{4,4′-Dibromo-2,2′-[2,2-dimethyl­propane-1,3-diylbis(nitrilo­methanylyl­idene)]diphenolato-κ4O,N,N′,O′}nickel(II)

Rayati, S.; Ghaemi, A.; Notash, B.

doi:10.1107/S1600536811009056

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m448

doi:10.1107/S1600536811009056

Open

access

{4,4′-Dibromo-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato-κ⁴O,N,N′,O′}nickel(II)

Saeed Rayati,^a ^* Akbar Ghaemi ^b and Behrouz Notash ^c

^aDepartment of Chemistry, K. N. Toosi University of Technology, PO Box 16315-1618, Tehran, Iran, ^bDepartment of Chemistry, Islamic Azad University, Saveh Branch, PO Box 39187-366, Saveh, Iran, and ^cDepartment of Chemistry, Shahid Beheshti University, G. C. Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: rayati@kntu.ac.ir

(Received 6 March 2011; accepted 9 March 2011; online 15 March 2011)

In the title compound, [Ni(C₁₉H₁₈Br₂N₂O₂)], the Ni^II ion, lying on a twofold rotation axis, is coordinated by two N atoms and two O atoms from the Schiff base ligand in a distorted square-planar geometry. Weak intermolecular C—H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For the catalytic properties of Schiff base complexes, see: Cozzi (2004 ). For related structures see: Fun et al. (2008 ); Kargar et al. (2008 ). For the synthesis of the ligand, see: Fairhurst et al. (1995 ).

Experimental

Crystal data

[Ni(C₁₉H₁₈Br₂N₂O₂)]
M_r = 524.84
Monoclinic, C 2/c
a = 24.227 (6) Å
b = 11.030 (3) Å
c = 7.535 (2) Å
β = 107.939 (19)°
V = 1915.6 (9) Å³
Z = 4
Mo Kα radiation
μ = 5.20 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.15 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ) T_min = 0.289, T_max = 0.449
7514 measured reflections
2575 independent reflections
1892 reflections with I > 2σ(I)
R_int = 0.142

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.211
S = 1.16
2575 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.99 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N1	1.874 (4)
Ni1—O1	1.856 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O1ⁱ	0.97	2.40	3.210 (6)	141
Symmetry code: (i) -x, -y, -z.

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009056/hy2415sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009056/hy2415Isup2.hkl

checkCIF report

Comment top

Schiff base complexes are found to exhibit large applications such as catalytic properties (Cozzi, 2004). N,N'-Bis(5-bromo-2-hydroxybenzylidene)- 2,2-dimethylpropane-1,3-diamine ligand has been previously synthesized and structurally characterized by X-ray diffraction (Fun et al., 2008). The structure of a copper(II) complex of this Schiff base ligand has been also reported by Fun's group (Kargar et al., 2008).

Herein, we report the synthesis and crystal structure of an Ni(II) complex with this Schiff base ligand. The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit of the title compound contains half of the molecule. The Ni^II ion, lying on a twofold rotation axis, is coordinated by two N atoms and two O atoms from a Schiff base ligand (Table 1). The coordination environment around the Ni^II ion can be described as distorted squar-planar. In the crystal, weak intermolecular C—H···O hydrogen bonds stabilize the structure (Table 2, Fig. 2).

Related literature top

For the catalytic properties of Schiff base complexes, see: Cozzi (2004). For related structures see: Fun et al. (2008); Kargar et al. (2008). For the synthesis of the ligand, see: Fairhurst et al. (1995).

Experimental top

N,N'-Bis(5-bromo-2-hydroxybenzylidene)- 2,2-dimethylpropane-1,3-diamine was prepared according to the described procedure (Fairhurst et al., 1995). To a stirred ethanolic solution (30 ml) of 2,2-dimethylpropylenediamine (0.102 g, 1 mmol), 5-bromo-2-hydroxybenzaldehyde (0.402 g, 2 mmol) was added. The bright yellow solution was stirred and heated to reflux for 1 h. A yellow precipitate was obtained that was filtered off, washed with diethyl ether (yield: 70%; m.p.: 140 °C).

