Chloridobis(dimethyl-glyoximato-κN,N')(4-methyl-pyridine-κN)cobalt(III) hemihydrate.

In the title complex, [Co(C(4)H(7)N(2)O(2))(2)Cl(C(6)H(7)N)]·0.5H(2)O, the central Co(III) ion, chelated by four N atoms of the two bidenate glyoximate ligands, exhibits a slightly distorted octa-hedral geometry. The axial positions are occupied by a chloride ion and the 4-methyl-pyridine N atom. Inter-molecular O-H⋯O hydrogen bonds link the mol-ecules in the crystal via the water mol-ecules, while the glyoximate ligands exhibit intra-molecular O-H⋯O hydrogen bonds.

Related literature

For similar structures, see: Revathi et al. (2009 ▶); Kavitha et al. (2008 ▶). For vitamin-B12 models, see: Brown et al. (2005 ▶); Randaccio et al. (1989 ▶). For structure–property relationships, see: Gupta et al. (2004 ▶); Dutta et al. (2009 ▶). For intra­molecular hydrogen bonding, see: Reemers & Englert (2002 ▶); Dolphin (1982 ▶); For details of the synthesis, see: Ramesh et al. (2008 ▶); Toscano et al. (1983 ▶). For spectroscopic details, see: Dayalan & Vijayaraghavan (2001 ▶); Silverstein & Bassler (1984 ▶); Bline & Hadzi (1958 ▶). For chemical properties of cobaloximes, see: Schrauzer & Windgassen (1966 ▶).

Experimental

Crystal data

[Co(C4H7N2O2)2Cl(C6H7N)]·0.5H2O

M = 425.74

Orthorhombic,

a = 8.330 (5) Å

b = 14.365 (5) Å

c = 15.634 (5) Å

V = 1870.8 (14) Å3

Z = 4

Mo Kα radiation

μ = 1.09 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2008 ▶) T min = 0.772, T max = 0.811

10519 measured reflections

4642 independent reflections

4143 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.077

S = 1.02

4642 reflections

248 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.38 e Å−3

Absolute structure: Flack (1983 ▶), 1983 Friedel pairs

Flack parameter: 0.014 (13)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2008 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020162/jh2292sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020162/jh2292Isup2.hkl

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

[Co(C4H7N2O2)2Cl(C6H7N)]·0.5H2O	Dx = 1.512 Mg m−3
Mr = 425.74	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5528 reflections
a = 8.330 (5) Å	θ = 2.6–28.2°
b = 14.365 (5) Å	µ = 1.09 mm−1
c = 15.634 (5) Å	T = 293 K
V = 1870.8 (14) Å3	Block, brown
Z = 4	0.25 × 0.20 × 0.20 mm
F(000) = 880

Bruker SMART APEXII CCD diffractometer	4642 independent reflections
Radiation source: fine-focus sealed tube	4143 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω and φ scans	θmax = 28.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker 2008)	h = −10→10
Tmin = 0.772, Tmax = 0.811	k = −19→18
10519 measured reflections	l = −20→20

