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

Hong, Z.

doi:10.1107/S1600536809004279

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m273

doi:10.1107/S1600536809004279

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

Zhe Hong ^a ^*

^aCollege of Chemical Engineering and Materials Science, Liaodong University, Dandong 118003, People's Republic of China
^*Correspondence e-mail: hongzhe57@126.com

(Received 4 February 2009; accepted 5 February 2009; online 13 February 2009)

In the title centrosymmetric mononuclear nickel(II) complex, [Ni(C₇H₅ClNO)₂], the Ni^II 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.

Related literature

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

Experimental

Crystal data

[Ni(C₇H₅ClNO)₂]
M_r = 367.85
Monoclinic, P 2₁ /c
a = 15.775 (6) Å
b = 5.685 (2) Å
c = 7.894 (3) Å
β = 93.864 (18)°
V = 706.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.76 mm⁻¹
T = 298 (2) K
0.18 × 0.17 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.743, T_max = 0.755
4102 measured reflections
1532 independent reflections
1296 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.084
S = 1.04
1532 reflections
100 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.54	3.318 (3)	142
Symmetry code: (i) $[x, -y+{1\over 2}, z+{1\over 2}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004279/ci2768sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004279/ci2768Isup2.hkl

checkCIF report

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.

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

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
M_r = 367.85	D_x = 1.730 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1954 reflections
a = 15.775 (6) Å	θ = 2.8–27.6°
b = 5.685 (2) Å	µ = 1.76 mm⁻¹
c = 7.894 (3) Å	T = 298 K
β = 93.864 (18)°	Block, brown
V = 706.3 (5) Å³	0.18 × 0.17 × 0.17 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1532 independent reflections
Radiation source: fine-focus sealed tube	1296 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→18
T_min = 0.743, T_max = 0.755	k = −7→7
4102 measured reflections	l = −10→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0495P)² + 0.0905P] where P = (F_o² + 2F_c²)/3
1532 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.45 e Å⁻³
1 restraint	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Ni(C₇H₅ClNO)₂]	V = 706.3 (5) Å³
M_r = 367.85	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.775 (6) Å	µ = 1.76 mm⁻¹
b = 5.685 (2) Å	T = 298 K
c = 7.894 (3) Å	0.18 × 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)
T_min = 0.743, T_max = 0.755	R_int = 0.029
4102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.45 e Å⁻³
1532 reflections	Δρ_min = −0.30 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.0000	0.03469 (15)
Cl1	0.06466 (4)	0.34882 (15)	0.19374 (11)	0.0778 (3)
N1	0.45858 (11)	0.2416 (3)	0.1094 (2)	0.0421 (4)
O1	0.39683 (9)	0.6527 (2)	−0.01584 (18)	0.0411 (3)
C1	0.31247 (13)	0.3565 (3)	0.1140 (3)	0.0374 (4)
C2	0.32363 (13)	0.5745 (4)	0.0315 (3)	0.0369 (4)
C3	0.25045 (14)	0.7137 (4)	−0.0045 (3)	0.0445 (5)
H3	0.2554	0.8554	−0.0619	0.053*
C4	0.17234 (15)	0.6450 (4)	0.0433 (3)	0.0501 (6)
H4	0.1252	0.7403	0.0189	0.060*
C5	0.16322 (14)	0.4331 (5)	0.1283 (3)	0.0493 (6)
C6	0.23191 (14)	0.2906 (4)	0.1628 (3)	0.0439 (5)
H6	0.2252	0.1487	0.2190	0.053*
C7	0.38261 (14)	0.1990 (4)	0.1480 (3)	0.0412 (5)
H7	0.3722	0.0571	0.2015	0.049*
H1	0.4993 (14)	0.133 (4)	0.131 (4)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0430 (2)	0.0274 (2)	0.0335 (2)	0.00107 (14)	0.00128 (15)	0.00308 (13)
Cl1	0.0488 (4)	0.0872 (6)	0.0994 (6)	−0.0016 (3)	0.0197 (3)	0.0169 (4)
N1	0.0470 (10)	0.0325 (9)	0.0465 (10)	0.0054 (7)	0.0023 (8)	0.0076 (7)
O1	0.0437 (8)	0.0314 (7)	0.0483 (9)	0.0025 (6)	0.0049 (6)	0.0063 (6)
C1	0.0467 (11)	0.0305 (10)	0.0348 (10)	−0.0012 (8)	0.0020 (8)	−0.0010 (8)
C2	0.0447 (11)	0.0312 (9)	0.0345 (10)	0.0018 (8)	0.0017 (8)	−0.0021 (8)
C3	0.0510 (12)	0.0351 (11)	0.0469 (13)	0.0042 (9)	0.0004 (10)	0.0025 (9)
C4	0.0470 (12)	0.0463 (14)	0.0565 (14)	0.0086 (10)	−0.0006 (10)	−0.0021 (10)
C5	0.0454 (13)	0.0497 (13)	0.0530 (14)	−0.0026 (10)	0.0052 (10)	−0.0009 (11)
C6	0.0517 (12)	0.0379 (11)	0.0424 (12)	−0.0045 (10)	0.0060 (9)	0.0008 (9)
C7	0.0513 (12)	0.0316 (10)	0.0406 (11)	−0.0007 (9)	0.0037 (9)	0.0066 (8)

