Butyl-bis-(dimethyl-glyoximato-κN,N')(pyridine-κN)cobalt(III).

In the title compound, [Co(C(4)H(9))(C(4)H(7)N(2)O(2))(2)(C(5)H(5)N)], which was prepared as a model complex of vitamin B(12), the Co(III) atom is coordinated by a butyl group, a pyridine and two N,N'-bidentate dimethyl-glyoximate ligands in a distorted octa-hedral geometry. The bis-chelating dimethyl-glyoximate ligands, which occupy equatorial sites, are linked by strong intra-molecular O-H⋯O hydrogen bonds.

Related literature

For general background to organocobaloximes, see: Schrauzer & Kohnle (1964 ▶); Schrauzer (1968 ▶, 1976 ▶). For applications of cobaloximes, see: Rockenbaur et al. (1982 ▶); Giese (1986 ▶). For structure–property relationships of cobaloximes, see: Gupta et al. (2004 ▶). For related structures, see: Mandal & Gupta (2005 ▶, 2007 ▶); Kumar & Gupta (2011 ▶).

Experimental

Crystal data

[Co(C4H9)(C4H7N2O2)2(C5H5N)]

M = 425.37

Monoclinic,

a = 8.365 (2) Å

b = 10.408 (2) Å

c = 11.487 (3) Å

β = 91.768 (4)°

V = 999.7 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.89 mm−1

T = 100 K

0.22 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.828, T max = 0.871

5174 measured reflections

3400 independent reflections

3144 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.100

S = 1.05

3400 reflections

256 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.90 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack (1983 ▶), 1551 Friedel pairs

Flack parameter: 0.038 (16)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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: DIAMOND (Brandenburg, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812000967/is5041sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000967/is5041Isup2.hkl

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

[Co(C4H9)(C4H7N2O2)2(C5H5N)]	F(000) = 448
Mr = 425.37	Dx = 1.413 Mg m−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 1911 reflections
a = 8.365 (2) Å	θ = 2.6–28.2°
b = 10.408 (2) Å	µ = 0.89 mm−1
c = 11.487 (3) Å	T = 100 K
β = 91.768 (4)°	Prism, orange
V = 999.7 (4) Å3	0.22 × 0.18 × 0.16 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	3400 independent reflections
Radiation source: fine-focus sealed tube	3144 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and w scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
Tmin = 0.828, Tmax = 0.871	k = −12→8
5174 measured reflections	l = −13→13