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.0405P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
4642 reflections	Δρmax = 0.40 e Å−3
248 parameters	Δρmin = −0.38 e Å−3
2 restraints	Absolute structure: Flack (1983), 1983 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.014 (13)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7398 (3)	0.39874 (18)	0.25266 (16)	0.0398 (5)
C2	0.7058 (3)	0.49050 (18)	0.28872 (15)	0.0408 (6)
C3	0.8891 (3)	0.3435 (2)	0.2701 (2)	0.0643 (9)
H3A	0.8637	0.2783	0.2702	0.097*
H3B	0.9319	0.3608	0.3249	0.097*
H3C	0.9672	0.3560	0.2265	0.097*
C4	0.8147 (4)	0.5421 (3)	0.3478 (2)	0.0741 (10)
H4A	0.7709	0.6026	0.3591	0.111*
H4B	0.9185	0.5485	0.3218	0.111*
H4C	0.8248	0.5083	0.4005	0.111*
C5	0.1881 (3)	0.40417 (17)	0.08949 (15)	0.0406 (6)
C6	0.1538 (3)	0.49521 (17)	0.12558 (16)	0.0392 (5)
C7	0.0753 (4)	0.3542 (3)	0.0314 (2)	0.0759 (10)
H7A	0.0627	0.3891	−0.0206	0.114*
H7B	−0.0270	0.3477	0.0589	0.114*
H7C	0.1177	0.2937	0.0183	0.114*
C8	0.0047 (3)	0.5485 (3)	0.1072 (2)	0.0644 (9)
H8A	0.0054	0.6055	0.1393	0.097*
H8B	−0.0870	0.5121	0.1232	0.097*
H8C	−0.0004	0.5625	0.0472	0.097*
C9	0.2872 (3)	0.43850 (15)	0.35158 (13)	0.0331 (4)
H9	0.2853	0.5030	0.3467	0.040*
C10	0.2280 (3)	0.39842 (16)	0.42473 (15)	0.0387 (5)
H10	0.1854	0.4358	0.4677	0.046*
C11	0.2313 (3)	0.30297 (17)	0.43490 (15)	0.0376 (5)
C12	0.2910 (3)	0.25176 (16)	0.36721 (16)	0.0376 (5)
H12	0.2935	0.1871	0.3707	0.045*
C13	0.3464 (3)	0.29497 (15)	0.29503 (15)	0.0351 (5)
H13	0.3846	0.2588	0.2501	0.042*
C14	0.1738 (4)	0.2569 (2)	0.51559 (18)	0.0596 (8)
H14A	0.0587	0.2530	0.5148	0.089*
H14B	0.2075	0.2928	0.5641	0.089*
H14C	0.2184	0.1954	0.5193	0.089*
N1	0.6300 (2)	0.36941 (12)	0.20091 (12)	0.0341 (4)
N2	0.5693 (3)	0.52355 (12)	0.26275 (11)	0.0349 (4)
N3	0.3268 (3)	0.37229 (13)	0.11255 (12)	0.0346 (4)
N4	0.2679 (2)	0.52672 (12)	0.17406 (12)	0.0334 (4)
N5	0.3474 (2)	0.38848 (11)	0.28726 (11)	0.0269 (4)
O1	0.6426 (2)	0.28837 (12)	0.15990 (12)	0.0484 (4)
O2	0.5187 (3)	0.60675 (11)	0.28888 (12)	0.0476 (5)
O3	0.3788 (3)	0.29032 (14)	0.08378 (12)	0.0524 (5)
O4	0.2592 (2)	0.61073 (11)	0.21081 (12)	0.0483 (5)
Cl1	0.56856 (8)	0.51419 (4)	0.07531 (4)	0.04044 (14)
Co1	0.44843 (3)	0.447668 (17)	0.188051 (17)	0.02570 (8)
O5	0.8676 (9)	0.1476 (5)	0.1002 (5)	0.117 (2)	0.50
H3	0.4797 (19)	0.288 (2)	0.104 (2)	0.066 (11)*
H2	0.426 (3)	0.621 (3)	0.261 (2)	0.087 (13)*

