)
N20.5778 (4)0.0526 (5)0.3203 (2)0.0490 (11)
O10.4388 (3)0.4024 (4)0.16747 (19)0.0506 (9)
H10.36910.39710.15580.076*
S10.68424 (13)−0.17410 (19)0.41381 (8)0.0573 (5)
C10.5087 (4)0.4002 (8)0.1015 (3)0.0516 (14)
H1A0.50700.50570.07760.062*
H1B0.47790.32110.06630.062*
C20.6329 (4)0.3572 (6)0.1224 (3)0.0431 (12)
C30.7262 (5)0.4016 (7)0.0772 (3)0.0576 (15)
H30.71330.46070.03340.069*
C40.8373 (5)0.3579 (8)0.0975 (3)0.0593 (16)
H40.90080.38350.06670.071*
C50.8549 (5)0.2756 (7)0.1639 (4)0.0592 (16)
H50.93040.24910.17990.071*
C60.7586 (5)0.2337 (6)0.2058 (3)0.0482 (13)
H60.76990.17460.24980.058*
C70.6233 (4)−0.0404 (6)0.3589 (3)0.0392 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0326 (5)0.0353 (6)0.0419 (6)0.0000.0008 (4)0.000
N10.045 (2)0.043 (2)0.036 (2)−0.0052 (18)0.0000 (18)−0.0067 (19)
N20.047 (3)0.043 (2)0.057 (3)−0.004 (2)−0.003 (2)0.008 (2)
O10.047 (2)0.054 (2)0.051 (2)0.0069 (17)−0.0007 (17)0.0056 (17)
S10.0566 (9)0.0564 (9)0.0590 (9)0.0030 (7)−0.0096 (7)0.0154 (7)
C10.053 (3)0.062 (4)0.039 (3)−0.005 (3)−0.004 (2)0.004 (3)
C20.050 (3)0.043 (3)0.037 (3)−0.010 (2)0.004 (2)−0.005 (2)
C30.071 (4)0.062 (3)0.040 (3)−0.020 (3)0.004 (3)−0.009 (3)
C40.052 (3)0.074 (4)0.052 (4)−0.014 (3)0.021 (3)−0.014 (3)
C50.038 (3)0.072 (4)0.067 (4)−0.007 (3)0.000 (3)−0.016 (3)
C60.044 (3)0.045 (3)0.056 (3)−0.005 (2)−0.002 (2)−0.004 (2)
C70.034 (2)0.039 (3)0.045 (3)−0.008 (2)−0.001 (2)−0.004 (2)
Geometric parameters (Å, °) top
Co1—N2i2.039 (5)C1—C21.502 (7)
Co1—N22.039 (5)C1—H1A0.9700
Co1—N12.093 (4)C1—H1B0.9700
Co1—N1i2.093 (4)C2—C31.381 (7)
Co1—O1i2.239 (4)C3—C41.363 (8)
Co1—O12.239 (4)C3—H30.9300
N1—C21.333 (6)C4—C51.377 (9)
N1—C61.344 (7)C4—H40.9300
N2—C71.152 (6)C5—C61.369 (8)
O1—C11.417 (6)C5—H50.9300
O1—H10.8200C6—H60.9300
S1—C71.629 (5)
N2i—Co1—N297.4 (2)O1—C1—C2109.0 (4)
N2i—Co1—N199.78 (17)O1—C1—H1A109.9
N2—Co1—N197.81 (17)C2—C1—H1A109.9
N2i—Co1—N1i97.81 (17)O1—C1—H1B109.9
N2—Co1—N1i99.78 (17)C2—C1—H1B109.9
N1—Co1—N1i153.2 (2)H1A—C1—H1B108.3
N2i—Co1—O1i172.34 (15)N1—C2—C3121.9 (5)
N2—Co1—O1i85.30 (16)N1—C2—C1117.1 (4)
N1—Co1—O1i86.92 (15)C3—C2—C1121.0 (5)
N1i—Co1—O1i74.63 (15)C4—C3—C2119.2 (5)
N2i—Co1—O185.30 (16)C4—C3—H3120.4
N2—Co1—O1172.34 (15)C2—C3—H3120.4
N1—Co1—O174.63 (15)C3—C4—C5119.5 (5)
N1i—Co1—O186.92 (15)C3—C4—H4120.2
O1i—Co1—O193.0 (2)C5—C4—H4120.2
C2—N1—C6118.3 (4)C6—C5—C4118.3 (5)
C2—N1—Co1118.2 (3)C6—C5—H5120.8
C6—N1—Co1123.4 (4)C4—C5—H5120.8
C7—N2—Co1178.7 (4)N1—C6—C5122.7 (5)
C1—O1—Co1111.0 (3)N1—C6—H6118.7
C1—O1—H1109.4C5—C6—H6118.7
Co1—O1—H1115.4N2—C7—S1178.5 (4)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···S1ii0.822.513.296 (5)161
Symmetry codes: (ii) x−1/2, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Co1—N2i2.039 (5)Co1—N12.093 (4)
Co1—N22.039 (5)Co1—O12.239 (4)
N2i—Co1—N297.4 (2)N1—Co1—O1i86.92 (15)
N2—Co1—N197.81 (17)N2—Co1—O1172.34 (15)
N2—Co1—N1i99.78 (17)N1—Co1—O174.63 (15)
N1—Co1—N1i153.2 (2)O1i—Co1—O193.0 (2)
N2—Co1—O1i85.30 (16)
Symmetry codes: (i) −x+1, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···S1ii0.822.513.296 (5)161
Symmetry codes: (ii) x−1/2, y+1/2, −z+1/2.
Acknowledgements top

This work was supported by the National Natural Science Foundation of the People's Republic of China (project No. 20371025).

references
References top

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

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

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

Yang, E.-C., Harden, N., Wernsdorfer, W., Zakharov, L., Brechin, E. K., Rheingold, A. L., Christou, G. & Hendrickson, D. N. (2003). Polyhedron, 22, 1857–1863.

Yoo, J., Brechin, E. K., Yamaguchi, A., Nakano, M., Huffman, J. C., Maniero, A. L., Brunel, L.-C., Awaga, K., Ishimoto, H., Christou, G. & Hendrickson, D. N. (2000). Inorg. Chem. 39, 3615–3623. AUTHOR; for future reference, please note that all author names should be given here; only the first three of each reference were provided in the original CIF.