supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2298    [ doi:10.1107/S1600536807038214 ]

Bis[2-(1H-benzimidazol-2-yl-[kappa]N3)-4,6-dibromophenolato-[kappa]O]nickel(II)

Y. Wu, B. Xie, L. Zou, J.-S. Feng and Z. Hu

Abstract top

The title compound, [Ni(C13H7Br2N2O)2], an NiII complex of the Schiff base 2-(3,5-dibromo-2-hydroxyphenyl)benzimidazole, was synthesized by the reaction of 3,5-dibromosalicylaldehyde and 1,2-phenylenediamine. The molecule resides on a twofold rotation axis. The NiII atom exists in a distorted tetrahedral geometry and is coordinated by one O and one N atom from each of two 2-(3,5-dibromo-2-hydroxyphenyl)benzimidazole ligands. The crystal structure is stabilized by N-H...Br and N-H...O hydrogen bonds, which link the molecules into a chain along the b axis.

Comment top

Crystal structure and properties of 1,2-N,N-disallicydene-phenylamineato nickel(II) has been reported (Wang et al., 2003). We report here the synthesis and crystal structure of bis[2-(3,5-dibromo-2-hydroxyphenyl) benzimidazole]nickel(II).

The asymmetric unit of the title compound consists of a half-molecule, with the NiII atom lying on a crystallographic twofold axis; the other half of the molecule is generated by the twofold axis (Fig. 1). The NiII atom exists in a distorted tetrahedral geometry (Table 1) and is coordinated by the O and one N atom each from two 3,5-dibromo-2-hydroxyphenyl benzimidazole ligands.

The crystal structure is stabilized by N—H···Br and N—H···O type hydrogen bonds which link the molecules into a chain along the b axis.

Related literature top

For ligand synthesis, see: Elzbieta et al. (1964). For a related structure, see: Wang et al. (2003).

Experimental top

3,5-Dibromosalicylaldehyde was prepared according to the literature method (Elzbieta et al., 1964). To a solution of 1,2-phenylenediamine (1 g) in pyridine (30 ml), one mole equivalent of 3,5-dibromosalicylaldehyde in pyridine (30 ml) was added slowly under continuous stirring and refluxed for 1 h. Then Ni(Ac)2 (10 mmol) in DMF (10 ml) was added and the solution were refluxed for 1 h. The hot solution was filtered and allowed to stand at room temperature undisturbed for about three weeks, resulting in yellow crystals.

