Chloridobis(dimethyl-glyoximato-κN,N')(ethyl pyridine-4-carboxyl-ate-κN)cobalt(III) chloro-form monosolvate.

The title compound, [Co(C(4)H(7)N(2)O(2))(2)Cl(C(8)H(9)NO(2))]·CHCl(3), was synthesized as a model complex of vitamin B(12). The Co(III) cation displays an approximately octa-hedral coordination environment, being displaced by 0.0240 (15) Å from the mean plane of the four N atoms of the equatorial plane. The O-H distances in the dimethyl-glyoximate hy-droxy groups are 0.89 (6) and 1.14 (6) Å; such long O-H bonds are very common in cobaloxime derivatives. Weak classical O-H⋯N and non-classical C-H⋯Cl hydrogen-bonding interactions further consolidate the crystal packing.

Related literature

For background on the chemistry of cobaloximes, see: Schrayzer (1968 ▶); Zangrando et al. (2003 ▶). For applications of cobaloximes in proton reduction, see: Raza­vet et al. (2005 ▶). For related structures, see: Bhuyan et al. (2007 ▶); Dutta et al. (2009 ▶); Mandal & Gupta (2005 ▶, 2007 ▶); William et al. (1973 ▶). For NMR research on O—H⋯O bridges, see: Bakac & Espenson (1984 ▶). For deprotonation of O—H⋯O bridges by BF3·Et2O, see: Magnuson & Weber (1974 ▶).

Experimental

Crystal data

[Co(C4H7N2O2)2Cl(C8H9NO2)]·CHCl3

M = 595.14

Orthorhombic,

a = 10.053 (3) Å

b = 22.357 (7) Å

c = 23.099 (8) Å

V = 5192 (3) Å3

Z = 8

Mo Kα radiation

μ = 1.11 mm−1

T = 293 K

0.29 × 0.14 × 0.06 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.829, T max = 0.935

24393 measured reflections

4558 independent reflections

3483 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.158

S = 1.08

4558 reflections

310 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.25 e Å−3

Δρmin = −0.78 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812002449/zl2444sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002449/zl2444Isup2.hkl

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

[Co(C4H7N2O2)2Cl(C8H9NO2)]·CHCl3	F(000) = 2432
Mr = 595.14	Dx = 1.523 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5509 reflections
a = 10.053 (3) Å	θ = 2.4–24.8°
b = 22.357 (7) Å	µ = 1.11 mm−1
c = 23.099 (8) Å	T = 293 K
V = 5192 (3) Å3	Needle, brown
Z = 8	0.29 × 0.14 × 0.06 mm

Bruker APEXII area-detector diffractometer	4558 independent reflections
Radiation source: fine-focus sealed tube	3483 reflections with I > 2σ(I)
graphite	Rint = 0.039
phi and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→9
Tmin = 0.829, Tmax = 0.935	k = −26→26
24393 measured reflections	l = −27→24

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0892P)2 + 4.4304P] where P = (Fo2 + 2Fc2)/3
4558 reflections	(Δ/σ)max = 0.001
310 parameters	Δρmax = 1.25 e Å−3
0 restraints	Δρmin = −0.78 e Å−3

