Phenyl­hydrazinium (6-carb­oxy­pyridine-2-carboxyl­ato)(pyridine-2,6-dicarboxyl­ato)cobaltate(II)–pyridine-2,6-dicarb­oxy­lic acid–water (1/1/3)

Consuelo Yuste; Manuela Ramos Silva; Mohammad Ghadermazi; Fariba Feizi; Elham Motieiyan

doi:10.1107/S1600536810048191

. 2010 Nov 24;66(Pt 12):m1643–m1644. doi: 10.1107/S1600536810048191

Phenylhydrazinium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cobaltate(II)–pyridine-2,6-dicarboxylic acid–water (1/1/3)

Consuelo Yuste ^a, Manuela Ramos Silva ^a,^*, Mohammad Ghadermazi ^b, Fariba Feizi ^b, Elham Motieiyan ^c

PMCID: PMC3011730 PMID: 21589313

Abstract

The asymmetric unit of the title compound, (C₆H₉N₂)[Co(C₇H₃NO₄)(C₇H₄NO₄)]·C₇H₅NO₄·3H₂O, contains one (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cobaltate(II) anion, one phenylhydrazinium cation, one pyridine-2,6-dicarboxylic acid molecule and three uncoordinated water molecules, part of which are disordered. The Co^II ion is coordinated by a pyridine-2,6-dicarboxylate ion and a 6-carboxypyridine-2-carboxylate ligand almost perpendicular to each other [the angle between the least-squares planes is 87.38 (4)°] and is surrounded by two O atoms and two N atoms in the equatorial plane and two O atoms in axial positions, resulting in a distorted octahedral coordination geometry. There is an extensive three-dimensional network of O—H⋯O and N—H⋯O hydrogen bonds, which link the components.

Related literature

For related cobalt, copper and cadmium complexes containing 2,6-dicarboxylato ligands, see: Aghabozorg et al. (2008 ▶); Aghabozorg et al. (2009 ▶); Moghimi et al. (2002 ▶). For an isotypic series of five related M(II) complexes, see: MacDonald et al. (2004 ▶). For the supramolecular chemistry and crystal structures of five bis(imidazolium 2,6-pyridinedicarboxylate)M(II) complexes, see: MacDonald et al. (2000 ▶).

Experimental

Crystal data

(C₆H₉N₂)[Co(C₇H₃NO₄)(C₇H₄NO₄)]·C₇H₅NO₄·3H₂O
M _r = 720.47
Triclinic,
a = 8.8019 (4) Å
b = 12.2378 (5) Å
c = 14.6559 (7) Å
α = 101.080 (2)°
β = 91.351 (3)°
γ = 98.749 (3)°
V = 1528.95 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 293 K
0.25 × 0.12 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.825, T _max = 0.999
27004 measured reflections
5526 independent reflections
4198 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.167
S = 1.13
5526 reflections
462 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810048191/si2309sup1.cif

e-66-m1643-sup1.cif^{(29KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048191/si2309Isup2.hkl

e-66-m1643-Isup2.hkl^{(270.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—N1	2.017 (2)
Co1—N2	2.033 (2)
Co1—O5	2.090 (2)
Co1—O1	2.148 (2)
Co1—O3	2.175 (2)
Co1—O7	2.281 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O14	0.82	1.67	2.491 (4)	174
O13—H13A⋯O6ⁱ	0.85 (2)	2.29 (2)	2.917 (4)	131 (3)
O13—H13B⋯O4ⁱⁱ	0.85 (3)	2.09 (2)	2.926 (4)	168 (3)
O14—H14A⋯O4ⁱⁱ	0.85 (2)	1.80 (2)	2.645 (4)	174 (3)
O14—H14B⋯O15	0.85 (3)	1.98 (4)	2.658 (6)	136 (4)
O9—H9⋯O2ⁱⁱⁱ	0.82	1.70	2.520 (3)	173
O11—H11A⋯O13^iv	0.82	1.84	2.634 (4)	163
N4—H4A⋯O6ⁱ	0.89	2.06	2.935 (3)	167
N4—H4A⋯O5ⁱ	0.89	2.53	2.993 (3)	113
N4—H4A⋯O11^v	0.89	2.58	3.011 (3)	110
N4—H4B⋯O10^vi	0.89	2.05	2.834 (3)	146
N4—H4C⋯O9^v	0.89	2.41	2.964 (3)	121
N5—H5A⋯O1^vii	0.99 (3)	2.12 (3)	3.060 (3)	158 (3)

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

Acknowledgments

This work was supported by the Fundo Europeu de Desenvolvimento Regional-QREN-COMPETE through project PTDC/FIS/102284/2008-Fundação para a Ciência e a Tecnologia (FCT).

supplementary crystallographic information

Comment

Many complexes containing pyridine-2,6-dicarboxylate, Co^II ions and various bases have been reported (Aghabozorg et al. 2008, 2009; Moghimi et al., 2002; MacDonald et al., 2004, 2000).

In the title compound (I), Fig. 1, the metal ion Co^II is six-coordinated by two pyridine-2,6-dicarboxylate ligands, with -2 and -1 negative charges (Table 1). Both ligands are tridentate and the coordination sphere around the cobalt is a distorted octahedral with the N—Co—N angle equal to 177.68 (9)°. The angle between the least-squares plane of the non-H atoms of the two ligands is 87.38 (4)°. Each complex of total charge -1 is accompanied in the asymmetric unit cell by one phenylhydrazinium ion as a counter ion, a neutral pyridine-2,6-dicarboxylic acid molecule and three water molecules. In the cation the terminal N4 is deviated by 1.188 (3)Å from the C22—C27 plane. The bond angle sum around N5 is 327°, indicative of a sp³ hybridization for this atom. There is an extensive three-dimensional network of H-bonds linking the molecules and ions together. Water O13 links the cobalt complexes along the b axis and water O14 links the cobalt complexes along the a axis. The neutral acidic molecule is H-bonded to the complex and the cation shares the NH and NH₃ hydrogen atoms with two symmetry related complexes and the neutral acid molecule (Table 2 and Fig. 2).

Experimental

From a solution of phenylhydrazine (0.4 mmol) and of pyridine-2,6-dicarboxylic acid (0.4 mmol) in THF (30 ml), a white precipitate was obtained. By mixing the precipitate with cobalt (II) nitrate (0.2 mmol) in water (25 ml), brown crystals of the title compound were obtained after allowing the mixture to stand for 2 weeks at room temperature.