Dichlorido(dimethyl­glyoximato-κ2 N,N′)(dimethyl­glyoxime-κ2 N,N′)cobalt(III)

P Ramesh; A SubbiahPandi; P Jothi; C Revathi; A Dayalan

doi:10.1107/S1600536807068407

. 2008 Jan 4;64(Pt 2):m300–m301. doi: 10.1107/S1600536807068407

Dichlorido(dimethylglyoximato-κ² N,N′)(dimethylglyoxime-κ² N,N′)cobalt(III)

P Ramesh ^a, A SubbiahPandi ^a,^*, P Jothi ^b, C Revathi ^b, A Dayalan ^b

PMCID: PMC2960257 PMID: 21201276

Abstract

In the title compound, [Co(C₄H₇N₂O₂)Cl₂(C₄H₈N₂O₂)], the Co^III ion has a distorted octahedral coordination environment. The equatorial plane consists of four N atoms, two each from the dimethylglyoxime and dimethylglyoximate ligands, while the two axial positions are occupied by two chloride ions. Strong intramolecular O—H⋯O hydrogen bonds are observed between the dimethylglyoxime and dimethylglyoximate ligands. Molecules are linked into a chain running along the [101] direction by O—H⋯O and C—H⋯Cl hydrogen bonds. The chains are cross-linked through intermolecular C—H⋯Cl hydrogen bonds.

Related literature

For related literature, see: Dayalan & Vijayaraghavan (2001 ▶); Lee et al. (2007 ▶); Gupta et al. (2000 ▶, 2001 ▶, 2004 ▶); Ohkubo & Fukuzumi (2005 ▶); Razavelt et al. (2005 ▶). Trommel et al. (2001 ▶).

Experimental

Crystal data

[Co(C₄H₇N₂O₂)Cl₂(C₄H₈N₂O₂)]
M _r = 361.07
Monoclinic,
a = 8.1901 (2) Å
b = 8.1261 (2) Å
c = 10.4463 (3) Å
β = 102.007 (1)°
V = 680.03 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.67 mm⁻¹
T = 293 (2) K
0.20 × 0.12 × 0.12 mm

Data collection

Bruker–Nonius Kappa-APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.786, T _max = 0.819
10990 measured reflections
5284 independent reflections
4711 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.057
S = 0.99
5284 reflections
179 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ▶), 2067 Friedel pairs
Flack parameter: 0.008 (7)

Data collection: APEX2 (Bruker–Nonius, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker–Nonius, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068407/ci2517sup1.cif

e-64-0m300-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068407/ci2517Isup2.hkl

e-64-0m300-Isup2.hkl^{(253.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cl1—Co	2.2292 (4)
Cl2—Co	2.2261 (4)
Co—N2	1.8870 (12)
Co—N3	1.9048 (13)
Co—N1	1.9051 (12)
Co—N4	1.9181 (12)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.82	1.81	2.5875 (16)	158
O4—H4⋯O2	0.82	1.89	2.6604 (18)	156
O2—H2⋯O1ⁱ	0.82	1.73	2.5297 (17)	163
C4—H4C⋯Cl1ⁱ	0.96	2.73	3.6473 (19)	160
C5—H5A⋯Cl1ⁱⁱ	0.96	2.67	3.6317 (18)	175

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors are grateful to Dr S. Ramanathan, Principal, Presidency College (Autonomous), Chennai, India, and Rev. Fr A. Albert Muthumalai, S. J., Principal, Loyola College (Autonomous), Chennai, India, for providing the necessary facilities. The Head, SAIF, CDRI, Lucknow, India, is thanked for supplying the elemental analysis data and the Head, SAIF, IIT Madras, Chennai, India, for recording the NMR spectra and for the X-ray data collection.

supplementary crystallographic information

Comment

Dimethylglyoximatocobalt(III) complexes, generally known as cobaloximes, have been studied extensively as model compounds for vitamine-B₁₂ (Trommel et al., 2001; Ohkubo & Fukuzumi, 2005). Most of the work on cobaloximes include electron-transfer reactions (Dayalan & Vijayaraghavan, 2001) and catalytic activity (Razavelt et al., 2005) in solution. There are few literature evidences relating the structural aspects of cobaloximes (Gupta et al., 2000; Gupta et al., 2001; Gupta et al., 2004). We report here the synthesis and X-ray crystal structure of the title compoud.

The coordination geometry around the Co^III ion can be described as a slightly distorted octahedron. The axial positions are occupied by the chloride ions. The glyoxime moieties are individually planar. The Co^III ion and the four N atoms of dimethylglyoxime ligands are approximately coplanar. The Co—N and Co—Cl bond lengths are normal (Table 1), and are comparable with the corresponding values observed in a related complex (Lee et al., 2007).

Strong intramolecular O—H···O hydrogen bonds are observed between the dimethylglyoxime and dimethylglyoximate ligands (Table 2). The crystal packing is stabilized by O—H···O and C—H···Cl hydrogen bonds. Atoms O2 and C4 of the molecule at (x, y, z) act as donors to atoms O1 and Cl1, respectively, of the molecule at (-1/2 + x, -y, -1/2 + z). These two hydrogen bonds form a chain running along the [1 0 1] direction. The chains are cross-linked through C—H···Cl intermolecular hydrogen bonds.

Experimental

Cobalt(II) chloride hexahydrate was thoroughly grinded and exposed to microwave for 30 s. Dehydrated cobalt(II) chloride (1.3 g) was mixed with dimethyl glyoxime (2.32 g). The mixture was intimately grinded and made into a paste using acetone and exposed to microwave radiation for 60 s. The microwave treated reaction mixture was exposed to atmosphere, till it became green. The green coloured product was recrystallized from acetone. Single crystals were obtained by slow evaporation of the acetone solution.