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Acta Cryst. (2009). E65, m273    [ doi:10.1107/S1600536809004279 ]

Bis[4-chloro-2-(iminomethyl)phenolato]nickel(II)

Z. Hong

Abstract top

In the title centrosymmetric mononuclear nickel(II) complex, [Ni(C7H5ClNO)2], the NiII ion, lying on an inversion center, is four-coordinated by two O and two imine N atoms from two 4-chloro-2-iminomethylphenolate ligands, forming a distorted square-planar geometry. In the crystal structure, molecules are linked into a two-dimensional network parallel to the bc plane by C-H...O hydrogen bonds.

Comment top

Recently, the author has reported the crystal structure of a Schiff base nickel(II) complex (Hong, 2007). As an extension of the work on the structural investigation of nickel(II) complexes, the title complex is reported here.

The title compound is a centrosymmetric mononuclear nickel(II) complex (Fig. 1), which is similar to those reported previously (Kamenar et al., 1990). The Ni atom, lying on the inversion center, is four-coordinated by two O and two imine N atoms from two 4-chloro-2-iminomethylphenol ligands, forming a square-planar geometry. The bond lengths (Table 1) related to the metal centre are comparable to the values in similar nickel(II) complexes (Zhou et al., 2004; Li et al., 2005; Li et al., 2007).

In the crystal structure, the molecules are linked into a two-dimensional network parallel to the bc plane by C—H···O hydrogen bonds (Table 1).

Related literature top

For related structures, see: Hong (2007); Kamenar et al. (1990); Li et al. (2005, 2007); Zhou et al. (2004).

Experimental top

5-Chlorosalicylaldehyde (1.0 mmol, 156.6 mg) and Ni(CH3COO)2.4H2O (0.5 mmol, 125.0 mg) were dissolved in methanol solution containing a small quantity of ammonia (30 ml). The mixture was stirred at room temperature for 30 min to give a clear brown solution. After keeping the solution in air for a few days, brown block-shaped crystals were formed.

