Tris(3,5-dimethyl-1H-pyrazole-κN 2)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)cobalt(II) monohydrate

Kun-Hua Lin; Zhe-Yin Yu; Yan-Hua Zhong; Min Shao

doi:10.1107/S1600536809010538

. 2009 Mar 28;65(Pt 4):m449. doi: 10.1107/S1600536809010538

Tris(3,5-dimethyl-1H-pyrazole-κN ²)(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)cobalt(II) monohydrate

Kun-Hua Lin ^a, Zhe-Yin Yu ^a,^*, Yan-Hua Zhong ^a, Min Shao ^b

PMCID: PMC2969004 PMID: 21582386

Abstract

The reaction of Co(NO₃)₂·3H₂O with pyridine-2,6-dicarboxylic acid and 3,5-dimethyl-1H-pyrazole in a 1:1:3 molar ratio affords the title complex, [Co(C₇H₃NO₄)(C₅H₈N₂)₃]·H₂O. The Co^II atom is coordinated by one pyridine-2,6-dicarboxylate chelating ligand and three 3,5-dimethyl-1H-pyrazole ligands in a distorted octahedral geometry. Hydrogen-bonding interactions involving the coordinated carboxylate group, 3,5-dimethyl-1H-pyrazole and water help to consolidate the crystal structure

Related literature

For the use of complexes with pyrazole-based ligands in studying the relationship between the structure and the activity of the active site of metalloproteins, see: Haanstra et al. (1990 ▶). For the coordination modes of pyrazole complexes, see: Grotjahn et al. (2003 ▶).

Experimental

Crystal data

[Co(C₇H₃NO₄)(C₅H₈N₂)₃]·H₂O
M _r = 530.45
Triclinic,
a = 8.4220 (8) Å
b = 11.9936 (12) Å
c = 13.1418 (13) Å
α = 75.1290 (10)°
β = 84.7720 (10)°
γ = 70.0940 (10)°
V = 1206.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 296 K
0.30 × 0.30 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.804, T _max = 0.833
6298 measured reflections
4183 independent reflections
3769 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.077
S = 1.03
4183 reflections
331 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010538/bq2127sup1.cif

e-65-0m449-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010538/bq2127Isup2.hkl

e-65-0m449-Isup2.hkl^{(205KB, hkl)}

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

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

Co1—N1	2.0407 (16)
Co1—N4	2.0798 (16)
Co1—O1	2.1453 (14)
Co1—O3	2.1522 (14)
Co1—N2	2.2336 (17)
Co1—N6	2.2477 (17)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1Wⁱ	0.86	2.22	2.926 (2)	139
N3—H3A⋯O1	0.86	2.61	3.048 (2)	113
N5—H5⋯O2ⁱⁱ	0.86	2.10	2.945 (2)	168
N7—H7⋯O2ⁱⁱ	0.86	2.08	2.838 (2)	146
N7—H7⋯O3	0.86	2.42	2.906 (2)	116
O1W—H1WA⋯O4ⁱⁱⁱ	0.844 (17)	1.967 (18)	2.797 (2)	168 (3)
O1W—H1WB⋯O3^iv	0.828 (17)	2.204 (19)	3.009 (2)	164 (3)

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

supplementary crystallographic information

Comment

Complexes with pyrazole-based ligands are a frequent subject of chemical investigations giving an opportunity for a better understanding of the relationship between the structure and the activity of the active site of metalloproteins (Haanstra et al., 1990). Nowadays, attention is paid to the design of various pyrazole ligands, and some coordination modes of pyrazole complexes were reported (Grotjahn et al., 2003). In our systematic studies on transition metal comlexes with the pyrazole derivatives, the title compound was prepared and its X-ray structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The compound assumes a distorted octahedron geometry, formed by three 3,5-Dimethyl-1-H-pyrazole molecules and a pyridine-2,6-dicarboxylate. Tridentate ligand pyridine-2,6-dicarboxylate dianion chelates to the Co atom by a N atom of pyridine ring and two O atoms of carboxyl groups with a meridional configuration. Monodentate ligand 3,5-Dimethyl-1-H-pyrazole coordinated to the Co atom by N atoms of pyrazole rings. The bond distances of Co1—N1 and Co1—N4 are 2.0407 (16)Å and 2.0798 (16)Å (Table 1), which are shorter than the the bond distances of Co1—N2 and Co1—N6 with 2.2336 (17)Å and 2.2477 (17)Å.

Experimental

An ethanol solution (6 ml) containing 3,5-Dimethyl-1-H-pyrazole(0.1153 g, 1.2 mmol) and Co(NO₃)₂.3H₂O(0.0870 g, 0.3 mmol) was mixed with an aqueous solution (6 ml) of pyridine-2,6-dicarboxylic acid(0.0501 g, 0.3 mmol) and NaOH (0.0240 g, 0.6 mmol). The mixture was refluxed for 6 h. The solution was filtered after cooling to room temperature. Pink single crystals suitable for X-ray diffraction were obtained from the filtrate after 11 d.