Bis[4-bromo-2-(ethyl­imino­meth­yl)phenolato-κ2N,O]nickel(II)

Chen, F.L.; Zhang, S.H.; Guo, J.J.; Zhang, Y.D.; Feng, C.

doi:10.1107/S1600536811020885

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m858

doi:10.1107/S1600536811020885

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Bis[4-bromo-2-(ethyliminomethyl)phenolato-κ²N,O]nickel(II)

Fu Li Chen,^a Shu Hua Zhang,^a ^* Jing Jing Guo,^a Yi Dong Zhang ^a and Chao Feng ^a

^aCollege of Chemistry and Bioengineering, Guilin University of Technology, Key Laboratory of Non-ferrous Metal Materials and Processing Technology, Ministry of Education, Guilin 541004, People's Republic of China
^*Correspondence e-mail: zsh720108@163.com

(Received 13 May 2011; accepted 31 May 2011; online 4 June 2011)

In the title complex, [Ni(C₉H₉BrNO)₂], the Ni^II ion lies on an inversion centre and is coordinated in a slightly distorted square-planar geometry by two N atoms and two O atoms from two symmetry-related bidentate 4-bromo-2-(ethyliminomethyl)phenolate ligands. The complex forms a one-dimensional chain in the crystal structure through short C—H⋯Br contacts (H⋯Br = 3.009 Å).

Related literature

For background to Schiff base compounds, see: Gupta & Sutar (2008 ); Zhang et al. (2008 , 2009 ); Zhang & Feng (2010 ); Ge et al. (2011 ). For Schiff base coordination models, see: Nakagima et al. (1989 ); Zhang et al. (2007 ).

Experimental

Crystal data

[Ni(C₉H₉BrNO)₂]
M_r = 512.83
Monoclinic, P 2₁ /n
a = 13.456 (6) Å
b = 4.803 (2) Å
c = 14.743 (6) Å
β = 102.157 (8)°
V = 931.4 (7) Å³
Z = 2
Mo Kα radiation
μ = 5.35 mm⁻¹
T = 293 K
0.15 × 0.12 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.465, T_max = 0.558
4567 measured reflections
1651 independent reflections
995 reflections with I > 2σ(I)
R_int = 0.164

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.142
S = 1.03
1651 reflections
116 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020885/bh2357sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020885/bh2357Isup2.hkl

checkCIF report

Comment top

Schiff base complexes have been studied for many years (Gupta & Sutar, 2008; Zhang et al., 2008, 2009; Zhang & Feng, 2010; Ge et al., 2011) and produced increasing interest because of their anticancer, antiviral, catalytic and fluorescent properties. Most model studies of metal complexes of Schiff base ligands containing salicylaldehyde and amino acids have focused on the binding mode of these ligands (Nakagima et al., 1989; Zhang et al., 2007). The crystal structures of the complexes obtained demonstrate that the Schiff base ligands act in a bidentate, tridentate, tetradentate or pentadentate mode, coordinating through the phenolate O, imine N and carboxylate O atoms. Our research group is interested in bidentate Schiff bases derived from 5-bromo-2-hydroxy-benzaldehyde and ethylamine.

In the title complex, the Ni^II ion lies on a centre of inversion and is coordinated by two O and two N atoms from two bidentate 5-bromo-N-ethylsalicylaldimino ligands, forming a slightly distorted square-planar geometry (Fig. 1). The compound further form a one-dimensional crystal structure (Fig. 2) through C—H···Br contacts (C9···Br1ⁱ = 3.871 (1) Å, H9···Br1 = 3.009 Å, symmetry code: (i) -x, -y, 1 - z).

Related literature top

For background to Schiff base compounds, see: Gupta & Sutar (2008); Zhang et al. (2008, 2009); Zhang & Feng (2010); Ge et al. (2011). For Schiff base coordination models, see: Nakagima et al. (1989); Zhang et al. (2007).

Experimental top

To a solution of 5-bromo-2-hydroxy-benzaldehyde (0.181 g, 1.0 mmol), ethylamine (0.044 g, 1 mmol), and sodium hydroxide (0.040 g, 1 mmol) in 20 ml absolute methanol was added slowly a solution of nickel nitrate hexahydrate (0.145 g, 0.5 mmol) in methanol. The mixture was stirred for 3 h at room temperature to give a green solution, which was filtered and the filtrate was left to stand at room temperature. Green block crystals suitable for X-ray diffraction were obtained by slow evaporation. yield: 84.6% (based on Ni). Elemental analysis, calculated: C 42.12, H 3.57, N 5.48%; Found: C 42.15, H 3.54, N 5.46%.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, showing 30% probability displacement ellipsoids. H atoms were omitted.
	Fig. 2. Packing drawing of the title compound.