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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.048P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3400 reflections	Δρmax = 0.90 e Å−3
256 parameters	Δρmin = −0.25 e Å−3
4 restraints	Absolute structure: Flack (1983), 1551 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.038 (16)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.5829 (5)	0.3423 (5)	0.8074 (3)	0.0196 (11)
C2	0.5910 (5)	0.2031 (5)	0.8137 (4)	0.0211 (11)
C3	0.7089 (6)	0.4250 (5)	0.7546 (4)	0.0340 (13)
H3A	0.7145	0.4059	0.6713	0.051*
H3B	0.8127	0.4073	0.7931	0.051*
H3C	0.6815	0.5157	0.7650	0.051*
C4	0.7261 (5)	0.1253 (5)	0.7673 (4)	0.0334 (12)
H4A	0.7155	0.0357	0.7922	0.050*
H4B	0.8282	0.1600	0.7974	0.050*
H4C	0.7229	0.1294	0.6820	0.050*
C5	0.0468 (5)	0.1913 (5)	1.0286 (4)	0.0224 (11)
C6	0.0360 (5)	0.3328 (5)	1.0188 (3)	0.0218 (12)
C7	−0.0980 (6)	0.4091 (5)	1.0639 (4)	0.0284 (12)
H7A	−0.0928	0.4970	1.0336	0.043*
H7B	−0.0903	0.4110	1.1492	0.043*
H7C	−0.1998	0.3698	1.0388	0.043*
C8	−0.0731 (6)	0.1105 (5)	1.0866 (4)	0.0323 (12)
H8A	−0.0743	0.0245	1.0518	0.048*
H8B	−0.1792	0.1496	1.0764	0.048*
H8C	−0.0451	0.1039	1.1698	0.048*
C9	0.1611 (4)	0.1295 (4)	0.7124 (3)	0.0202 (8)
H9	0.1899	0.0561	0.7576	0.024*
C10	0.0893 (4)	0.1114 (4)	0.6052 (3)	0.0235 (8)
H10	0.0691	0.0272	0.5765	0.028*
C11	0.0463 (5)	0.2182 (4)	0.5392 (3)	0.0234 (9)
H11	−0.0039	0.2082	0.4644	0.028*
C12	0.0774 (5)	0.3386 (4)	0.5834 (3)	0.0237 (8)
H12	0.0491	0.4133	0.5399	0.028*
C13	0.1511 (4)	0.3484 (4)	0.6931 (3)	0.0222 (8)
H13	0.1725	0.4316	0.7238	0.027*
C14	0.4381 (5)	0.2916 (4)	1.0654 (4)	0.0230 (10)
H14A	0.5480	0.2602	1.0529	0.028*
H14B	0.4463	0.3853	1.0789	0.028*
C15	0.3839 (4)	0.2318 (4)	1.1776 (3)	0.0197 (8)
H15A	0.3773	0.1374	1.1682	0.024*
H15B	0.2757	0.2640	1.1949	0.024*
C16	0.4999 (5)	0.2642 (4)	1.2799 (3)	0.0255 (9)
H16A	0.6055	0.2256	1.2650	0.031*
H16B	0.5139	0.3585	1.2840	0.031*
C17	0.4431 (6)	0.2162 (4)	1.3960 (3)	0.0351 (10)
H17A	0.5216	0.2394	1.4576	0.053*
H17B	0.4312	0.1226	1.3933	0.053*
H17C	0.3398	0.2556	1.4124	0.053*
N1	0.4540 (4)	0.3883 (4)	0.8523 (3)	0.0197 (9)
N2	0.4708 (4)	0.1519 (4)	0.8647 (3)	0.0198 (9)
N3	0.1770 (4)	0.1474 (4)	0.9832 (3)	0.0186 (9)
N4	0.1586 (4)	0.3816 (4)	0.9692 (3)	0.0174 (9)
N5	0.1929 (5)	0.2471 (3)	0.7568 (3)	0.0181 (8)
O1	0.1700 (4)	0.5107 (3)	0.9556 (2)	0.0255 (8)
O2	0.2086 (4)	0.0191 (3)	0.9865 (2)	0.0259 (8)
O3	0.4583 (4)	0.0245 (3)	0.8781 (3)	0.0266 (8)
O4	0.4259 (4)	0.5151 (3)	0.8549 (2)	0.0242 (8)
Co1	0.31315 (6)	0.26668 (4)	0.91509 (5)	0.01707 (14)
H1	0.261 (4)	0.517 (5)	0.923 (5)	0.072 (19)*
H2	0.374 (5)	0.016 (6)	0.921 (5)	0.09 (2)*