	U11	U22	U33	U12	U13	U23
C1	0.0293 (12)	0.0521 (14)	0.0381 (12)	−0.0008 (10)	−0.0037 (10)	0.0140 (11)
C2	0.0345 (12)	0.0535 (14)	0.0345 (12)	−0.0124 (11)	−0.0104 (10)	0.0099 (10)
C3	0.0362 (14)	0.080 (2)	0.076 (2)	0.0095 (14)	−0.0095 (14)	0.0267 (18)
C4	0.069 (2)	0.090 (2)	0.0638 (19)	−0.023 (2)	−0.0352 (17)	0.0010 (18)
C5	0.0370 (13)	0.0506 (13)	0.0341 (12)	−0.0111 (11)	−0.0101 (10)	0.0045 (10)
C6	0.0277 (12)	0.0510 (13)	0.0388 (12)	0.0003 (11)	−0.0027 (10)	0.0144 (10)
C7	0.071 (2)	0.089 (2)	0.068 (2)	−0.024 (2)	−0.0365 (18)	−0.0029 (18)
C8	0.0343 (14)	0.087 (2)	0.0724 (19)	0.0160 (14)	−0.0032 (13)	0.0242 (18)
C9	0.0363 (11)	0.0300 (10)	0.0331 (10)	−0.0003 (9)	0.0018 (9)	−0.0065 (9)
C10	0.0412 (13)	0.0441 (12)	0.0309 (10)	−0.0013 (10)	0.0052 (11)	−0.0101 (10)
C11	0.0328 (12)	0.0482 (13)	0.0317 (11)	−0.0059 (10)	−0.0030 (10)	0.0040 (10)
C12	0.0405 (13)	0.0306 (10)	0.0415 (12)	0.0002 (10)	0.0020 (11)	0.0042 (9)
C13	0.0402 (12)	0.0278 (9)	0.0372 (12)	0.0029 (9)	0.0023 (10)	−0.0032 (8)
C14	0.067 (2)	0.0712 (18)	0.0405 (16)	−0.0139 (16)	0.0089 (15)	0.0088 (14)
N1	0.0303 (9)	0.0373 (9)	0.0348 (10)	0.0051 (7)	0.0020 (8)	0.0029 (8)
N2	0.0413 (11)	0.0320 (8)	0.0312 (9)	−0.0089 (9)	−0.0018 (9)	−0.0001 (7)
N3	0.0401 (12)	0.0355 (9)	0.0283 (9)	−0.0036 (8)	−0.0025 (8)	−0.0054 (7)
N4	0.0344 (10)	0.0315 (8)	0.0343 (10)	0.0049 (7)	0.0001 (8)	0.0037 (7)
N5	0.0273 (9)	0.0251 (7)	0.0282 (8)	0.0018 (7)	−0.0005 (7)	−0.0013 (6)
O1	0.0480 (10)	0.0418 (8)	0.0553 (11)	0.0150 (8)	0.0079 (9)	−0.0052 (8)
O2	0.0639 (13)	0.0307 (7)	0.0482 (10)	−0.0095 (8)	−0.0048 (9)	−0.0084 (7)
O3	0.0678 (13)	0.0433 (9)	0.0463 (11)	0.0021 (9)	−0.0060 (10)	−0.0203 (8)
O4	0.0586 (12)	0.0314 (8)	0.0549 (11)	0.0134 (8)	0.0025 (9)	−0.0017 (8)
Cl1	0.0367 (3)	0.0529 (3)	0.0317 (2)	−0.0044 (3)	−0.0007 (3)	0.0089 (2)
Co1	0.02577 (13)	0.02728 (12)	0.02404 (12)	0.00065 (11)	−0.00294 (11)	−0.00153 (10)
O5	0.119 (5)	0.121 (4)	0.111 (5)	0.036 (5)	0.008 (4)	0.015 (4)

