Aqua-bis(1H-imidazole-κN)bis-(4-methyl-benzoato)-κO;κO,O'-nickel(II).

Abstract

In the mononuclear title compound, [Ni(C(8)H(7)O(2))(2)(C(3)H(4)N(2))(2)(H(2)O)], the Ni(II) atom is coordinated by three carboxylate O atoms (from a bidentate 4-methyl-benzoate ligand and a monodentate 4-methyl-benzoate ligand), two N atoms (from two imidazole ligands) and a water mol-ecule in an octa-hedral geometry. Inter-molecular O-H⋯O hydrogen-bonding inter-actions lead to infinite chains, which are further self-assembled into a supra-molecular network through inter-molecular N-H⋯O hydrogen-bonding inter-actions and π-π stacking [centroid-centroid distance = 3.717 (2) Å].

Full text

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Aquabis(1H-imidazole-jN3)bis(4-methyl-
benzoato)-jO;jO,O0 0 0-nickel(II)
Wen-Dong Song,a* Run-Zhen Fanaand Hong-Mian Wub
aCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People’s
Republic of China, andbCollege of Food Science and Technology, Guang Dong
Ocean University, Zhanjiang 524088, People’s Republic of China
Correspondence e-mail: songwd60@126.com
Received 4 April 2008; accepted 7 April 2008
Key indicators: single-crystal X-ray study; T = 296 K; mean ?(C–C) = 0.007 A ˚;
R factor = 0.061; wR factor = 0.171; data-to-parameter ratio = 12.7.
In the mononuclear title compound, [Ni(C8H7O2)2(C3H4N2)2-
(H2O)], the NiIIatom is coordinated by three carboxylate O
atoms (from a bidentate 4-methylbenzoate ligand and a
monodentate 4-methylbenzoate ligand), two N atoms (from
two imidazole ligands) and a water molecule in an octahedral
geometry. Intermolecular O—H???O hydrogen-bonding inter-
actions lead to infinite chains, which are further self-assembled
into a supramolecular network through intermolecular N—
H???O hydrogen-bonding interactions and ?–? stacking
[centroid–centroid distance = 3.717 (2) A˚].
Related literature
For related literature, see: Song et al. (2007).
Experimental
Crystal data
[Ni(C8H7O2)2(C3H4N2)2(H2O)]
Mr= 483.16
Monoclinic, P21=n
a = 18.9456 (12) A˚
b = 5.8755 (4) A˚
c = 20.3209 (14) A˚
? = 101.813 (4)?
V = 2214.1 (3) A˚3
Z = 4
Mo K? radiation
? = 0.92 mm?1
T = 296 (2) K
0.30 ? 0.26 ? 0.25 mm
Data collection
Bruker APEXII area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin= 0.770, Tmax= 0.803
20580 measured reflections
3776 independent reflections
2815 reflections with I > 2?(I)
Rint= 0.077
Refinement
R[F2> 2?(F2)] = 0.060
wR(F2) = 0.171
S = 1.07
3776 reflections
297 parameters
3 restraints
H atoms treated by a mixture of
independent and constrained
refinement
??max= 1.02 e A˚?3
??min= ?0.71 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O1W—H1W???O3i
O1W—H1W???O2i
N2—H2???O2ii
N4—H22???O4iii
Symmetry codes: (i) x;y þ 1;z; (ii) ?x þ 1;?y;?z þ 2; (iii) ?x þ3
D—HH???AD???AD—H???A
0.826 (10)
0.826 (10)
0.86
0.86
2.31 (4)
2.21 (3)
1.96
2.02
2.782 (4)
2.772 (4)
2.816 (5)
2.865 (4)
116 (4)
126 (3)
175
167
2;y ?1
2;?z þ3
2.
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: SHELXTL.
The authors acknowledge Guang Dong Ocean University
for supporting this work.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: NG2442).
References
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin,
USA.
Sheldrick, G. M. (1996). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Song, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63,
m1023–m1024.
metal-organic compounds
m648
Song et al.
doi:10.1107/S1600536808009471
Acta Cryst. (2008). E64, m648
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
sup-1
Acta Cryst. (2008). E64, m648 [ doi:10.1107/S1600536808009471 ]
Aquabis(1H-imidazole- N3)bis(4-methylbenzoato)- O; O,O'-nickel(II)
W.-D. Song, R.-Z. Fan and H.-M. Wu
Comment
In the structural investigation of 4-methylbenzate 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, imidazole and
nickel chloride in alkaline aqueous solution.
As illustrated in Figure 1, the NiII atom exists in a disordered octahedral environment, defined by three carboxyl O
atoms from one bisdentate 4-methylbenzate ligand and one monodentate 4-methylbenzate ligand, two N atoms from two
imidazole ligands and one water molecule. Intermolecular O—H···O hydrogen bonding interactions (Table 1) form infinite
chains involving the coordinating water molecule as donors and O atoms of 4-methylbenzate ligands as acceptors, which
are further self-assembled into a supramolecular network through intermolecular N—H···O hydrogen bonding interactions
and π-π stacking interactions of neighboring complexes, with a centroid-centroid distance of 3.717 (2) Å. (Fig. 2).
Experimental
A mixture of nickel chloride(1 mmol), 4-methylbenzoic acid (1 mmol), imidazole(1 mmol), NaOH (1.5 mmol) and H2O
(12 ml) was placed in 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.
Refinement
H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 - 0.97 Å,
N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N).
Figures
Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown
as 30% probability displacement ellipsoids.

