catena-Poly[cobalt(II)-bis­(μ-3,7-dichloro­quinoline-8-carboxyl­ato-κ3 N,O:O′)]

Zequan Li; Fengjing Wu; Yun Gong; Yunhuai Zhang; Chenguang Bai

doi:10.1107/S1600536807066755

. 2007 Dec 21;64(Pt 1):m227. doi: 10.1107/S1600536807066755

catena-Poly[cobalt(II)-bis(μ-3,7-dichloroquinoline-8-carboxylato-κ³ N,O:O′)]

Zequan Li ^a, Fengjing Wu ^a, Yun Gong ^a,^*, Yunhuai Zhang ^a, Chenguang Bai ^b

PMCID: PMC2915151 PMID: 21200573

Abstract

In the crystal structure of the title compound, [Co(C₁₀H₄Cl₂NO₂)₂]_n, the Co^II cation lies on a twofold rotation axis. Each cation is N,O-chelated by the carboxylate anions of two 3,7-dichloroquinoline-8-carboxylate ligands. The second carboxylate O atom of each ligand coordinates to the Co^II cation of an adjacent molecule, linking the cations into a linear chain. Strong interchain π–π stacking interactions are observed in the crystal structure (perpendicular distance 3.42 Å, centroid-to-centroid distance 3.874 Å)

Related literature

For the use of 3,7-dichloro-8-quinolinecarboxylic acid as a herbicide, see: Nuria et al. (1997 ▶); Pornprom et al. (2006 ▶); Sunohara & Matsumoto (2004 ▶); Tresch & Grossmann (2002 ▶). For related vanadium and cadmium complexes, see Chen et al. (2001 ▶); Yang et al. (2005 ▶). For related literature, see: Turel et al. (2004 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

[Co(C₁₀H₄Cl₂NO₂)₂]
M _r = 541.01
Orthorhombic,
a = 13.5109 (14) Å
b = 15.964 (2) Å
c = 9.2157 (16) Å
V = 1987.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.43 mm⁻¹
T = 298 (2) K
0.49 × 0.33 × 0.31 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.57, T _max = 0.64
9558 measured reflections
1752 independent reflections
1404 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.089
S = 1.11
1752 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066755/sj2456sup1.cif

e-64-0m227-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066755/sj2456Isup2.hkl

e-64-0m227-Isup2.hkl^{(86.4KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Co1—O1	2.093 (2)
Co1—O2ⁱ	2.057 (2)
Co1—N1	2.197 (2)

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O2ⁱ—Co1—O2ⁱⁱ	103.60 (12)
O2ⁱ—Co1—O1	170.96 (9)
O2ⁱⁱ—Co1—O1	85.43 (8)
O1—Co1—O1ⁱⁱⁱ	85.55 (12)
O2ⁱ—Co1—N1	90.97 (9)
O2ⁱⁱ—Co1—N1	87.24 (9)
O1—Co1—N1	89.82 (9)
O1ⁱⁱⁱ—Co1—N1	92.31 (9)
N1ⁱⁱⁱ—Co1—N1	177.10 (14)

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

Acknowledgments

This work was supported by the Natural Science Young Scholars Foundation of Chongqing University and Chongqing University Postgraduate Science and Innovation Fund.

supplementary crystallographic information

Comment

Quinolinecarboxylates generally chelate to metal atoms, and some metal quinolinecarboxylates have been reported such as, for example, bis(6-methyl-4-hydroxy-3-quinolinecarboxylate) mono(oxo)monohydroxyvanadium(V) and Cd(H₂O)(4-quinolinecarboxylato)₂ (Chen et al., 2001; Yang et al., 2005). Quinclorac (3,7-dichloro-8-quinolinecarboxylic acid) is a most effective herbicides (Nuria et al., 1997; Pornprom et al., 2006; Sunohara & Matsumoto, 2004; Tresch & Grossmann, 2002). We have reported a nickel-quinclorac complex in our previous work (Zhang et al., 2007). The title compound is a cobalt(II) derivative (I) (Fig. 1) with the Co^II cation located on a twofold rotation axis. The Co^II center exhibits a distorted octahedral geometry defined by four carboxylato oxygen atoms from four quinclorac and two nitrogen atoms from two quinclorac units. Each quinclorac ligand chelates to the cobalt atom via a quinoline N atom and a carboxylate O atom. Adjacent molecules are linked by carboxylate bridges into a linear chain. The chains are assembled into a three-dimensional supramolecular architecture by strong offset face-to-face π–π stacking interactions (perpendicular distance: 3.42 Å, centroid-centroid distance: 3.874 Å) between the C2–C7 and C2ⁱ–C7ⁱ benzene rings [symmetry code: (i) 2 - x, 1 - y, - z].

Experimental

A mixture of quinclorac (0.5 mmol, 0.121 g), CoCl₂.6H₂O (1 mmol, 0.238 g), Na₂MoO₄.2H₂O (0.5 mmol, 0.121 g) and H₂O (10 ml) was treated with aqueous HCl to a pH of 5. The mixture was placed in a Teflon-lined autoclave; this was heated at 403 K for three days. Red crystals were collected and washed with water. C H & N elemental analysis. Calculated for C₂₀H₈Cl₄N₂O₄Co: C 44.36, H 1.48, N 5.18%; found: C 44.48, H 1.69, N 5.31%. Selected FT—IR (KBr, cm^-1): 3301(w), 1581(s), 1553(m), 1482(m), 1402(m), 1383(s), 1232(m), 1139 (m), 1101(s), 761(m), 553(m), 449(m).