Bis(1H-imidazole-κN3)bis­(2-oxidopyridinium-3-carboxyl­ato-κ2O2,O3)cobalt(II)

Zhang, B.-Y.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536809028694

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m987-m988

doi:10.1107/S1600536809028694

Open

access

Bis(1H-imidazole-κN³)bis(2-oxidopyridinium-3-carboxylato-κ²O²,O³)cobalt(II)

Bing-Yu Zhang,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 18 July 2009; accepted 20 July 2009; online 25 July 2009)

In the molecule of the title Co^II complex, [Co(C₆H₄NO₃)₂(C₃H₄N₂)₂], the Co^II atom is located on a twofold rotation axis and chelated by two oxidopyridiniumcarboxylate anions and further cis-coordinated by two imidazole ligands in a distorted octahedral 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 carboxylate O atom links with the imidazole and pyridinium rings of adjacent molecules via N—H⋯O hydrogen bonding. Weak C—H⋯O hydrogen bonding is also present in the crystal structure.

Related literature

For the isostructural Ni^II 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_r = 471.30
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.028
wR(F²) = 0.065
S = 1.07
1824 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

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) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x, -y, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

The title Co^II complex is isostructural with the Ni^II complex (Zhang et al. 2009).

In the title molecule, the Co atom is located on a twofold axis and is coordinated by two imidazole molecules in cis-configuration, two oxidopyridinium-carboxylate anions further chelate to the Co atom with carboxyl-O and deprotonated hydroxy-O atoms to complete the distorted octahedral coordination geometry (Fig. 1 and Table 1). The benzene ring is twisted with respect to the carboxyl group and O1/O3/Co coordination plane with dihedral angles of 21.52 (13)° and 41.05 (7)°, respectively. The shorter C1—O3 [1.260 (2) Å] bond agrees with those found in the isostructural Ni complex (Zhang et al. 2009) and in the other transition metal complexes of oxidopyridinium-carboxylate (Yao et al., 2004; Yan & Hu, 2007a, b; Wen & Liu, 2007), it is also consistent with that found in hydroxy-pyridinecarboxylate complexes (Quintal et al. 2002). This finding suggests the electron delocalization between pyridine ring and hydroxy group. But this shorter C1—O3 bond is much different from the C—O bond distance of ca 1.35 Å between benzene ring and hydroxy-O atom found in hydroxybenzencarboxylic acid (Munshi & Row, 2006) and metal complexes of hydroxybenzenecarboxylate (Su & Xu, 2005; Li et al., 2005).

The uncoordinated carboxyl O atom simultaneously links with the imidazole and pyridinium rings via N—H···O hydrogen bonding of adjacent molecules (Table 2). Weak C—H···O hydrogen bonding is also present in the crystal structure.

Related literature top

For the isostructural Ni^II complex, see: Zhang et al. (2009). For the shorter C—O bond distance between the pyridine ring and 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 & Row (2006); Su & Xu (2005); Li et al. (2005).

Experimental top

2-Hydroxy-pyridine-3-carboxylic acid (0.13 g, 1 mmol), NaOH (0.04 g, 1 mmol), imidazole (0.14 g, 2 mmol) and CoCl₂.6H₂O (0.24 g, 1 mmol) were dissolved in water (15 ml). The solution was refluxed for 4.5 h, after cooling to room temperature the solution was filtered. The single crystals of the title complex were obtained from the filtrate after one week.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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).

Figures top

Fig. 1. The molecular structure of the title complex with 40% probability displacement ellipsoids (arbitrary spheres for H atoms) [symmetry code: (i) 1 - x, y, 1/2 - z].

Bis(1H-imidazole-κN³)bis(2-oxidopyridinium-3-carboxylato- κ²O²,O³)cobalt(II) top

Crystal data top

[Co(C₆H₄NO₃)₂(C₃H₄N₂)₂]	F(000) = 964
M_r = 471.30	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0231P)² + 1.9358P] where P = (F_o² + 2F_c²)/3
1824 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Co(C₆H₄NO₃)₂(C₃H₄N₂)₂]	V = 1992.1 (4) Å³
M_r = 471.30	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.594 (2) Å	µ = 0.91 mm⁻¹
b = 10.0524 (12) Å	T = 294 K
c = 12.8271 (15) Å	0.40 × 0.30 × 0.26 mm
β = 111.407 (4)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1824 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1527 reflections with I > 2σ(I)
T_min = 0.665, T_max = 0.790	R_int = 0.034
10627 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.07	Δρ_max = 0.24 e Å⁻³
1824 reflections	Δρ_min = −0.22 e Å⁻³
141 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.93	2.43	3.341 (3)	168

Symmetry codes: (ii) x, −y, z−1/2; (iii) x, −y+1, z−1/2; (iv) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₄NO₃)₂(C₃H₄N₂)₂]
M_r	471.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	16.594 (2), 10.0524 (12), 12.8271 (15)
β (°)	111.407 (4)
V (Å³)	1992.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.40 × 0.30 × 0.26

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.665, 0.790
No. of measured, independent and observed [I > 2σ(I)] reflections	10627, 1824, 1527
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.065, 1.07
No. of reflections	1824
No. of parameters	141
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

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) x, −y, z−1/2; (ii) x, −y+1, z−1/2; (iii) x, −y, z+1/2.

Acknowledgements

The project was supported by the ZIJIN project of Zhejiang University, China.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, H., Yin, K.-L. & Xu, D.-J. (2005). Acta Cryst. C61, m19–m21. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Munshi, P. & Guru Row, T. N. (2006). Acta Cryst. B62, 612–626. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Quintal, S. M. O., Nogueira, H. I. S., Felix, V. & Drew, M. G. B. (2002). Polyhedron, 21, 2783–2791. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, J.-R. & Xu, D.-J. (2005). Acta Cryst. C61, m256–m258. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Wen, D.-C. & Liu, S.-X. (2007). Chin. J. Struct. Chem. 26, 1281–1284. CAS Google Scholar
Yan, H.-Y. & Hu, T.-Q. (2007a). Acta Cryst. E63, m2325. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yan, H.-Y. & Hu, T.-Q. (2007b). Acta Cryst. E63, m2326. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yao, Y., Cai, Q., Kou, H., Li, H., Wang, D., Yu, R., Chen, Y. & Xing, X. (2004). Chem. Lett. 33, 1270–1271. Web of Science CSD CrossRef CAS Google Scholar
Zhang, B.-Y., Nie, J.-J. & Xu, D.-J. (2009). Acta Cryst. E65, m977. Web of Science CSD CrossRef IUCr Journals Google Scholar