Bis(1H-imidazole-κN)bis-(2-oxidopyridinium-3-carboxyl-ato-κO,O)cobalt(II).

In the mol-ecule of the title Co(II) complex, [Co(C(6)H(4)NO(3))(2)(C(3)H(4)N(2))(2)], the Co(II) atom is located on a twofold rotation axis and chelated by two oxidopyridiniumcarboxyl-ate anions and further cis-coordinated by two imidazole ligands in a distorted octa-hedral geometry. The shorter C-O bond distance of 1.260 (2) Å suggests electron delocalization between the oxido group and the pyridinium ring. The uncoordinated carboxyl-ate O atom links with the imidazole and pyridinium rings of adjacent mol-ecules via N-H⋯O hydrogen bonding. Weak C-H⋯O hydrogen bonding is also present in the crystal structure.

Related literature

For the isostructural NiII complex, see: Zhang et al. (2009 ▶). For the shorter C—O bond distance between the pyridine ring and the hydr­oxy-O atom in 2-oxidopyridinium-3-carboxyl­ate complexes and in 2-hydroxy­pyridine­carboxyl­ate complexes, see: Yao et al. (2004 ▶); Yan & Hu (2007a ▶,b ▶); Wen & Liu (2007 ▶); Quintal et al. (2002 ▶). For the corresponding C—O bond distances in 2-hydroxy­benzencarboxylic acid and in metal complexes of 2-hydroxy­benzencarboxyl­ate, see: Munshi & Guru Row (2006 ▶); Su & Xu (2005 ▶); Li et al. (2005 ▶).

Experimental

Crystal data

[Co(C6H4NO3)2(C3H4N2)2]

M = 471.30

Monoclinic,

a = 16.594 (2) Å

b = 10.0524 (12) Å

c = 12.8271 (15) Å

β = 111.407 (4)°

V = 1992.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.91 mm−1

T = 294 K

0.40 × 0.30 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.665, T max = 0.790

10627 measured reflections

1824 independent reflections

1527 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.065

S = 1.07

1824 reflections

141 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.22 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028694/hk2743sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028694/hk2743Isup2.hkl

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

[Co(C6H4NO3)2(C3H4N2)2]	F(000) = 964
Mr = 471.30	Dx = 1.571 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4226 reflections
a = 16.594 (2) Å	θ = 2.5–25.2°
b = 10.0524 (12) Å	µ = 0.91 mm−1
c = 12.8271 (15) Å	T = 294 K
β = 111.407 (4)°	Block, pink
V = 1992.1 (4) Å3	0.40 × 0.30 × 0.26 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	1824 independent reflections
Radiation source: fine-focus sealed tube	1527 reflections with I > 2σ(I)
graphite	Rint = 0.034
Detector resolution: 10.00 pixels mm-1	θmax = 25.4°, θmin = 2.4°
ω scans	h = −20→20
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.665, Tmax = 0.790	l = −14→15
10627 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0231P)2 + 1.9358P] where P = (Fo2 + 2Fc2)/3
1824 reflections	(Δ/σ)max < 0.001
141 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.22 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
Co	0.5000	0.24771 (3)	0.2500	0.02958 (13)
N1	0.61270 (11)	−0.12644 (16)	0.30331 (13)	0.0369 (4)
H1	0.6138	−0.1391	0.2376	0.044*
N2	0.58362 (11)	0.39282 (16)	0.22623 (13)	0.0348 (4)
N3	0.62322 (13)	0.56271 (17)	0.14899 (16)	0.0468 (5)
H3	0.6198	0.6308	0.1070	0.056*
O1	0.56130 (10)	0.24739 (13)	0.42230 (11)	0.0392 (4)
O2	0.62213 (10)	0.16732 (14)	0.59300 (10)	0.0410 (4)
O3	0.58952 (9)	0.09062 (13)	0.25972 (10)	0.0352 (3)
C1	0.59989 (12)	0.00073 (18)	0.33196 (15)	0.0293 (4)
C2	0.60117 (12)	0.01700 (18)	0.44393 (15)	0.0288 (4)
C3	0.61152 (14)	−0.0923 (2)	0.51100 (17)	0.0375 (5)
H3A	0.6115	−0.0814	0.5830	0.045*
C4	0.62211 (16)	−0.2203 (2)	0.47472 (18)	0.0454 (6)
H4	0.6278	−0.2938	0.5209	0.055*
C5	0.62375 (16)	−0.2340 (2)	0.37099 (19)	0.0449 (6)
H5	0.6325	−0.3175	0.3457	0.054*
C6	0.59387 (12)	0.15307 (19)	0.48875 (15)	0.0299 (4)
C7	0.55679 (15)	0.4904 (2)	0.15344 (18)	0.0396 (5)
H7	0.4990	0.5071	0.1105	0.048*
C8	0.67219 (15)	0.4046 (2)	0.27010 (19)	0.0458 (6)
H8	0.7094	0.3488	0.3242	0.055*
C9	0.69703 (16)	0.5089 (2)	0.2231 (2)	0.0510 (6)
H9	0.7533	0.5381	0.2383	0.061*