Refinement top

Atom H1 was located from a difference Fourier map and refined isotropically, with the N1–H1 distance restrained to 0.90 (1) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms with C–H distances of 0.93 Å, and with Uiso(H) set to 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Unlabelled atoms are related to labelled atoms by the symmetry operation (1 - x, 1 - y, - z).
Bis[4-chloro-2-(iminomethyl)phenolato]nickel(II) top
Crystal data top
[Ni(C7H5ClNO)2]F(000) = 372
Mr = 367.85Dx = 1.730 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1954 reflections
a = 15.775 (6) Åθ = 2.8–27.6°
b = 5.685 (2) ŵ = 1.76 mm−1
c = 7.894 (3) ÅT = 298 K
β = 93.864 (18)°Block, brown
V = 706.3 (5) Å30.18 × 0.17 × 0.17 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		1532 independent reflections
Radiation source: fine-focus sealed tube1296 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 27.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→18
Tmin = 0.743, Tmax = 0.755k = −7→7
4102 measured reflectionsl = −10→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0495P)2 + 0.0905P]
where P = (Fo2 + 2Fc2)/3
1532 reflections(Δ/σ)max = 0.001
100 parametersΔρmax = 0.45 e Å−3
1 restraintΔρmin = −0.30 e Å−3
Crystal data top
[Ni(C7H5ClNO)2]V = 706.3 (5) Å3
Mr = 367.85Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.775 (6) ŵ = 1.76 mm−1
b = 5.685 (2) ÅT = 298 K
c = 7.894 (3) Å0.18 × 0.17 × 0.17 mm
β = 93.864 (18)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1532 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1296 reflections with I > 2σ(I)
Tmin = 0.743, Tmax = 0.755Rint = 0.029
4102 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084Δρmax = 0.45 e Å−3
S = 1.04Δρmin = −0.30 e Å−3
1532 reflectionsAbsolute structure: ?
100 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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 matrix. 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, conventional 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) top
xyzUiso*/Ueq
Ni10.50000.50000.00000.03469 (15)
Cl10.06466 (4)0.34882 (15)0.19374 (11)0.0778 (3)
N10.45858 (11)0.2416 (3)0.1094 (2)0.0421 (4)
O10.39683 (9)0.6527 (2)−0.01584 (18)0.0411 (3)
C10.31247 (13)0.3565 (3)0.1140 (3)0.0374 (4)
C20.32363 (13)0.5745 (4)0.0315 (3)0.0369 (4)
C30.25045 (14)0.7137 (4)−0.0045 (3)0.0445 (5)
H30.25540.8554−0.06190.053*
C40.17234 (15)0.6450 (4)0.0433 (3)0.0501 (6)
H40.12520.74030.01890.060*
C50.16322 (14)0.4331 (5)0.1283 (3)0.0493 (6)
C60.23191 (14)0.2906 (4)0.1628 (3)0.0439 (5)
H60.22520.14870.21900.053*
C70.38261 (14)0.1990 (4)0.1480 (3)0.0412 (5)
H70.37220.05710.20150.049*
H10.4993 (14)0.133 (4)0.131 (4)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0430 (2)0.0274 (2)0.0335 (2)0.00107 (14)0.00128 (15)0.00308 (13)
Cl10.0488 (4)0.0872 (6)0.0994 (6)−0.0016 (3)0.0197 (3)0.0169 (4)
N10.0470 (10)0.0325 (9)0.0465 (10)0.0054 (7)0.0023 (8)0.0076 (7)
O10.0437 (8)0.0314 (7)0.0483 (9)0.0025 (6)0.0049 (6)0.0063 (6)
C10.0467 (11)0.0305 (10)0.0348 (10)−0.0012 (8)0.0020 (8)−0.0010 (8)
C20.0447 (11)0.0312 (9)0.0345 (10)0.0018 (8)0.0017 (8)−0.0021 (8)
C30.0510 (12)0.0351 (11)0.0469 (13)0.0042 (9)0.0004 (10)0.0025 (9)
C40.0470 (12)0.0463 (14)0.0565 (14)0.0086 (10)−0.0006 (10)−0.0021 (10)
C50.0454 (13)0.0497 (13)0.0530 (14)−0.0026 (10)0.0052 (10)−0.0009 (11)
C60.0517 (12)0.0379 (11)0.0424 (12)−0.0045 (10)0.0060 (9)0.0008 (9)
C70.0513 (12)0.0316 (10)0.0406 (11)−0.0007 (9)0.0037 (9)0.0066 (8)
Geometric parameters (Å, °) top
Ni1—O1i1.8414 (15)C1—C71.434 (3)
Ni1—O11.8414 (15)C2—C31.412 (3)
Ni1—N1i1.8455 (18)C3—C41.370 (3)
Ni1—N11.8455 (18)C3—H30.93
Cl1—C51.738 (2)C4—C51.391 (4)
N1—C71.280 (3)C4—H40.93
N1—H10.897 (10)C5—C61.365 (3)
O1—C21.315 (2)C6—H60.93
C1—C61.403 (3)C7—H70.93
C1—C21.417 (3)
O1i—Ni1—O1180.00 (4)C4—C3—C2121.5 (2)
O1i—Ni1—N1i93.89 (7)C4—C3—H3119.2
O1—Ni1—N1i86.11 (7)C2—C3—H3119.2
O1i—Ni1—N186.11 (7)C3—C4—C5120.3 (2)
O1—Ni1—N193.89 (7)C3—C4—H4119.9
N1i—Ni1—N1180.00 (10)C5—C4—H4119.9
C7—N1—Ni1128.97 (15)C6—C5—C4120.2 (2)
C7—N1—H1120 (2)C6—C5—Cl1119.4 (2)
Ni1—N1—H1111 (2)C4—C5—Cl1120.37 (19)
C2—O1—Ni1127.63 (13)C5—C6—C1120.6 (2)
C6—C1—C2120.15 (18)C5—C6—H6119.7
C6—C1—C7118.94 (19)C1—C6—H6119.7
C2—C1—C7120.91 (19)N1—C7—C1124.10 (19)
O1—C2—C3118.37 (19)N1—C7—H7118.0
O1—C2—C1124.41 (18)C1—C7—H7118.0
C3—C2—C1117.21 (19)
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O1ii0.932.543.318 (3)142
Symmetry codes: (ii) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O1i0.932.543.318 (3)142
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

The author acknowledges Liaodong University for funding this study.

references
References top

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Hong, Z. (2007). Acta Cryst. E63, m2026.

Kamenar, B., Kaitner, B., Ferguson, G. & Waters, T. N. (1990). Acta Cryst. C46, 1920–1923.

Li, J.-M., Jiang, Y.-M., Li, C.-Z. & Zhang, S.-H. (2007). Acta Cryst. E63, m447–m449.

Li, J.-M., Jiang, Y.-M., Wang, Y.-F. & Liang, D.-W. (2005). Acta Cryst. E61, m2160–m2162.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhou, J., Chen, Z.-F., Wang, X.-W., Tan, Y.-S., Liang, H. & Zhang, Y. (2004). Acta Cryst. E60, m568–m570.