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
Co1	0.23591 (5)	0.00646 (2)	0.63484 (2)	0.03477 (19)
Cl1	0.08443 (9)	0.07824 (5)	0.62035 (4)	0.0473 (3)
N2	0.2686 (3)	0.00560 (14)	0.55381 (14)	0.0387 (7)
N4	0.3608 (3)	0.06594 (13)	0.65679 (12)	0.0364 (7)
O2	0.3577 (3)	0.04186 (12)	0.52883 (11)	0.0489 (7)
N3	0.1977 (3)	0.00927 (14)	0.71495 (13)	0.0407 (7)
N5	0.3706 (3)	−0.05592 (13)	0.64728 (13)	0.0406 (7)
O4	0.4372 (3)	0.09421 (12)	0.61771 (11)	0.0473 (7)
O3	0.1032 (3)	−0.02516 (14)	0.73944 (11)	0.0558 (7)
C4	0.3647 (4)	0.07978 (16)	0.71110 (15)	0.0384 (8)
N1	0.1090 (3)	−0.05257 (15)	0.61321 (13)	0.0443 (8)
C2	0.2011 (4)	−0.03273 (18)	0.52384 (15)	0.0438 (9)
O1	0.0261 (3)	−0.07852 (15)	0.65120 (13)	0.0617 (9)
C3	0.2708 (3)	0.04442 (17)	0.74594 (16)	0.0406 (9)
C1	0.1055 (4)	−0.06658 (18)	0.55898 (16)	0.0478 (10)
C6	0.2193 (5)	−0.0395 (2)	0.45984 (18)	0.0661 (13)
H6A	0.3024	−0.0591	0.4522	0.099*
H6B	0.2193	−0.0008	0.4420	0.099*
H6C	0.1478	−0.0630	0.4443	0.099*
C7	0.2605 (4)	0.0476 (2)	0.81032 (17)	0.0580 (12)
H7A	0.1723	0.0599	0.8210	0.087*
H7B	0.3238	0.0760	0.8248	0.087*
H7C	0.2787	0.0089	0.8266	0.087*
C9	0.4808 (4)	−0.05867 (19)	0.61441 (18)	0.0514 (10)
H9A	0.4920	−0.0307	0.5850	0.062*
C8	0.4506 (4)	0.12779 (18)	0.73592 (18)	0.0522 (10)
H8A	0.5049	0.1446	0.7059	0.078*
H8B	0.5065	0.1111	0.7655	0.078*
H8C	0.3955	0.1585	0.7524	0.078*
C10	0.5774 (4)	−0.10112 (19)	0.6225 (2)	0.0571 (11)
H10A	0.6512	−0.1022	0.5982	0.069*
C13	0.3583 (4)	−0.09637 (18)	0.68994 (17)	0.0518 (10)
H13A	0.2825	−0.0953	0.7130	0.062*
C5	0.0100 (5)	−0.1112 (2)	0.5347 (2)	0.0683 (13)
H5A	−0.0506	−0.1237	0.5645	0.102*
H5B	0.0582	−0.1452	0.5205	0.102*
H5C	−0.0389	−0.0933	0.5035	0.102*
C11	0.5646 (5)	−0.14251 (19)	0.66696 (19)	0.0548 (11)
C12	0.4530 (5)	−0.1392 (2)	0.70090 (19)	0.0601 (12)
H12A	0.4414	−0.1659	0.7313	0.072*
O5	0.7541 (4)	−0.1941 (2)	0.6368 (2)	0.1054 (16)
O6	0.6596 (6)	−0.2213 (2)	0.7205 (2)	0.134 (2)
C14	0.6648 (6)	−0.1899 (2)	0.6788 (3)	0.0737 (15)
C15	0.8560 (7)	−0.2399 (3)	0.6427 (4)	0.130 (3)
H15A	0.8681	−0.2498	0.6833	0.156*
H15B	0.9399	−0.2252	0.6277	0.156*
C16	0.8152 (9)	−0.2930 (4)	0.6107 (3)	0.127 (3)
H16A	0.8815	−0.3236	0.6149	0.191*
H16B	0.8053	−0.2831	0.5705	0.191*
H16C	0.7318	−0.3072	0.6256	0.191*
Cl2	0.3288 (3)	0.21423 (11)	0.52934 (9)	0.1438 (9)
Cl3	0.2763 (2)	0.24725 (11)	0.64763 (12)	0.1451 (11)
Cl4	0.0658 (2)	0.24578 (13)	0.56700 (13)	0.1782 (13)
C17	0.2161 (6)	0.2156 (3)	0.5858 (2)	0.0785 (15)
H17A	0.1983	0.1736	0.5954	0.094*
H2	0.406 (6)	0.064 (3)	0.568 (3)	0.105 (19)*
H1	0.053 (6)	−0.060 (3)	0.683 (3)	0.10 (2)*