Bis[4-bromo-2-(ethyliminomethyl)phenolato-κ²N,O]nickel(II) top

Crystal data top

[Ni(C₉H₉BrNO)₂]	F(000) = 508
M_r = 512.83	D_x = 1.829 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1651 reflections
a = 13.456 (6) Å	θ = 2.3–25.1°
b = 4.803 (2) Å	µ = 5.35 mm⁻¹
c = 14.743 (6) Å	T = 293 K
β = 102.157 (8)°	Block, green
V = 931.4 (7) Å³	0.15 × 0.12 × 0.11 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1651 independent reflections
Radiation source: fine-focus sealed tube	995 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.164
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→16
T_min = 0.465, T_max = 0.558	k = −5→5
4567 measured reflections	l = −17→14

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0386P)²] where P = (F_o² + 2F_c²)/3
1651 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³
0 constraints

Crystal data top

[Ni(C₉H₉BrNO)₂]	V = 931.4 (7) Å³
M_r = 512.83	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.456 (6) Å	µ = 5.35 mm⁻¹
b = 4.803 (2) Å	T = 293 K
c = 14.743 (6) Å	0.15 × 0.12 × 0.11 mm
β = 102.157 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1651 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	995 reflections with I > 2σ(I)
T_min = 0.465, T_max = 0.558	R_int = 0.164
4567 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.03	Δρ_max = 0.79 e Å⁻³
1651 reflections	Δρ_min = −0.52 e Å⁻³
116 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.14681 (6)	0.5969 (2)	0.56509 (5)	0.0835 (4)
C1	0.0224 (5)	0.9743 (16)	0.8127 (5)	0.0595 (18)
C2	−0.0114 (6)	1.0740 (16)	0.7195 (5)	0.069 (2)
H2	−0.0590	1.2170	0.7075	0.083*
C3	0.0255 (5)	0.9609 (18)	0.6489 (4)	0.067 (2)
H3	0.0025	1.0257	0.5887	0.080*
C4	0.0964 (5)	0.7519 (18)	0.6657 (4)	0.065 (2)
C5	0.1313 (5)	0.6526 (17)	0.7529 (4)	0.064 (2)
H5	0.1806	0.5139	0.7635	0.077*
C6	0.0921 (5)	0.7616 (15)	0.8278 (4)	0.0556 (17)
C7	0.1305 (5)	0.6525 (16)	0.9196 (5)	0.0638 (19)
H7	0.1794	0.5130	0.9257	0.077*
C8	0.1627 (6)	0.5937 (18)	1.0814 (5)	0.080 (3)
H8A	0.1164	0.5395	1.1206	0.096*
H8B	0.1951	0.4265	1.0646	0.096*
C9	0.2412 (6)	0.783 (2)	1.1336 (6)	0.100 (3)
H9A	0.2914	0.8198	1.0976	0.150*
H9B	0.2730	0.6973	1.1913	0.150*
H9C	0.2100	0.9548	1.1459	0.150*
N1	0.1026 (4)	0.7322 (12)	0.9936 (3)	0.0560 (15)
Ni1	0.0000	1.0000	1.0000	0.0544 (4)
O1	−0.0152 (4)	1.0925 (11)	0.8785 (3)	0.0712 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0908 (6)	0.1153 (9)	0.0524 (5)	−0.0021 (5)	0.0331 (4)	−0.0090 (4)
C1	0.069 (4)	0.064 (5)	0.049 (4)	−0.013 (4)	0.021 (3)	0.003 (3)
C2	0.086 (5)	0.078 (6)	0.046 (4)	0.012 (4)	0.017 (4)	0.013 (4)
C3	0.075 (5)	0.090 (6)	0.038 (4)	−0.002 (5)	0.017 (3)	0.011 (4)
C4	0.070 (4)	0.089 (6)	0.043 (4)	−0.017 (4)	0.026 (3)	−0.005 (4)
C5	0.067 (5)	0.081 (6)	0.050 (4)	0.011 (4)	0.022 (3)	−0.001 (4)
C6	0.060 (4)	0.061 (5)	0.049 (4)	0.001 (4)	0.019 (3)	0.001 (3)
C7	0.075 (5)	0.060 (5)	0.062 (5)	0.012 (4)	0.026 (4)	0.008 (4)
C8	0.110 (6)	0.078 (6)	0.059 (5)	0.040 (5)	0.033 (5)	0.024 (4)
C9	0.087 (6)	0.141 (9)	0.066 (5)	0.012 (6)	0.001 (5)	0.029 (6)
N1	0.071 (4)	0.061 (4)	0.038 (3)	0.000 (3)	0.018 (3)	0.004 (3)
Ni1	0.0691 (8)	0.0562 (8)	0.0417 (7)	0.0038 (6)	0.0205 (5)	0.0068 (6)
O1	0.093 (4)	0.083 (4)	0.044 (3)	0.027 (3)	0.030 (2)	0.013 (2)