The title complex was prepared by the following procedure. The Schiff base ligand (0.467 g, 1 mmol) was dissolved in 20 ml ethanol. A solution of nickel(II) acetate (0.248 g, 1 mmol) in ethanol was added to the solution of ligand and the reaction mixture was refluxed for 1 h. The colored solution was concentrated to yield brown powders. The product washed with ethanol and air dried (yield: 95%; decomposition temperature: 242°C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x, y, -z+1/2].
	Fig. 2. The packing diagram of the title compound. Hydrogen bonds are shown as blue dashed lines.

{4,4'-Dibromo-2,2'-[2,2-dimethylpropane-1,3- diylbis(nitrilomethanylylidene)]diphenolato- κ⁴O,N,N',O'}nickel(II) top

Crystal data top

[Ni(C₁₉H₁₈Br₂N₂O₂)]	F(000) = 1040.0
M_r = 524.84	D_x = 1.820 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2575 reflections
a = 24.227 (6) Å	θ = 3.2–29.2°
b = 11.030 (3) Å	µ = 5.20 mm⁻¹
c = 7.535 (2) Å	T = 298 K
β = 107.939 (19)°	Plate, brown
V = 1915.6 (9) Å³	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection top

Stoe IPDS-2 diffractometer	2575 independent reflections
Radiation source: fine-focus sealed tube	1892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.142
ω scans	θ_max = 29.2°, θ_min = 3.2°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	h = −33→24
T_min = 0.289, T_max = 0.449	k = −15→13
7514 measured reflections	l = −10→10

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.211	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0955P)² + 1.9321P] where P = (F_o² + 2F_c²)/3
2575 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.99 e Å⁻³

Crystal data top

[Ni(C₁₉H₁₈Br₂N₂O₂)]	V = 1915.6 (9) Å³
M_r = 524.84	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.227 (6) Å	µ = 5.20 mm⁻¹
b = 11.030 (3) Å	T = 298 K
c = 7.535 (2) Å	0.30 × 0.20 × 0.15 mm
β = 107.939 (19)°

Data collection top

Stoe IPDS-2 diffractometer	2575 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	1892 reflections with I > 2σ(I)
T_min = 0.289, T_max = 0.449	R_int = 0.142
7514 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.211	H-atom parameters constrained
S = 1.16	Δρ_max = 0.74 e Å⁻³
2575 reflections	Δρ_min = −0.99 e Å⁻³
119 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.0516 (4)	0.4164 (6)	0.2433 (9)	0.0606 (17)
H1A	0.0407	0.4647	0.1319	0.073*
H1B	0.0836	0.3650	0.2432	0.073*
H1C	0.0629	0.4685	0.3505	0.073*
C2	0.0000	0.3381 (7)	0.2500	0.0386 (14)
C3	−0.0173 (2)	0.2567 (5)	0.0764 (6)	0.0376 (10)
H3A	−0.0428	0.3023	−0.0268	0.045*
H3B	0.0173	0.2364	0.0438	0.045*
C4	−0.0989 (2)	0.1277 (5)	−0.0094 (7)	0.0411 (11)
H4	−0.1172	0.1946	−0.0780	0.049*
C5	−0.1317 (2)	0.0172 (5)	−0.0337 (7)	0.0425 (11)
C6	−0.1902 (3)	0.0171 (7)	−0.1506 (8)	0.0546 (14)
H6	−0.2078	0.0894	−0.2018	0.065*
C7	−0.2206 (3)	−0.0880 (7)	−0.1878 (9)	0.0591 (17)
C8	−0.1955 (3)	−0.1976 (7)	−0.1126 (9)	0.0587 (16)
H8	−0.2172	−0.2687	−0.1381	0.070*
C9	−0.1388 (3)	−0.2006 (6)	−0.0009 (8)	0.0518 (14)
H9	−0.1223	−0.2746	0.0462	0.062*
C10	−0.1048 (2)	−0.0934 (5)	0.0447 (7)	0.0404 (11)
N1	−0.04685 (19)	0.1431 (4)	0.0982 (5)	0.0357 (9)
O1	−0.05103 (17)	−0.1011 (3)	0.1491 (5)	0.0427 (8)
Ni1	0.0000	0.02440 (9)	0.2500	0.0336 (3)
Br1	−0.29838 (4)	−0.08575 (11)	−0.35030 (14)	0.0979 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.074 (5)	0.048 (4)	0.053 (3)	−0.013 (3)	0.010 (3)	0.002 (3)
C2	0.037 (3)	0.038 (4)	0.036 (3)	0.000	0.004 (3)	0.000
C3	0.041 (3)	0.035 (3)	0.036 (2)	0.000 (2)	0.0104 (19)	0.0032 (18)
C4	0.046 (3)	0.040 (3)	0.036 (2)	0.004 (2)	0.0100 (19)	0.0043 (19)
C5	0.038 (2)	0.046 (3)	0.039 (2)	−0.005 (2)	0.0036 (19)	−0.001 (2)
C6	0.040 (3)	0.058 (4)	0.054 (3)	0.000 (3)	−0.003 (2)	0.008 (3)
C7	0.031 (3)	0.073 (5)	0.060 (3)	−0.014 (3)	−0.007 (2)	−0.003 (3)
C8	0.045 (3)	0.060 (4)	0.064 (3)	−0.018 (3)	0.007 (3)	−0.005 (3)
C9	0.057 (4)	0.039 (3)	0.055 (3)	−0.007 (3)	0.011 (3)	−0.003 (2)
C10	0.040 (3)	0.044 (3)	0.036 (2)	−0.005 (2)	0.0105 (19)	−0.0033 (19)
N1	0.040 (2)	0.036 (2)	0.0277 (15)	−0.0035 (18)	0.0057 (14)	−0.0005 (14)
O1	0.0371 (19)	0.0349 (19)	0.0495 (19)	0.0004 (15)	0.0035 (15)	−0.0030 (14)
Ni1	0.0339 (5)	0.0315 (5)	0.0325 (4)	0.000	0.0060 (3)	0.000
Br1	0.0519 (5)	0.1002 (8)	0.1070 (7)	−0.0251 (5)	−0.0265 (4)	0.0188 (5)