	U11	U22	U33	U12	U13	U23
Co1	0.0347 (3)	0.0443 (3)	0.0253 (3)	−0.0059 (2)	0.00124 (18)	0.00086 (19)
Cl1	0.0387 (5)	0.0631 (6)	0.0401 (5)	0.0045 (4)	−0.0007 (4)	0.0016 (4)
N2	0.0389 (17)	0.0465 (18)	0.0306 (17)	−0.0038 (14)	0.0041 (12)	0.0030 (13)
N4	0.0354 (16)	0.0430 (16)	0.0308 (16)	−0.0006 (13)	−0.0008 (12)	0.0025 (13)
O2	0.0527 (17)	0.0618 (17)	0.0321 (14)	−0.0127 (14)	0.0075 (12)	0.0021 (12)
N3	0.0389 (17)	0.0536 (19)	0.0296 (16)	−0.0037 (14)	0.0033 (13)	0.0034 (13)
N5	0.0424 (17)	0.0409 (17)	0.0384 (17)	−0.0040 (14)	−0.0010 (13)	0.0012 (13)
O4	0.0460 (15)	0.0562 (16)	0.0398 (15)	−0.0164 (13)	0.0049 (11)	0.0074 (12)
O3	0.0506 (17)	0.0802 (19)	0.0366 (15)	−0.0215 (15)	0.0116 (12)	0.0071 (14)
C4	0.0384 (19)	0.0416 (19)	0.035 (2)	0.0047 (16)	−0.0036 (15)	0.0002 (15)
N1	0.0430 (18)	0.0542 (19)	0.0358 (18)	−0.0111 (15)	−0.0005 (13)	0.0029 (14)
C2	0.052 (2)	0.051 (2)	0.0293 (18)	−0.0015 (18)	−0.0021 (17)	−0.0057 (17)
O1	0.065 (2)	0.078 (2)	0.0422 (17)	−0.0358 (17)	0.0040 (14)	0.0046 (16)
C3	0.037 (2)	0.056 (2)	0.0287 (18)	0.0056 (17)	−0.0011 (15)	−0.0013 (17)
C1	0.052 (2)	0.055 (2)	0.037 (2)	−0.0067 (19)	−0.0063 (17)	−0.0052 (18)
C6	0.075 (3)	0.090 (4)	0.033 (2)	−0.014 (3)	0.003 (2)	−0.013 (2)
C7	0.057 (3)	0.086 (3)	0.031 (2)	−0.006 (2)	0.0015 (17)	−0.005 (2)
C9	0.047 (2)	0.051 (2)	0.056 (3)	0.0002 (19)	0.0069 (19)	0.0105 (19)
C8	0.056 (2)	0.056 (2)	0.044 (2)	−0.007 (2)	−0.0107 (19)	−0.0058 (18)
C10	0.049 (2)	0.054 (2)	0.068 (3)	0.004 (2)	0.004 (2)	0.002 (2)
C13	0.059 (3)	0.054 (2)	0.042 (2)	−0.001 (2)	0.0035 (18)	0.0085 (19)
C5	0.081 (3)	0.070 (3)	0.053 (3)	−0.029 (3)	−0.013 (2)	−0.007 (2)
C11	0.061 (3)	0.048 (2)	0.055 (3)	0.003 (2)	−0.015 (2)	−0.002 (2)
C12	0.080 (3)	0.052 (2)	0.048 (3)	0.001 (2)	−0.006 (2)	0.012 (2)
O5	0.074 (3)	0.078 (3)	0.164 (5)	0.031 (2)	0.017 (3)	0.036 (3)
O6	0.180 (5)	0.134 (4)	0.089 (3)	0.091 (4)	−0.008 (3)	0.028 (3)
C14	0.084 (4)	0.057 (3)	0.081 (4)	0.016 (3)	−0.028 (3)	0.000 (3)
C15	0.086 (5)	0.098 (5)	0.207 (9)	0.052 (4)	0.016 (5)	0.038 (6)
C16	0.151 (8)	0.114 (6)	0.118 (6)	0.072 (6)	0.003 (5)	0.020 (5)
Cl2	0.159 (2)	0.167 (2)	0.1055 (15)	0.0384 (17)	0.0411 (14)	0.0400 (13)
Cl3	0.1212 (16)	0.178 (2)	0.1355 (19)	0.0474 (15)	−0.0562 (14)	−0.0717 (16)
Cl4	0.1211 (17)	0.229 (3)	0.185 (3)	0.0840 (18)	−0.0778 (17)	−0.087 (2)
C17	0.081 (4)	0.079 (4)	0.075 (4)	−0.007 (3)	−0.009 (3)	0.001 (3)