Geometric parameters (Å, º) top

Br1—C4	1.907 (7)	C7—H7	0.9300
C1—O1	1.314 (9)	C8—C9	1.481 (12)
C1—C6	1.373 (10)	C8—N1	1.527 (8)
C1—C2	1.435 (10)	C8—H8A	0.9700
C2—C3	1.358 (10)	C8—H8B	0.9700
C2—H2	0.9300	C9—H9A	0.9600
C3—C4	1.371 (10)	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600
C4—C5	1.359 (9)	N1—Ni1	1.904 (6)
C5—C6	1.420 (9)	Ni1—O1ⁱ	1.815 (4)
C5—H5	0.9300	Ni1—O1	1.815 (4)
C6—C7	1.442 (9)	Ni1—N1ⁱ	1.904 (6)
C7—N1	1.284 (8)

O1—C1—C6	124.0 (6)	C9—C8—H8A	109.3
O1—C1—C2	117.9 (7)	N1—C8—H8A	109.3
C6—C1—C2	118.1 (7)	C9—C8—H8B	109.3
C3—C2—C1	120.5 (7)	N1—C8—H8B	109.3
C3—C2—H2	119.8	H8A—C8—H8B	108.0
C1—C2—H2	119.8	C8—C9—H9A	109.5
C2—C3—C4	120.5 (6)	C8—C9—H9B	109.5
C2—C3—H3	119.8	H9A—C9—H9B	109.5
C4—C3—H3	119.8	C8—C9—H9C	109.5
C5—C4—C3	121.1 (7)	H9A—C9—H9C	109.5
C5—C4—Br1	119.4 (6)	H9B—C9—H9C	109.5
C3—C4—Br1	119.6 (5)	C7—N1—C8	113.2 (6)
C4—C5—C6	119.7 (7)	C7—N1—Ni1	126.0 (5)
C4—C5—H5	120.2	C8—N1—Ni1	120.8 (4)
C6—C5—H5	120.2	O1ⁱ—Ni1—O1	180.000 (2)
C1—C6—C5	120.1 (6)	O1ⁱ—Ni1—N1ⁱ	92.8 (2)
C1—C6—C7	121.3 (6)	O1—Ni1—N1ⁱ	87.2 (2)
C5—C6—C7	118.5 (6)	O1ⁱ—Ni1—N1	87.2 (2)
N1—C7—C6	125.3 (7)	O1—Ni1—N1	92.8 (2)
N1—C7—H7	117.3	N1ⁱ—Ni1—N1	180.0 (3)
C6—C7—H7	117.3	C1—O1—Ni1	129.9 (5)
C9—C8—N1	111.4 (7)

Symmetry code: (i) −x, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	[Ni(C₉H₉BrNO)₂]
M_r	512.83
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.456 (6), 4.803 (2), 14.743 (6)
β (°)	102.157 (8)
V (Å³)	931.4 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.35
Crystal size (mm)	0.15 × 0.12 × 0.11

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.465, 0.558
No. of measured, independent and observed [I > 2σ(I)] reflections	4567, 1651, 995
R_int	0.164
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.142, 1.03
No. of reflections	1651
No. of parameters	116
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.52

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge financial support from Guangxi Key Laboratory for Advanced Materials and New Preparation Technology (grant No. 0842003–25), the Young Science Foundation of Guangxi Province of China (grant No. 0832085) and the Startup Foundation for Doctorates of Guilin University of Technology.

References

Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ge, C. M., Zhang, S. H., Feng, C., Wang, Y. G. & Li, W. (2011). Z. Anorg. Allg. Chem. 637, 112–116. CrossRef CAS Google Scholar
Gupta, K. C. & Sutar, A. K. (2008). Coord. Chem. Rev. 252, 1420–1450. Web of Science CrossRef CAS Google Scholar
Nakagima, K., Kojima, M. M., Foriumi, K., Saito, K. & Gujita, J. (1989). Bull. Chem. Soc. Jpn, 62, 760–767. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, S. H. & Feng, C. (2010). J. Mol. Struct. 977, 62–66. Web of Science CSD CrossRef CAS Google Scholar
Zhang, S.-H., Feng, X.-Z., Li, G.-Z., Jing, L.-X. & Liu, Z. (2007). Acta Cryst. E63, m396–m398. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, S. H., Ge, C. M. & Feng, C. (2008). Acta Cryst. E64, m1627. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, S. H., Song, Y., Liang, H. & Zeng, M. H. (2009). CrystEngComm, 11, 865–872. Web of Science CSD CrossRef Google Scholar