Chloridobis[diphenyl­glyoximato(1–)-κ2 N,N′](1H-imidazole-κN 3)cobalt(III) hemihydrate

P Meera; C Revathi; A Dayalan

doi:10.1107/S160053680804347X

. 2009 Jan 8;65(Pt 2):m140–m141. doi: 10.1107/S160053680804347X

Chloridobis[diphenylglyoximato(1–)-κ² N,N′](1H-imidazole-κN ³)cobalt(III) hemihydrate

P Meera ^a,^*, C Revathi ^a, A Dayalan ^a

PMCID: PMC2968413 PMID: 21581756

Abstract

The Co centre in the title compound, [Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O, shows a slightly distorted octahedral coordination geometry. The glyoximate units of the molecule are linked by O—H⋯O hydrogen bonds with the H atom almost in the middle of the two O atoms. The crystal packing is stabilized through intermolecular N—H⋯O, N—H⋯N and O—H⋯Cl hydrogen bonds. The uncoordinated water molecule shows half-occupation.

Related literature

For related literature, see: Calleri et al. (1967 ▶); Gupta et al. (2001 ▶, 2004 ▶); Lopez et al. (1991 ▶); Mandal & Gupta (2005 ▶); Silverstein & Bassler (1984 ▶); Toscano et al. (1983 ▶).

Experimental

Crystal data

[Co(C₁₄H₁₁N₂O₂)₂Cl(C₃H₄N₂)]·0.5H₂O
M _r = 649.97
Orthorhombic,
a = 19.1004 (11) Å
b = 12.0462 (7) Å
c = 26.9627 (18) Å
V = 6203.8 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.732, T _max = 0.850
28473 measured reflections
5282 independent reflections
3705 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.104
S = 1.06
5282 reflections
415 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680804347X/bt2831sup1.cif

e-65-0m140-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804347X/bt2831Isup2.hkl

e-65-0m140-Isup2.hkl^{(253.5KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H2⋯O2	1.05 (4)	1.46 (4)	2.482 (3)	165 (3)
O3—H3⋯O1	1.07 (5)	1.39 (5)	2.456 (3)	174 (4)
N6—H6A⋯O2ⁱ	0.98 (4)	1.78 (4)	2.747 (4)	166 (3)
N6—H6A⋯N2ⁱ	0.98 (4)	2.50 (4)	3.326 (4)	141 (3)
O5—H5B⋯Cl1	0.946 (10)	2.69 (8)	3.331 (7)	126 (7)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to Rev. Fr A. Albert Muthumalai, S.J., Principal, Loyola College (Autonomous), Chennai, India, for providing the necessary facilities, the head, SAIF, CDRI, Lucknow, India, for supplying elemental 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

The coordination geometry around cobalt is octahedral with the four nitrogen atoms of the diphenyl glyoximato ligand forming an approximate square plane. The bite angles N1—Co—N2 and N3—Co—N4 of the ligand are 81.40 (10)° and 80.32 (10)°, respectively. The coordinating chlorine and imidazole nitrogen [N5—Co1—Cl1 = 179.11 (7)°] are perpendicular to the equatorial plane composed by the four N atoms. The two glyoximate moieties are linked by strong O—H···O hydrogen bonds. Similar hydrogen bonds are found in nickel(II)glyoximate (Calleri, et al., 1967). The molecule is linked to its b-glide equivalent through a N—H···O hydrogen bond The water molecule forms a short O—H···Cl contact.

Experimental

Cobaltous chloride hexahydrate was thoroughly ground and exposed to microwave for 30 s. The dehydrated salt was mixed with diphenylglyoxime in 1:2 molar ratio in acetone medium and was stirred for an hour (Toscano, et al., 1983; Gupta, et al., 2001). Since the dichloro complex of diphenyl glyoxime was non-isolable, the complex solution was as such refluxed with equimolar ratio of imidazole for six hours to get the title compound. The resulting brown mass was filtered, washed with ether and dried in a vaccuum desiccator. The complex was dissolved in ethanol and kept in a dark room for crystallization. Brown crystals of the complex appeared in three days. The elemental analysis data, obtained by analytical methods agree well with the theoretical data expected for the formula of the complex proposed: Anal%, (cald%): C, 62.07(62.57); H, 4.82(4.71); N, 14.50(14.13). The C=N stretching vibration of oxime in the complex was observed at 1629 cm^-1 and the intra molecular hydrogen bonded OH around 3400 cm^-1. A moderate peak around 1252 cm^-1 may be assigned to the C=N—O stretching of the oxime. The peak around 537 cm^-1 could be attributed to cobalt(III)-nitrogen stretching. The ¹H NMR spectra of the complex in acetone-d₆ shows three different signals corresponding to diphenyl glyoximate ring protons (Gupta, et al., 2004; Lopez, et al., 1991). The ortho H atoms of the ring shows a doublet at d= 7.4 p.p.m., the meta protons and the para proton give triplets at d = 7.6 and 7.9 p.p.m. respectively. The oxime –OH resonates at d=8.3 p.p.m.. The axial protons also appeared as multiplets along with phenyl protons at 7.2 and 7.4 p.p.m. as three proton signal (Silverstein & Bassler, 1984; Mandal & Gupta, 2005).