Aqua­bis(4-methyl­benzoato)-κO;κ2 O,O′-bis­(pyridine-κN)nickel(II)

Wen-Dong Song; Hao Wang; Li-Li Ji

doi:10.1107/S160053680800634X

. 2008 Mar 14;64(Pt 4):m548. doi: 10.1107/S160053680800634X

Aquabis(4-methylbenzoato)-κO;κ² O,O′-bis(pyridine-κN)nickel(II)

Wen-Dong Song ^a,^*, Hao Wang ^a, Li-Li Ji ^a

PMCID: PMC2961051 PMID: 21202005

Abstract

In the title mononuclear complex, [Ni(C₈H₇O₂)₂(C₅H₅N)₂(H₂O)], the Ni^II atom is in a distorted octahedral arrangement, coordinated by three carboxylate O atoms from one bidentate 4-methylbenzoate ligand and one monodentate 4-methylbenzoate ligand, two N atoms from pyridine ligands, axially positioned, and a water molecule. The equatorially positioned water molecule and uncoordinated carboxylate O atom form an intramolecular hydrogen bond. An intermolecular O—H⋯O hydrogen bond between the coordinated water molecule and carboxylate O atom of the 4-methylbenzoate ligand forms infinite chains along the b axis. These chains are connected by C—H⋯π interactions.

Related literature

For related literature, see: Song et al. (2007 ▶).

Experimental

Crystal data

[Ni(C₈H₇O₂)₂(C₅H₅N)₂(H₂O)]
M _r = 505.20
Monoclinic,
a = 13.6181 (1) Å
b = 5.9526 (1) Å
c = 15.1380 (2) Å
β = 107.215 (1)°
V = 1172.16 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 296 (2) K
0.26 × 0.23 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.806, T _max = 0.846
11325 measured reflections
5102 independent reflections
4798 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.065
S = 1.03
5102 reflections
315 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ▶)
Flack parameter: 0.00

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and XP in SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800634X/kp2154sup1.cif

e-64-0m548-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800634X/kp2154Isup2.hkl

e-64-0m548-Isup2.hkl^{(249.8KB, hkl)}

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

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

N1—Ni1	2.0941 (17)
N2—Ni1	2.0981 (16)
Ni1—O3	2.0165 (14)
Ni1—O1W	2.0412 (15)
Ni1—O2	2.1107 (12)
Ni1—O1	2.1710 (15)

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O3—Ni1—O1W	94.41 (6)
O3—Ni1—N1	86.71 (6)
O1W—Ni1—N1	89.53 (6)
O3—Ni1—N2	89.22 (6)
O1W—Ni1—N2	92.99 (6)
N1—Ni1—N2	175.36 (7)
O3—Ni1—O2	165.26 (7)
O1W—Ni1—O2	99.83 (8)
N1—Ni1—O2	89.57 (6)
N2—Ni1—O2	93.83 (6)
O3—Ni1—O1	104.00 (6)
O1W—Ni1—O1	161.59 (5)
N1—Ni1—O1	91.67 (6)
N2—Ni1—O1	87.17 (6)
O2—Ni1—O1	61.82 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O4	0.819 (9)	1.834 (13)	2.587 (2)	152 (2)
O1W—H1W⋯O1ⁱ	0.809 (9)	1.957 (12)	2.739 (2)	162 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge Guang Dong Ocean University for supporting this work.

supplementary crystallographic information

Comment

In the structural investigation of 4-methylbenzoate complexes, it has been found that the 4-methylbenzoic acid functions as a multidentate ligand [Song et al. (2007)] with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Ni complex obtained by the reaction of 4-methylbenzoic acid, pyridine and nickel chloride in alkaline aqueous solution.

The Ni^II atom exhibits a disordered octahedral environment (Fig. 1, Table 1) defined by three carboxyl O atoms from one bidentate 4-methylbenzoate ligand and one monodentate 4-methylbenzoate ligand, two N atoms from two pyridine ligands and a water molecule. The intermolecular O—H···O hydrogen bond (Table 2, Fig. 2) between the coordinated water molecule and carboxy O atom of 4-methylbenzoate ligand generates a chain along the axis b. The intermolecular hydrogen bond C1—H1···O also involves water molecule [3.339 (3) %A, 145%]. An intramolecular hydrogen bond connects the coordinated water molecule and uncoordinated oxygen atom O4 (Table 2). C—H···π interactions connect hydrogen bonded chains: C₃– H₃···C_g (C₁₂→ C₁₇, symmetry code: -2 - x, 1/2 + y, 2 - z) of 3.482 (2) %A; 132%, and C₁₄– H14···C_g(C₁₂→ C₁₇, symmetry code: 1 - x, -1/2 + y, 2 - z) of 3.603 (2) %A; 134%; C₂₂– H22···C_g(C₂₀→ C₂₅, symmetry code: 2 - x, -1/2 + y, 1 - z) of 3.504 (2) %A; 133%.

Experimental

A mixture of nickel chloride (1 mmol), 4-methylbenzoic acid (1 mmol), pyridine(1 mmol), NaOH (1.5 mmol) and H₂O (12 ml) were placed into a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dryed in air.