Geometric parameters (Å, º) top

C1—C2	1.533 (8)	C5—C6	1.421 (8)
C1—H1A	0.9600	C5—C10	1.423 (8)
C1—H1B	0.9600	C6—C7	1.354 (10)
C1—H1C	0.9600	C6—H6	0.9300
C2—C1ⁱ	1.533 (8)	C7—C8	1.393 (11)
C2—C3	1.535 (7)	C7—Br1	1.906 (6)
C2—C3ⁱ	1.535 (7)	C8—C9	1.372 (9)
C3—N1	1.476 (7)	C8—H8	0.9300
C3—H3A	0.9700	C9—C10	1.423 (8)
C3—H3B	0.9700	C9—H9	0.9300
C4—N1	1.284 (7)	C10—O1	1.300 (7)
C4—C5	1.435 (8)	Ni1—N1	1.874 (4)
C4—H4	0.9300	Ni1—O1	1.856 (4)

C2—C1—H1A	109.5	C7—C6—H6	119.9
C2—C1—H1B	109.5	C5—C6—H6	119.9
H1A—C1—H1B	109.5	C6—C7—C8	121.2 (6)
C2—C1—H1C	109.5	C6—C7—Br1	119.2 (5)
H1A—C1—H1C	109.5	C8—C7—Br1	119.5 (5)
H1B—C1—H1C	109.5	C9—C8—C7	119.9 (6)
C1—C2—C1ⁱ	111.4 (8)	C9—C8—H8	120.0
C1—C2—C3	108.3 (3)	C7—C8—H8	120.0
C1ⁱ—C2—C3	110.2 (3)	C8—C9—C10	121.7 (6)
C1—C2—C3ⁱ	110.2 (3)	C8—C9—H9	119.2
C1ⁱ—C2—C3ⁱ	108.3 (3)	C10—C9—H9	119.2
C3—C2—C3ⁱ	108.4 (6)	O1—C10—C5	123.6 (5)
N1—C3—C2	114.6 (4)	O1—C10—C9	119.4 (5)
N1—C3—H3A	108.6	C5—C10—C9	117.0 (5)
C2—C3—H3A	108.6	C4—N1—C3	117.2 (4)
N1—C3—H3B	108.6	C4—N1—Ni1	125.9 (4)
C2—C3—H3B	108.6	C3—N1—Ni1	116.0 (3)
H3A—C3—H3B	107.6	C10—O1—Ni1	128.0 (4)
N1—C4—C5	126.2 (5)	O1—Ni1—O1ⁱ	83.5 (2)
N1—C4—H4	116.9	O1—Ni1—N1ⁱ	166.70 (17)
C5—C4—H4	116.9	O1ⁱ—Ni1—N1ⁱ	93.97 (18)
C6—C5—C10	119.9 (6)	O1—Ni1—N1	93.97 (18)
C6—C5—C4	119.1 (6)	O1ⁱ—Ni1—N1	166.70 (17)
C10—C5—C4	120.7 (5)	N1ⁱ—Ni1—N1	91.3 (3)
C7—C6—C5	120.2 (6)