Co1—N3	1.891 (3)	C7—H7C	0.9600
Co1—N4	1.898 (3)	C9—C10	1.370 (6)
Co1—N2	1.901 (3)	C9—H9A	0.9300
Co1—N1	1.902 (3)	C8—H8A	0.9600
Co1—N5	1.965 (3)	C8—H8B	0.9600
Co1—Cl1	2.2375 (12)	C8—H8C	0.9600
N2—C2	1.294 (5)	C10—C11	1.389 (6)
N2—O2	1.339 (4)	C10—H10A	0.9300
N4—C4	1.293 (5)	C13—C12	1.374 (6)
N4—O4	1.344 (4)	C13—H13A	0.9300
O2—H2	1.14 (6)	C5—H5A	0.9600
N3—C3	1.292 (5)	C5—H5B	0.9600
N3—O3	1.347 (4)	C5—H5C	0.9600
N5—C13	1.343 (5)	C11—C12	1.371 (6)
N5—C9	1.345 (5)	C11—C14	1.487 (6)
O4—H2	1.37 (6)	C12—H12A	0.9300
C4—C3	1.471 (5)	O5—C14	1.325 (7)
C4—C8	1.492 (5)	O5—C15	1.454 (7)
N1—C1	1.292 (5)	O6—C14	1.194 (7)
N1—O1	1.342 (4)	C15—C16	1.456 (11)
C2—C1	1.468 (6)	C15—H15A	0.9700
C2—C6	1.497 (5)	C15—H15B	0.9700
O1—H1	0.89 (6)	C16—H16A	0.9600
C3—C7	1.492 (5)	C16—H16B	0.9600
C1—C5	1.493 (6)	C16—H16C	0.9600
C6—H6A	0.9600	Cl2—C17	1.728 (6)
C6—H6B	0.9600	Cl3—C17	1.705 (6)
C6—H6C	0.9600	Cl4—C17	1.712 (6)
C7—H7A	0.9600	C17—H17A	0.9800
C7—H7B	0.9600
N3—Co1—N4	81.36 (13)	H7A—C7—H7B	109.5
N3—Co1—N2	177.80 (13)	C3—C7—H7C	109.5
N4—Co1—N2	98.96 (13)	H7A—C7—H7C	109.5
N3—Co1—N1	98.27 (13)	H7B—C7—H7C	109.5
N4—Co1—N1	179.30 (14)	N5—C9—C10	122.6 (4)
N2—Co1—N1	81.39 (13)	N5—C9—H9A	118.7
N3—Co1—N5	91.17 (13)	C10—C9—H9A	118.7
N4—Co1—N5	90.15 (13)	C4—C8—H8A	109.5
N2—Co1—N5	91.00 (13)	C4—C8—H8B	109.5
N1—Co1—N5	90.45 (14)	H8A—C8—H8B	109.5
N3—Co1—Cl1	89.10 (10)	C4—C8—H8C	109.5
N4—Co1—Cl1	89.28 (9)	H8A—C8—H8C	109.5
N2—Co1—Cl1	88.73 (10)	H8B—C8—H8C	109.5
N1—Co1—Cl1	90.12 (11)	C9—C10—C11	119.8 (4)
N5—Co1—Cl1	179.33 (10)	C9—C10—H10A	120.1
C2—N2—O2	121.4 (3)	C11—C10—H10A	120.1
C2—N2—Co1	116.3 (3)	N5—C13—C12	122.7 (4)
O2—N2—Co1	122.3 (2)	N5—C13—H13A	118.6
C4—N4—O4	121.5 (3)	C12—C13—H13A	118.6
C4—N4—Co1	116.6 (2)	C1—C5—H5A	109.5
O4—N4—Co1	121.9 (2)	C1—C5—H5B	109.5
N2—O2—H2	102 (3)	H5A—C5—H5B	109.5