C1—N1	1.292 (3)	C9—H9	0.9300
C1—C2	1.461 (4)	C10—C11	1.381 (3)
C1—C3	1.500 (3)	C10—H10	0.9300
C2—N2	1.297 (3)	C11—C12	1.382 (3)
C2—C4	1.491 (4)	C11—C14	1.503 (3)
C3—H3A	0.9600	C12—C13	1.368 (3)
C3—H3B	0.9600	C12—H12	0.9300
C3—H3C	0.9600	C13—N5	1.349 (3)
C4—H4A	0.9600	C13—H13	0.9300
C4—H4B	0.9600	C14—H14A	0.9600
C4—H4C	0.9600	C14—H14B	0.9600
C5—N3	1.294 (3)	C14—H14C	0.9600
C5—C6	1.453 (4)	N1—O1	1.333 (3)
C5—C7	1.491 (4)	N1—Co1	1.8951 (19)
C6—N4	1.297 (3)	N2—O2	1.332 (3)
C6—C8	1.487 (4)	N2—Co1	1.8885 (19)
C7—H7A	0.9600	N3—O3	1.333 (3)
C7—H7B	0.9600	N3—Co1	1.8953 (19)
C7—H7C	0.9600	N4—O4	1.339 (2)
C8—H8A	0.9600	N4—Co1	1.897 (2)
C8—H8B	0.9600	N5—Co1	1.9589 (18)
C8—H8C	0.9600	O2—H2	0.907 (10)
C9—N5	1.334 (3)	O3—H3	0.900 (10)
C9—C10	1.372 (3)	Cl1—Co1	2.2408 (8)
O1···O5	2.911 (8)	O5···O3i	3.013 (7)
N1—C1—C2	113.5 (2)	C13—C12—C11	120.8 (2)
N1—C1—C3	121.9 (3)	C13—C12—H12	119.6
C2—C1—C3	124.6 (2)	C11—C12—H12	119.6
N2—C2—C1	112.3 (2)	N5—C13—C12	121.9 (2)
N2—C2—C4	123.0 (3)	N5—C13—H13	119.1
C1—C2—C4	124.7 (3)	C12—C13—H13	119.1
C1—C3—H3A	109.5	C11—C14—H14A	109.5
C1—C3—H3B	109.5	C11—C14—H14B	109.5
H3A—C3—H3B	109.5	H14A—C14—H14B	109.5
C1—C3—H3C	109.5	C11—C14—H14C	109.5
H3A—C3—H3C	109.5	H14A—C14—H14C	109.5
H3B—C3—H3C	109.5	H14B—C14—H14C	109.5
C2—C4—H4A	109.5	C1—N1—O1	122.0 (2)
C2—C4—H4B	109.5	C1—N1—Co1	115.98 (16)
H4A—C4—H4B	109.5	O1—N1—Co1	122.00 (15)
C2—C4—H4C	109.5	C2—N2—O2	120.7 (2)
H4A—C4—H4C	109.5	C2—N2—Co1	116.73 (17)
H4B—C4—H4C	109.5	O2—N2—Co1	122.61 (17)
N3—C5—C6	112.7 (2)	C5—N3—O3	120.6 (2)
N3—C5—C7	124.2 (3)	C5—N3—Co1	116.65 (17)
C6—C5—C7	123.1 (3)	O3—N3—Co1	122.76 (18)
N4—C6—C5	113.4 (2)	C6—N4—O4	121.7 (2)
N4—C6—C8	123.0 (3)	C6—N4—Co1	116.06 (16)
C5—C6—C8	123.6 (2)	O4—N4—Co1	122.21 (15)
C5—C7—H7A	109.5	C9—N5—C13	117.81 (19)
C5—C7—H7B	109.5	C9—N5—Co1	121.65 (14)
H7A—C7—H7B	109.5	C13—N5—Co1	120.40 (15)
C5—C7—H7C	109.5	N2—O2—H2	109 (2)
H7A—C7—H7C	109.5	N3—O3—H3	103 (2)
H7B—C7—H7C	109.5	N2—Co1—N1	81.44 (9)
C6—C8—H8A	109.5	N2—Co1—N3	179.57 (9)
C6—C8—H8B	109.5	N1—Co1—N3	98.84 (9)
H8A—C8—H8B	109.5	N2—Co1—N4	98.54 (9)
C6—C8—H8C	109.5	N1—Co1—N4	179.31 (9)
H8A—C8—H8C	109.5	N3—Co1—N4	81.17 (9)
H8B—C8—H8C	109.5	N2—Co1—N5	89.43 (8)
N5—C9—C10	122.5 (2)	N1—Co1—N5	90.09 (8)
N5—C9—H9	118.7	N3—Co1—N5	90.89 (8)
C10—C9—H9	118.7	N4—Co1—N5	90.60 (8)
C9—C10—C11	120.4 (2)	N2—Co1—Cl1	90.12 (6)
C9—C10—H10	119.8	N1—Co1—Cl1	88.85 (7)
C11—C10—H10	119.8	N3—Co1—Cl1	89.57 (7)
C10—C11—C12	116.6 (2)	N4—Co1—Cl1	90.46 (6)