C1—C2—C3—N1	154.4 (5)	C8—C9—C10—C5	−1.2 (9)
C1ⁱ—C2—C3—N1	−83.4 (6)	C5—C4—N1—C3	168.8 (5)
C3ⁱ—C2—C3—N1	34.9 (3)	C5—C4—N1—Ni1	0.5 (7)
N1—C4—C5—C6	176.4 (5)	C2—C3—N1—C4	118.2 (5)
N1—C4—C5—C10	−8.9 (8)	C2—C3—N1—Ni1	−72.3 (5)
C10—C5—C6—C7	0.0 (9)	C5—C10—O1—Ni1	9.6 (7)
C4—C5—C6—C7	174.6 (6)	C9—C10—O1—Ni1	−172.6 (4)
C5—C6—C7—C8	0.3 (11)	C10—O1—Ni1—O1ⁱ	179.3 (5)
C5—C6—C7—Br1	−178.4 (5)	C10—O1—Ni1—N1ⁱ	99.5 (8)
C6—C7—C8—C9	−1.0 (11)	C10—O1—Ni1—N1	−13.9 (4)
Br1—C7—C8—C9	177.7 (5)	C4—N1—Ni1—O1	8.7 (4)
C7—C8—C9—C10	1.5 (10)	C3—N1—Ni1—O1	−159.7 (3)
C6—C5—C10—O1	178.3 (5)	C4—N1—Ni1—O1ⁱ	87.3 (9)
C4—C5—C10—O1	3.7 (8)	C3—N1—Ni1—O1ⁱ	−81.1 (9)
C6—C5—C10—C9	0.4 (8)	C4—N1—Ni1—N1ⁱ	−159.1 (5)
C4—C5—C10—C9	−174.1 (5)	C3—N1—Ni1—N1ⁱ	32.5 (3)
C8—C9—C10—O1	−179.1 (6)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1ⁱⁱ	0.97	2.40	3.210 (6)	141

Symmetry code: (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₉H₁₈Br₂N₂O₂)]
M_r	524.84
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	24.227 (6), 11.030 (3), 7.535 (2)
β (°)	107.939 (19)
V (Å³)	1915.6 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.20
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)
T_min, T_max	0.289, 0.449
No. of measured, independent and observed [I > 2σ(I)] reflections	7514, 2575, 1892
R_int	0.142
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.211, 1.16
No. of reflections	2575
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.99

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Ni1—N1

1.874 (4)

Ni1—O1

1.856 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1ⁱ	0.97	2.40	3.210 (6)	141

Symmetry code: (i) −x, −y, −z.

Acknowledgements

We gratefully acknowledge financial support of this study from K. N. Toosi University of Technology.

References

Cozzi, P. G. (2004). Chem. Soc. Rev. 33, 410–421. Web of Science CrossRef PubMed CAS Google Scholar
Fairhurst, S. A., Hughes, D. L., Kleinkes, U., Leigh, G. J., Sanders, J. R. & Weisner, J. (1995). J. Chem. Soc. Dalton Trans. pp. 321–326. CSD CrossRef Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fun, H.-K., Kia, R. & Kargar, H. (2008). Acta Cryst. E64, o1895–o1896. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kargar, H., Fun, H.-K. & Kia, R. (2008). Acta Cryst. E64, m1541–m1542. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.