	U11	U22	U33	U12	U13	U23
C1	0.010 (2)	0.034 (3)	0.015 (2)	−0.006 (2)	−0.0007 (17)	0.000 (2)
C2	0.008 (2)	0.041 (3)	0.014 (2)	0.004 (2)	0.0023 (17)	−0.001 (2)
C3	0.022 (3)	0.051 (3)	0.029 (2)	−0.011 (2)	0.011 (2)	0.007 (2)
C4	0.024 (3)	0.045 (3)	0.031 (3)	0.005 (2)	0.006 (2)	−0.004 (2)
C5	0.022 (3)	0.030 (3)	0.016 (2)	−0.003 (2)	−0.0005 (18)	−0.003 (2)
C6	0.014 (2)	0.035 (3)	0.016 (2)	−0.001 (2)	0.0005 (17)	−0.005 (2)
C7	0.019 (2)	0.044 (3)	0.022 (2)	0.005 (2)	−0.0013 (19)	−0.005 (2)
C8	0.021 (2)	0.044 (3)	0.033 (3)	−0.011 (2)	0.0120 (19)	0.000 (2)
C9	0.019 (2)	0.019 (2)	0.0230 (19)	0.0007 (15)	0.0031 (15)	−0.0017 (15)
C10	0.021 (2)	0.022 (2)	0.028 (2)	−0.0009 (16)	0.0005 (16)	−0.0066 (16)
C11	0.016 (2)	0.035 (2)	0.0193 (19)	−0.0010 (18)	0.0008 (16)	−0.0064 (17)
C12	0.022 (2)	0.025 (2)	0.0245 (19)	0.0074 (17)	0.0038 (15)	0.0073 (17)
C13	0.019 (2)	0.022 (2)	0.026 (2)	−0.0011 (16)	0.0002 (16)	−0.0016 (16)
C14	0.016 (2)	0.034 (3)	0.018 (2)	0.000 (2)	−0.0008 (16)	0.0003 (19)
C15	0.0129 (19)	0.028 (2)	0.0178 (19)	−0.0011 (15)	−0.0008 (15)	0.0010 (15)
C16	0.021 (2)	0.038 (3)	0.017 (2)	−0.0047 (19)	0.0017 (17)	−0.0026 (17)
C17	0.044 (3)	0.044 (3)	0.017 (2)	−0.002 (2)	−0.0005 (18)	0.0068 (18)
N1	0.0166 (19)	0.029 (3)	0.0132 (17)	−0.0046 (16)	−0.0033 (14)	0.0018 (15)
N2	0.018 (2)	0.023 (2)	0.0180 (17)	0.0051 (16)	−0.0003 (14)	0.0023 (14)
N3	0.019 (2)	0.021 (2)	0.0160 (17)	0.0008 (15)	0.0001 (14)	0.0036 (14)
N4	0.0196 (19)	0.018 (2)	0.0143 (17)	−0.0015 (16)	0.0019 (14)	−0.0003 (14)
N5	0.0103 (17)	0.032 (2)	0.0126 (18)	−0.0012 (14)	0.0030 (13)	−0.0020 (15)
O1	0.0329 (19)	0.0201 (18)	0.0240 (16)	0.0030 (14)	0.0065 (14)	0.0001 (12)
O2	0.0302 (18)	0.0167 (16)	0.0308 (17)	−0.0035 (13)	−0.0004 (13)	0.0030 (13)
O3	0.0254 (18)	0.0261 (18)	0.0284 (18)	0.0080 (13)	0.0035 (14)	0.0016 (13)
O4	0.0290 (17)	0.0201 (18)	0.0238 (15)	−0.0087 (14)	0.0032 (12)	−0.0009 (12)
Co1	0.0135 (2)	0.0219 (2)	0.0160 (2)	−0.0002 (4)	0.00278 (15)	0.0001 (4)