Geometric parameters (Å, º) top

Ni1—O1ⁱ	1.8414 (15)	C1—C7	1.434 (3)
Ni1—O1	1.8414 (15)	C2—C3	1.412 (3)
Ni1—N1ⁱ	1.8455 (18)	C3—C4	1.370 (3)
Ni1—N1	1.8455 (18)	C3—H3	0.93
Cl1—C5	1.738 (2)	C4—C5	1.391 (4)
N1—C7	1.280 (3)	C4—H4	0.93
N1—H1	0.897 (10)	C5—C6	1.365 (3)
O1—C2	1.315 (2)	C6—H6	0.93
C1—C6	1.403 (3)	C7—H7	0.93
C1—C2	1.417 (3)

O1ⁱ—Ni1—O1	180.00 (4)	C4—C3—C2	121.5 (2)
O1ⁱ—Ni1—N1ⁱ	93.89 (7)	C4—C3—H3	119.2
O1—Ni1—N1ⁱ	86.11 (7)	C2—C3—H3	119.2
O1ⁱ—Ni1—N1	86.11 (7)	C3—C4—C5	120.3 (2)
O1—Ni1—N1	93.89 (7)	C3—C4—H4	119.9
N1ⁱ—Ni1—N1	180.00 (10)	C5—C4—H4	119.9
C7—N1—Ni1	128.97 (15)	C6—C5—C4	120.2 (2)
C7—N1—H1	120 (2)	C6—C5—Cl1	119.4 (2)
Ni1—N1—H1	111 (2)	C4—C5—Cl1	120.37 (19)
C2—O1—Ni1	127.63 (13)	C5—C6—C1	120.6 (2)
C6—C1—C2	120.15 (18)	C5—C6—H6	119.7
C6—C1—C7	118.94 (19)	C1—C6—H6	119.7
C2—C1—C7	120.91 (19)	N1—C7—C1	124.10 (19)
O1—C2—C3	118.37 (19)	N1—C7—H7	118.0
O1—C2—C1	124.41 (18)	C1—C7—H7	118.0
C3—C2—C1	117.21 (19)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱⁱ	0.93	2.54	3.318 (3)	142

Symmetry code: (ii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₅ClNO)₂]
M_r	367.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	15.775 (6), 5.685 (2), 7.894 (3)
β (°)	93.864 (18)
V (Å³)	706.3 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.76
Crystal size (mm)	0.18 × 0.17 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.743, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	4102, 1532, 1296
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.04
No. of reflections	1532
No. of parameters	100
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.30

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.54	3.318 (3)	142

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The author acknowledges Liaodong University for funding this study.

References

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