	U11	U22	U33	U12	U13	U23
Co	0.0402 (2)	0.02722 (19)	0.0222 (2)	0.000	0.01241 (16)	0.000
N1	0.0554 (12)	0.0342 (9)	0.0257 (9)	0.0042 (8)	0.0204 (8)	−0.0020 (7)
N2	0.0400 (11)	0.0327 (9)	0.0318 (9)	0.0006 (8)	0.0132 (8)	0.0052 (7)
N3	0.0641 (14)	0.0341 (10)	0.0528 (12)	−0.0039 (9)	0.0340 (11)	0.0065 (9)
O1	0.0589 (10)	0.0309 (7)	0.0245 (7)	0.0071 (7)	0.0115 (7)	−0.0005 (6)
O2	0.0612 (10)	0.0410 (8)	0.0201 (7)	0.0046 (7)	0.0142 (7)	−0.0032 (6)
O3	0.0529 (9)	0.0334 (7)	0.0254 (7)	0.0071 (6)	0.0214 (7)	0.0040 (6)
C1	0.0330 (11)	0.0313 (10)	0.0254 (10)	0.0008 (8)	0.0129 (8)	−0.0023 (8)
C2	0.0332 (11)	0.0319 (10)	0.0227 (10)	0.0011 (8)	0.0118 (8)	−0.0005 (8)
C3	0.0507 (14)	0.0394 (11)	0.0271 (10)	0.0019 (10)	0.0196 (10)	0.0012 (9)
C4	0.0715 (17)	0.0337 (11)	0.0357 (12)	0.0057 (11)	0.0250 (12)	0.0072 (9)
C5	0.0686 (16)	0.0295 (11)	0.0415 (13)	0.0051 (10)	0.0259 (12)	0.0002 (9)
C6	0.0332 (11)	0.0354 (10)	0.0243 (10)	−0.0003 (9)	0.0142 (8)	−0.0014 (8)
C7	0.0446 (13)	0.0367 (11)	0.0375 (12)	0.0002 (10)	0.0149 (10)	0.0041 (9)
C8	0.0411 (14)	0.0475 (13)	0.0471 (14)	0.0035 (10)	0.0141 (11)	0.0018 (10)
C9	0.0435 (15)	0.0493 (14)	0.0666 (17)	−0.0068 (11)	0.0278 (13)	−0.0092 (12)

Co—O1i	2.0684 (13)	O2—C6	1.253 (2)
Co—O1	2.0684 (13)	O3—C1	1.260 (2)
Co—O3i	2.1402 (13)	C1—C2	1.438 (3)
Co—O3	2.1402 (13)	C2—C3	1.367 (3)
Co—N2	2.1107 (16)	C2—C6	1.506 (3)
Co—N2i	2.1107 (16)	C3—C4	1.401 (3)
N1—C5	1.357 (3)	C3—H3A	0.9300
N1—C1	1.368 (2)	C4—C5	1.348 (3)
N1—H1	0.8600	C4—H4	0.9300
N2—C7	1.315 (2)	C5—H5	0.9300
N2—C8	1.374 (3)	C7—H7	0.9300
N3—C7	1.339 (3)	C8—C9	1.347 (3)
N3—C9	1.359 (3)	C8—H8	0.9300
N3—H3	0.8600	C9—H9	0.9300
O1—C6	1.258 (2)
O1i—Co—O1	179.82 (7)	O3—C1—C2	126.95 (17)
O1i—Co—N2	86.54 (6)	N1—C1—C2	115.31 (16)
O1—Co—N2	93.59 (6)	C3—C2—C1	119.33 (17)
O1i—Co—N2i	93.59 (6)	C3—C2—C6	119.94 (16)
O1—Co—N2i	86.54 (6)	C1—C2—C6	120.71 (16)
N2—Co—N2i	92.57 (9)	C2—C3—C4	122.10 (18)
O1i—Co—O3i	82.90 (5)	C2—C3—H3A	119.0
O1—Co—O3i	96.97 (5)	C4—C3—H3A	119.0
N2—Co—O3i	168.64 (5)	C5—C4—C3	118.14 (19)
N2i—Co—O3i	92.26 (6)	C5—C4—H4	120.9
O1i—Co—O3	96.97 (5)	C3—C4—H4	120.9
O1—Co—O3	82.90 (5)	C4—C5—N1	120.26 (19)
N2—Co—O3	92.26 (6)	C4—C5—H5	119.9
N2i—Co—O3	168.64 (5)	N1—C5—H5	119.9
O3i—Co—O3	84.91 (8)	O2—C6—O1	122.54 (17)
C5—N1—C1	124.81 (17)	O2—C6—C2	117.41 (17)
C5—N1—H1	117.6	O1—C6—C2	120.05 (16)
C1—N1—H1	117.6	N2—C7—N3	111.4 (2)
C7—N2—C8	105.13 (18)	N2—C7—H7	124.3
C7—N2—Co	123.24 (15)	N3—C7—H7	124.3
C8—N2—Co	131.44 (14)	C9—C8—N2	109.9 (2)
C7—N3—C9	107.46 (18)	C9—C8—H8	125.1
C7—N3—H3	126.3	N2—C8—H8	125.1
C9—N3—H3	126.3	C8—C9—N3	106.1 (2)
C6—O1—Co	130.35 (12)	C8—C9—H9	126.9
C1—O3—Co	118.52 (12)	N3—C9—H9	126.9
O3—C1—N1	117.74 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ii	0.86	1.93	2.789 (2)	177
N3—H3···O2iii	0.86	2.04	2.806 (2)	148
C3—H3A···O3iv	0.93	2.43	3.341 (3)	168

Table 1

Selected bond lengths (Å)

Co—O1	2.0684 (13)
Co—O3	2.1402 (13)
Co—N2	2.1107 (16)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	1.93	2.789 (2)	177
N3—H3⋯O2ii	0.86	2.04	2.806 (2)	148
C3—H3A⋯O3iii	0.93	2.43	3.341 (3)	168

Symmetry codes: (i) ; (ii) ; (iii) .