C1—N1	1.301 (6)	C12—C13	1.390 (5)
C1—C2	1.452 (8)	C12—H12	0.9500
C1—C3	1.503 (6)	C13—N5	1.324 (5)
C2—N2	1.294 (6)	C13—H13	0.9500
C2—C4	1.502 (6)	C14—C15	1.513 (5)
C3—H3A	0.9800	C14—Co1	2.008 (4)
C3—H3B	0.9800	C14—H14A	0.9900
C3—H3C	0.9800	C14—H14B	0.9900
C4—H4A	0.9800	C15—C16	1.538 (5)
C4—H4B	0.9800	C15—H15A	0.9900
C4—H4C	0.9800	C15—H15B	0.9900
C5—N3	1.304 (6)	C16—C17	1.514 (5)
C5—C6	1.480 (8)	C16—H16A	0.9900
C5—C8	1.482 (6)	C16—H16B	0.9900
C6—N4	1.292 (5)	C17—H17A	0.9800
C6—C7	1.480 (6)	C17—H17B	0.9800
C7—H7A	0.9800	C17—H17C	0.9800
C7—H7B	0.9800	N1—O4	1.342 (5)
C7—H7C	0.9800	N1—Co1	1.887 (4)
C8—H8A	0.9800	N2—O3	1.340 (5)
C8—H8B	0.9800	N2—Co1	1.884 (4)
C8—H8C	0.9800	N3—O2	1.361 (5)
C9—N5	1.349 (5)	N3—Co1	1.873 (4)
C9—C10	1.366 (5)	N4—O1	1.357 (5)
C9—H9	0.9500	N4—Co1	1.881 (4)
C10—C11	1.387 (5)	N5—Co1	2.061 (4)
C10—H10	0.9500	O1—H1	0.86 (2)
C11—C12	1.374 (5)	O3—H2	0.87 (2)
C11—H11	0.9500
N1—C1—C2	112.7 (4)	C15—C14—H14B	107.0
N1—C1—C3	123.3 (5)	Co1—C14—H14B	107.0
C2—C1—C3	124.0 (4)	H14A—C14—H14B	106.8
N2—C2—C1	113.4 (4)	C14—C15—C16	111.2 (3)
N2—C2—C4	122.9 (5)	C14—C15—H15A	109.4
C1—C2—C4	123.7 (4)	C16—C15—H15A	109.4
C1—C3—H3A	109.5	C14—C15—H15B	109.4
C1—C3—H3B	109.5	C16—C15—H15B	109.4
H3A—C3—H3B	109.5	H15A—C15—H15B	108.0
C1—C3—H3C	109.5	C17—C16—C15	113.2 (4)
H3A—C3—H3C	109.5	C17—C16—H16A	108.9
H3B—C3—H3C	109.5	C15—C16—H16A	108.9
C2—C4—H4A	109.5	C17—C16—H16B	108.9
C2—C4—H4B	109.5	C15—C16—H16B	108.9
H4A—C4—H4B	109.5	H16A—C16—H16B	107.8
C2—C4—H4C	109.5	C16—C17—H17A	109.5
H4A—C4—H4C	109.5	C16—C17—H17B	109.5
H4B—C4—H4C	109.5	H17A—C17—H17B	109.5
N3—C5—C6	111.6 (4)	C16—C17—H17C	109.5
N3—C5—C8	124.5 (5)	H17A—C17—H17C	109.5
C6—C5—C8	123.9 (4)	H17B—C17—H17C	109.5
N4—C6—C5	112.2 (4)	C1—N1—O4	121.3 (4)
N4—C6—C7	124.3 (5)	C1—N1—Co1	116.1 (4)
C5—C6—C7	123.5 (4)	O4—N1—Co1	122.6 (3)
C6—C7—H7A	109.5	C2—N2—O3	121.6 (4)
C6—C7—H7B	109.5	C2—N2—Co1	116.1 (4)
H7A—C7—H7B	109.5	O3—N2—Co1	122.3 (3)
C6—C7—H7C	109.5	C5—N3—O2	119.8 (4)
H7A—C7—H7C	109.5	C5—N3—Co1	117.4 (4)
H7B—C7—H7C	109.5	O2—N3—Co1	122.8 (3)
C5—C8—H8A	109.5	C6—N4—O1	120.0 (4)
C5—C8—H8B	109.5	C6—N4—Co1	117.3 (3)
H8A—C8—H8B	109.5	O1—N4—Co1	122.7 (3)
C5—C8—H8C	109.5	C13—N5—C9	117.9 (4)
H8A—C8—H8C	109.5	C13—N5—Co1	121.4 (3)
H8B—C8—H8C	109.5	C9—N5—Co1	120.5 (3)
N5—C9—C10	122.8 (4)	N4—O1—H1	101 (4)
N5—C9—H9	118.6	N2—O3—H2	104 (4)
C10—C9—H9	118.6	N3—Co1—N4	81.38 (19)
C9—C10—C11	118.8 (3)	N3—Co1—N2	98.56 (11)
C9—C10—H10	120.6	N4—Co1—N2	178.50 (16)
C11—C10—H10	120.6	N3—Co1—N1	177.73 (16)
C12—C11—C10	119.1 (4)	N4—Co1—N1	98.26 (11)
C12—C11—H11	120.4	N2—Co1—N1	81.7 (2)
C10—C11—H11	120.4	N3—Co1—C14	91.91 (16)
C11—C12—C13	118.4 (4)	N4—Co1—C14	88.78 (17)
C11—C12—H12	120.8	N2—Co1—C14	89.72 (17)
C13—C12—H12	120.8	N1—Co1—C14	85.84 (16)
N5—C13—C12	123.0 (4)	N3—Co1—N5	90.94 (14)
N5—C13—H13	118.5	N4—Co1—N5	91.88 (14)
C12—C13—H13	118.5	N2—Co1—N5	89.62 (14)
C15—C14—Co1	121.2 (3)	N1—Co1—N5	91.32 (14)
C15—C14—H14A	107.0	C14—Co1—N5	177.14 (18)
Co1—C14—H14A	107.0

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.86 (2)	1.61 (2)	2.465 (3)	174 (6)
O3—H2···O2	0.87 (2)	1.60 (2)	2.465 (3)	171 (6)

Table 1

Selected bond lengths (Å)

N1—Co1	1.887 (4)
N2—Co1	1.884 (4)
N3—Co1	1.873 (4)
N4—Co1	1.881 (4)
N5—Co1	2.061 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4	0.86 (2)	1.61 (2)	2.465 (3)	174 (6)
O3—H2⋯O2	0.87 (2)	1.60 (2)	2.465 (3)	171 (6)