catena-Poly[[[tetra­aqua­cobalt(II)]-μ-4,4′-bipyridine-κ2 N:N′] pyridine-3,5-dicarboxyl­ate trihydrate]

Xian-Dong Zhu

doi:10.1107/S1600536811023816

. 2011 Jun 25;67(Pt 7):m970–m971. doi: 10.1107/S1600536811023816

catena-Poly[[[tetraaquacobalt(II)]-μ-4,4′-bipyridine-κ² N:N′] pyridine-3,5-dicarboxylate trihydrate]

Xian-Dong Zhu ^a,^*

PMCID: PMC3151975 PMID: 21836946

Abstract

The crystal structure of the title compound, {[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O}_n, consists of Co^II polymeric complex cations, uncoordinated pyridine-3,5-dicarboxylate anions and lattice water molecules. The Co^II cation is coordinated by two N atoms from two 4,4′-bipyridine ligands and four water molecules in a distorted octahedral geometry. The 4,4′-bipyridine ligands bridge Co cations, forming a polymeric chain running along the b axis. The two pyridine rings of the 4,4′-biyridine are twisted to each other by a dihedral angle of 8.95 (9)°. Extensive O—H⋯O hydrogen bonding network is present in the crystal structure.

Related literature

For the utility of 4,4′-bipyridine in assembling metal-organic frameworks, see: Briadha & Fujita (2001 ▶). For related complexes, see: Li et al. (2004 ▶); Zhang & Zhu (2005 ▶). For the synthesis, see: Whitfield et al. (2001 ▶).

Experimental

Crystal data

[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O
M _r = 506.33
Triclinic,
a = 7.0053 (18) Å
b = 11.449 (3) Å
c = 14.077 (4) Å
α = 105.352 (4)°
β = 92.837 (4)°
γ = 94.624 (2)°
V = 1082.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.669, T _max = 0.842
8332 measured reflections
4863 independent reflections
4345 reflections with I > 2σ(I)
R _int = 0.012

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.118
S = 0.96
4863 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.28 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811023816/xu5203sup1.cif

e-67-0m970-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023816/xu5203Isup2.hkl

e-67-0m970-Isup2.hkl^{(238.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1W	2.0898 (12)
Co1—O2W	2.0764 (14)
Co1—O3W	2.1245 (13)
Co1—O4W	2.0709 (14)
Co1—N1	2.1692 (14)
Co1—N2ⁱ	2.1543 (14)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2ⁱⁱ	0.85	1.84	2.6813 (19)	173
O1W—H1B⋯O1ⁱⁱⁱ	0.85	1.96	2.780 (2)	162
O2W—H2A⋯O1	0.85	1.91	2.760 (2)	176
O2W—H2B⋯O6W	0.85	1.87	2.707 (2)	168
O3W—H3A⋯O1ⁱⁱⁱ	0.85	2.12	2.897 (2)	152
O3W—H3B⋯O3^iv	0.85	1.89	2.7408 (19)	176
O4W—H4A⋯O5W	0.85	1.82	2.665 (3)	171
O4W—H4B⋯O7W	0.85	1.90	2.734 (2)	168
O5W—H5A⋯O4ⁱ	0.85	1.90	2.747 (3)	172
O5W—H5B⋯O4^v	0.85	2.19	2.856 (3)	135
O6W—H6A⋯N3ⁱ	0.85	1.98	2.829 (2)	173
O6W—H6B⋯O2^vi	0.85	1.99	2.830 (2)	172
O7W—H7A⋯O3^v	0.85	1.98	2.828 (2)	175
O7W—H7B⋯O3	0.85	1.96	2.800 (2)	168

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

Acknowledgments

This work was supported financially by the Science Foundation of the Education Department of Anhui Province (KJ2010B012) and the Funds of Talent Introduction Project of Anhui Polytechnic University, China (2008YQQ010).

supplementary crystallographic information

Comment

The utility of linear bifunctional ligands, such as 4,4'-bipyridine, has been widely explored in the field of the crystal engineering of metal-organic frameworks (Briadha et al., 2001). Recently, we are interested in the assembly of new compounds which contain not only 4,4'-bipyridine ligand but also carboxylate groups in the crystal structure. In this paper, we report the synthesis and crystal structure of the title compound.

In the title compound, the cation shows a slightly distorted octahedral coordination environment composed of a six-coordinated Co(II) center. The 4,4'-bipyridine units bridge the Co(II) atoms directly to form a one-dimensional chain; similar to a Co^II complex (Li et al., 2004) and and a Ni^II complex (Zhang & Zhu, 2005) reported previously. The pyridine-3,5-dicarboxylate anion does not take part in coordination, but acts as a charge balance with two deprotonated carboxylate groups, and supplies hydrogen-bonding donor and acceptors. O—H···O and N—H···O hydrogen-bonds exist between uncoordinated anion, uncoordinated water and coordinated water molecules, which connect the one-dimensional chain into three-dimensional supramolecular network.

Experimental

A mixture of Co(NO₃)₂.6H₂O (0.064 g, 0.2 mmol), 4,4-bipyridine (0.034 g, 0.2 mmol), pyridine-3,5-dicarboxylic acid (0.034 g, 0.2 mmol), NaOH (0.008 g, 0.2 mmol) in water (10 ml) was sealed in a 25 ml Teflon-lined stainless steel autoclave. The mixture was heated at 423 K for 72 h, then slowly cooled to room temperature during 48 h. Two kinds of crystals were obtained from the reaction mixture. One is purple and needle shaped, which structure was reported by Whitfield et al. (2001); the other one is red and prism shaped, the structure is reported here.