Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]nickel(II) tetra­hydrate

Kai Zhao; Xian-Hong Yin; Yu Feng; Jie Zhu; Cui-Wu Lin

doi:10.1107/S1600536807063003

. 2007 Dec 6;64(Pt 1):m64–m65. doi: 10.1107/S1600536807063003

Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]nickel(II) tetrahydrate

Kai Zhao ^a,^b, Xian-Hong Yin ^a,^*, Yu Feng ^a, Jie Zhu ^b, Cui-Wu Lin ^b

PMCID: PMC2914946 PMID: 21200635

Abstract

In the title complex, [Ni(C₁₁H₉ClN₃O₂)₂]·4H₂O, the Ni atom is coordinated by four N atoms and two O atoms derived from two tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The cis-N₄O₂ donor set defines a distorted octahedral geometry. In the crystal structure, the complex and water molecules are linked by O—H⋯O hydrogen bonds.

Related literature

For related literature, see: Yin et al. (2007 ▶); Zhao et al. (2007 ▶).

Experimental

Crystal data

[Ni(C₁₁H₉ClN₃O₂)₂]·4H₂O
M _r = 632.10
Triclinic,
a = 9.5907 (10) Å
b = 11.2776 (17) Å
c = 14.2659 (19) Å
α = 92.593 (2)°
β = 105.206 (3)°
γ = 113.820 (3)°
V = 1342.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 298 (2) K
0.52 × 0.49 × 0.37 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.630, T _max = 0.713
6957 measured reflections
4644 independent reflections
3549 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.107
S = 1.01
4644 reflections
356 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.41 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 I, global. DOI: 10.1107/S1600536807063003/tk2215sup1.cif

e-64-00m64-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063003/tk2215Isup2.hkl

e-64-00m64-Isup2.hkl^{(227.5KB, hkl)}

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

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

Ni1—N4	1.998 (2)
Ni1—N1	2.000 (2)
Ni1—O1	2.069 (2)
Ni1—O3	2.079 (2)
Ni1—N3	2.096 (3)
Ni1—N6	2.112 (3)

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N4—Ni1—N1	178.42 (10)
N4—Ni1—O1	101.86 (9)
N1—Ni1—O1	78.75 (9)
N4—Ni1—O3	78.49 (9)
N1—Ni1—O3	100.08 (9)
O1—Ni1—O3	90.29 (10)
N4—Ni1—N3	102.51 (10)
N1—Ni1—N3	76.82 (9)
O1—Ni1—N3	155.49 (9)
O3—Ni1—N3	92.01 (10)
N4—Ni1—N6	76.94 (10)
N1—Ni1—N6	104.50 (10)
O1—Ni1—N6	93.55 (10)
O3—Ni1—N6	155.40 (9)
N3—Ni1—N6	94.43 (10)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O4	0.85	1.96	2.800 (4)	170
O5—H5B⋯O6ⁱ	0.85	1.95	2.790 (4)	170
O6—H6A⋯O2ⁱⁱ	0.85	2.21	3.063 (5)	176
O6—H6B⋯O7ⁱⁱⁱ	0.85	1.84	2.693 (4)	176
O7—H7D⋯O4^iv	0.85	2.13	2.942 (4)	161
O7—H7E⋯O2^v	0.85	1.94	2.758 (4)	160
O8—H8A⋯O5^vi	0.85	1.95	2.802 (5)	179
O8—H8B⋯O5^vii	0.85	2.09	2.939 (5)	178

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20761002). This research was sponsored by the Fund of the Talent Highland Research Programme of Guangxi University (grant No. 205121), the Science Foundation of the State Ethnic Affairs Commission (grant No. 07GX05), the Development Foundation of Guangxi Research Institute of Chemical Industry and the Science Foundation of Guangxi University for Nationalities (grant Nos. 0409032, 0409012 and 0509ZD047).

supplementary crystallographic information

Comment

Recently we reported the crystal structures of bis[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]zinc(II) trihydrate (Yin et al., 2007) and bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]cobalt(II) 2.5- hydrate (Zhao et al., 2007). As a continuation of these investigations, the crystal structure of the title complex, (I), is described.

In (I), Fig. 1, the Ni atom is six-coordinated by four N atoms and two O atoms derived from two uninegative tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The resultant cis-N₄O₂ donor set defines an approximate octahedral geometry with the range of the angles around Ni(II) center being 76.82 (9) to 178.42 (10)°. A complex network of O—H···O hydrogen bonds involving the ligand-O and water molecules of crystallization consolidate the crystal structure (Table 1).

Experimental

6-(3,5-Dimethyl-1H-pyrazol-1-yl)picolinic acid (1 mmol, 250 mg) was dissolved in anhydrous alcohol (15 ml) and stirred until a clear solution resulted. A solution of NiCl₂.6H₂O (0.5 mmol, 113 mg) in anhydrous alcohol (10 ml) was then added. After keeping the resulting solution in air to evaporate about half of the volume, blue prisms of (I) formed. The crystals were isolated, washed with ethanol three times and dried in a vacuum desiccator using silica gel as the dessicant; yield 75%. Elemental analysis: Found: C 41.70, H 4.25, N 13.20, O 20.35%. C₂₂H₂₆NiN₆O₈ requires: C 41.80, H 4.15, N 13.30, O 20.25%.