C3—N3—O3	121.0 (3)	C1—C5—H5C	109.5
C3—N3—Co1	116.5 (3)	H5A—C5—H5C	109.5
O3—N3—Co1	122.4 (2)	H5B—C5—H5C	109.5
C13—N5—C9	117.3 (4)	C12—C11—C10	117.6 (4)
C13—N5—Co1	121.5 (3)	C12—C11—C14	119.2 (5)
C9—N5—Co1	121.2 (3)	C10—C11—C14	123.2 (5)
N4—O4—H2	102 (2)	C11—C12—C13	120.0 (4)
N4—C4—C3	112.5 (3)	C11—C12—H12A	120.0
N4—C4—C8	124.3 (3)	C13—C12—H12A	120.0
C3—C4—C8	123.2 (3)	C14—O5—C15	117.3 (5)
C1—N1—O1	120.8 (3)	O6—C14—O5	125.3 (5)
C1—N1—Co1	116.2 (3)	O6—C14—C11	122.5 (6)
O1—N1—Co1	123.0 (2)	O5—C14—C11	112.1 (5)
N2—C2—C1	112.9 (3)	O5—C15—C16	109.1 (7)
N2—C2—C6	122.1 (4)	O5—C15—H15A	109.9
C1—C2—C6	125.0 (4)	C16—C15—H15A	109.9
N1—O1—H1	99 (4)	O5—C15—H15B	109.9
N3—C3—C4	112.9 (3)	C16—C15—H15B	109.9
N3—C3—C7	122.8 (4)	H15A—C15—H15B	108.3
C4—C3—C7	124.3 (3)	C15—C16—H16A	109.5
N1—C1—C2	113.1 (3)	C15—C16—H16B	109.5
N1—C1—C5	122.9 (4)	H16A—C16—H16B	109.5
C2—C1—C5	123.9 (4)	C15—C16—H16C	109.5
C2—C6—H6A	109.5	H16A—C16—H16C	109.5
C2—C6—H6B	109.5	H16B—C16—H16C	109.5
H6A—C6—H6B	109.5	Cl3—C17—Cl4	111.2 (3)
C2—C6—H6C	109.5	Cl3—C17—Cl2	114.0 (3)
H6A—C6—H6C	109.5	Cl4—C17—Cl2	113.2 (4)
H6B—C6—H6C	109.5	Cl3—C17—H17A	105.9
C3—C7—H7A	109.5	Cl4—C17—H17A	105.9
C3—C7—H7B	109.5	Cl2—C17—H17A	105.9

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	1.14 (6)	1.37 (6)	2.495 (4)	168 (5)
O2—H2···N4	1.14 (6)	2.10 (6)	3.004 (4)	133 (4)
O1—H1···O3	0.89 (6)	1.60 (6)	2.486 (4)	177 (6)
O1—H1···N3	0.89 (6)	2.25 (6)	3.000 (4)	142 (5)
C17—H17A···Cl1	0.98	2.49	3.437 (6)	163
C6—H6C···Cl1i	0.96	2.79	3.675 (5)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4	1.14 (6)	1.37 (6)	2.495 (4)	168 (5)
O2—H2⋯N4	1.14 (6)	2.10 (6)	3.004 (4)	133 (4)
O1—H1⋯O3	0.89 (6)	1.60 (6)	2.486 (4)	177 (6)
O1—H1⋯N3	0.89 (6)	2.25 (6)	3.000 (4)	142 (5)
C17—H17A⋯Cl1	0.98	2.49	3.437 (6)	163
C6—H6C⋯Cl1i	0.96	2.79	3.675 (5)	153

Symmetry code: (i) .