C10—C11—C14	121.9 (2)	N5—Co1—Cl1	178.90 (6)
C12—C11—C14	121.5 (2)
N1—C1—C2—N2	1.4 (3)	C2—N2—Co1—Cl1	−90.64 (17)
C3—C1—C2—N2	179.3 (2)	O2—N2—Co1—Cl1	89.93 (16)
N1—C1—C2—C4	−177.8 (3)	C1—N1—Co1—N2	2.65 (17)
C3—C1—C2—C4	0.1 (4)	O1—N1—Co1—N2	−178.23 (18)
N3—C5—C6—N4	−0.3 (3)	C1—N1—Co1—N3	−177.67 (17)
C7—C5—C6—N4	−179.6 (2)	O1—N1—Co1—N3	1.44 (18)
N3—C5—C6—C8	178.2 (2)	C1—N1—Co1—N4	91 (8)
C7—C5—C6—C8	−1.1 (4)	O1—N1—Co1—N4	−89 (8)
N5—C9—C10—C11	1.1 (4)	C1—N1—Co1—N5	−86.76 (17)
C9—C10—C11—C12	−2.2 (4)	O1—N1—Co1—N5	92.35 (17)
C9—C10—C11—C14	177.4 (2)	C1—N1—Co1—Cl1	92.94 (17)
C10—C11—C12—C13	1.3 (4)	O1—N1—Co1—Cl1	−87.94 (17)
C14—C11—C12—C13	−178.4 (2)	C5—N3—Co1—N2	−50 (13)
C11—C12—C13—N5	0.9 (4)	O3—N3—Co1—N2	130 (13)
C2—C1—N1—O1	177.96 (19)	C5—N3—Co1—N1	179.18 (17)
C3—C1—N1—O1	0.0 (3)	O3—N3—Co1—N1	−0.80 (19)
C2—C1—N1—Co1	−2.9 (3)	C5—N3—Co1—N4	−1.52 (17)
C3—C1—N1—Co1	179.11 (19)	O3—N3—Co1—N4	178.50 (19)
C1—C2—N2—O2	−179.79 (19)	C5—N3—Co1—N5	88.95 (18)
C4—C2—N2—O2	−0.5 (4)	O3—N3—Co1—N5	−91.03 (18)
C1—C2—N2—Co1	0.8 (3)	C5—N3—Co1—Cl1	−92.05 (17)
C4—C2—N2—Co1	−180.0 (2)	O3—N3—Co1—Cl1	87.97 (18)
C6—C5—N3—O3	−178.62 (19)	C6—N4—Co1—N2	−178.99 (16)
C7—C5—N3—O3	0.7 (4)	O4—N4—Co1—N2	2.02 (18)
C6—C5—N3—Co1	1.4 (3)	C6—N4—Co1—N1	92 (8)
C7—C5—N3—Co1	−179.3 (2)	O4—N4—Co1—N1	−87 (8)
C5—C6—N4—O4	178.05 (19)	C6—N4—Co1—N3	1.33 (16)
C8—C6—N4—O4	−0.4 (3)	O4—N4—Co1—N3	−177.66 (18)
C5—C6—N4—Co1	−0.9 (3)	C6—N4—Co1—N5	−89.47 (17)
C8—C6—N4—Co1	−179.41 (19)	O4—N4—Co1—N5	91.53 (17)
C10—C9—N5—C13	1.1 (3)	C6—N4—Co1—Cl1	90.82 (16)
C10—C9—N5—Co1	−174.48 (18)	O4—N4—Co1—Cl1	−88.17 (16)
C12—C13—N5—C9	−2.1 (4)	C9—N5—Co1—N2	47.81 (18)
C12—C13—N5—Co1	173.54 (18)	C13—N5—Co1—N2	−127.67 (19)
C2—N2—Co1—N1	−1.82 (17)	C9—N5—Co1—N1	129.25 (18)
O2—N2—Co1—N1	178.75 (18)	C13—N5—Co1—N1	−46.23 (18)
C2—N2—Co1—N3	−133 (13)	C9—N5—Co1—N3	−131.90 (18)
O2—N2—Co1—N3	47 (13)	C13—N5—Co1—N3	52.61 (18)
C2—N2—Co1—N4	178.87 (17)	C9—N5—Co1—N4	−50.73 (18)
O2—N2—Co1—N4	−0.56 (18)	C13—N5—Co1—N4	133.79 (18)
C2—N2—Co1—N5	88.36 (17)	C9—N5—Co1—Cl1	114 (3)
O2—N2—Co1—N5	−91.07 (17)	C13—N5—Co1—Cl1	−62 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.90 (1)	1.61 (1)	2.499 (3)	168 (3)
O2—H2···O4	0.91 (1)	1.60 (2)	2.483 (3)	162 (4)

Table 1

Selected interatomic distances (Å)

O1⋯O5	2.911 (8)
O5⋯O3i	3.013 (7)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.90 (1)	1.61 (1)	2.499 (3)	168 (3)
O2—H2⋯O4	0.91 (1)	1.60 (2)	2.483 (3)	162 (4)