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Fig. 2. The packing of structure (I).
Aquabis(1H-imidazole-κN3)bis(4-methylbenzoato)-κO;κO,O'-nickel(II)
Crystal data
[Ni(C8H7O2)2(C3H4N2)2(H2O)]
F000 = 1008
Dx = 1.449 Mg m−3
Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 3600 reflections
θ = 1.4–28º
µ = 0.92 mm−1
T = 296 (2) K
Block, blue
Mr = 483.16
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 18.9456 (12) Å
b = 5.8755 (4) Å
c = 20.3209 (14) Å
β = 101.813 (4)º
V = 2214.1 (3) Å3
Z = 4
0.30 × 0.26 × 0.25 mm
Data collection
Bruker APEXII area-detector
diffractometer
Radiation source: fine-focus sealed tube
Monochromator: graphite
T = 296(2) K
φ and ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.770, Tmax = 0.803
20580 measured reflections
3776 independent reflections
2815 reflections with I > 2σ(I)
Rint = 0.077
θmax = 25.2º
θmin = 1.7º
h = −22→22
k = −7→7
l = −22→21
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
H atoms treated by a mixture of
independent and constrained refinement
w = 1/[σ2(Fo2) + (0.1064P)2 + 0.0659P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 1.02 e Å−3
R[F2 > 2σ(F2)] = 0.060
wR(F2) = 0.171
S = 1.07
3776 reflections

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supplementary materials
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297 parameters
Δρmin = −0.71 e Å−3
Extinction correction: none3 restraints
Primary atom site location: structure-invariant direct
methods
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance mat-
rix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations
between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of
cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.68032 (18)
0.72717 (19)
0.7618 (2)
0.7552
0.8066 (2)
0.8302
0.8171 (2)
0.7816 (2)
0.7875
0.7377 (2)
0.7144
0.8676 (3)
0.9136
0.8482
0.8733
0.56235 (18)
0.51866 (17)
0.5069 (2)
0.5271
0.4665 (2)
0.4593
0.4360 (2)
0.4474 (2)
0.4271
0.4884 (2)
0.4960
0.3904 (3)
0.4187
0.3490
y
0.0732 (7)
0.1141 (7)
0.3198 (8)
0.4352
0.3558 (9)
0.4949
0.1911 (9)
−0.0143 (9)
−0.1286
−0.0515 (8)
−0.1910
0.2326 (11)
0.1655
0.1655
0.3935
0.1063 (7)
0.0039 (6)
0.1198 (8)
0.2633
0.0269 (8)
0.1088
−0.1874 (8)
−0.3059 (8)
−0.4496
−0.2135 (7)
−0.2964
−0.2924 (10)
−0.3031
−0.1985
z
0.9997 (2)
1.0678 (2)
1.0827 (2)
1.0507
1.1451 (3)
1.1538
1.1943 (3)
1.1796 (3)
1.2119
1.1177 (3)
1.1090
1.2602 (3)
1.2593
1.2957
1.2677
0.7571 (2)
0.6958 (2)
0.6345 (2)
0.6325
0.5775 (2)
0.5375
0.5782 (3)
0.6384 (3)
0.6398
0.6964 (2)
0.7362
0.5148 (3)
0.4807
0.4989
Uiso*/Ueq
0.0328 (10)
0.0318 (10)
0.0434 (12)
0.052*
0.0515 (13)
0.062*
0.0450 (12)
0.0532 (13)
0.064*
0.0473 (12)
0.057*
0.0676 (17)
0.101*
0.101*
0.101*
0.0291 (9)
0.0282 (9)
0.0402 (11)
0.048*
0.0463 (12)
0.056*
0.0442 (12)
0.0406 (12)
0.049*
0.0351 (11)
0.042*
0.0693 (17)
0.104*
0.104*
C1
C2
C3
H3
C4
H4
C5
C6
H6
C7
H7
C8
H8A
H8B
H8C
C9
C10
C11
H11
C12
H12
C13
C14
H14
C15
H15
C16
H16A
H16B