Refinement top

The N-bound H atom was located in a difference map and refined with a N—H distance restraint of 0.86 (2) Å. C-bound H atoms were placed at calculated positions and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing labelling of the non-H atoms and 20% probability displacement ellipsoids. Atoms labelled with the suffixe a are generated by the symmetry operation (2 − x, 1/2 − y, z).
Bis[2-(1H-benzimidazol-2-yl-κN3)-4,6-dibromophenolato-κO]nickel(II) top
Crystal data top
[Ni(C13H7Br2N2O)2]Z = 8
Mr = 792.76F000 = 3056
Tetragonal, I41/aDx = 2.045 Mg m−3
Hall symbol: -I 4adMo Kα radiation
λ = 0.71073 Å
a = 12.4177 (14) ÅCell parameters from 1302 reflections
b = 12.4177 (14) Åθ = 2.4–16.7º
c = 33.389 (6) ŵ = 7.00 mm−1
α = 90ºT = 292 (2) K
β = 90ºBlock, yellow
γ = 90º0.30 × 0.20 × 0.20 mm
V = 5148.6 (12) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2510 independent reflections
Radiation source: fine-focus sealed tube1324 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.127
T = 292(2) Kθmax = 26.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −15→9
Tmin = 0.228, Tmax = 0.335k = −15→14
13205 measured reflectionsl = −41→41
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.180  w = 1/[σ2(Fo2) + (0.0739P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max = 0.001
2510 reflectionsΔρmax = 0.90 e Å−3
172 parametersΔρmin = −0.48 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C13H7Br2N2O)2]γ = 90º
Mr = 792.76V = 5148.6 (12) Å3
Tetragonal, I41/aZ = 8
a = 12.4177 (14) ÅMo Kα
b = 12.4177 (14) ŵ = 7.00 mm−1
c = 33.389 (6) ÅT = 292 (2) K
α = 90º0.30 × 0.20 × 0.20 mm
β = 90º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2510 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1324 reflections with I > 2σ(I)
Tmin = 0.228, Tmax = 0.335Rint = 0.127
13205 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.180Δρmax = 0.90 e Å−3
S = 0.95Δρmin = −0.48 e Å−3
2510 reflectionsAbsolute structure: ?
172 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
Ni11.00000.25000.00587 (4)0.0486 (4)
Br10.69106 (11)0.20197 (9)−0.08406 (3)0.0957 (5)
Br20.54458 (11)0.61501 (10)−0.04228 (4)0.1101 (6)
N10.9689 (5)0.3813 (5)0.03615 (18)0.0519 (17)
C10.7060 (8)0.3281 (7)−0.0523 (2)0.068 (3)
C20.6348 (8)0.4068 (8)−0.0575 (3)0.069 (3)
H20.57840.3992−0.07560.083*
C30.6467 (8)0.5014 (8)−0.0351 (3)0.073 (3)
C40.7292 (8)0.5120 (7)−0.0096 (3)0.066 (2)
H40.73660.57590.00460.080*
C50.8040 (7)0.4306 (6)−0.0038 (2)0.054 (2)
C60.7982 (7)0.3334 (7)−0.0261 (2)0.054 (2)
C70.8901 (6)0.4497 (6)0.0259 (2)0.0455 (18)
C81.0267 (6)0.4270 (6)0.0663 (2)0.0498 (19)
C91.1152 (8)0.3939 (7)0.0879 (3)0.073 (3)
H91.14590.32670.08330.087*
C101.1577 (9)0.4622 (9)0.1164 (3)0.085 (3)
H101.21950.44180.13020.102*
C111.1105 (10)0.5600 (9)0.1249 (3)0.094 (3)
H111.13880.60180.14540.112*
C121.0223 (9)0.5978 (8)0.1038 (3)0.082 (3)
H120.99060.66410.10920.098*
C130.9851 (7)0.5306 (7)0.0744 (2)0.057 (2)
O10.8626 (5)0.2535 (4)−0.02442 (16)0.0602 (15)
N20.8956 (6)0.5388 (6)0.0481 (2)0.0577 (18)
H2A0.867 (8)0.601 (5)0.052 (3)0.11 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0612 (10)0.0366 (8)0.0480 (7)0.0184 (7)0.0000.000
Br10.1218 (10)0.0805 (8)0.0850 (7)0.0258 (7)−0.0409 (7)−0.0212 (6)
Br20.1109 (10)0.0997 (9)0.1197 (10)0.0604 (8)−0.0217 (7)0.0026 (7)
N10.066 (4)0.033 (3)0.056 (4)0.014 (3)0.003 (3)−0.001 (3)
C10.085 (7)0.064 (6)0.056 (5)0.021 (5)−0.005 (5)−0.003 (4)
C20.073 (6)0.073 (7)0.061 (5)0.020 (5)−0.021 (4)−0.004 (5)
C30.082 (7)0.064 (6)0.072 (6)0.041 (5)−0.003 (5)0.012 (5)
C40.081 (7)0.058 (6)0.060 (5)0.027 (5)0.001 (5)0.005 (4)
C50.067 (6)0.051 (5)0.042 (4)0.013 (4)0.000 (4)−0.001 (4)
C60.066 (6)0.051 (5)0.046 (4)0.013 (4)0.001 (4)0.009 (4)
C70.059 (5)0.031 (4)0.047 (4)0.001 (4)0.017 (4)0.009 (3)
C80.045 (5)0.055 (5)0.049 (4)0.006 (4)0.003 (4)0.010 (4)
C90.091 (7)0.047 (5)0.080 (6)−0.004 (5)−0.007 (5)0.007 (5)
C100.098 (8)0.098 (9)0.060 (6)−0.018 (7)−0.020 (5)0.004 (5)
C110.118 (10)0.073 (8)0.090 (7)0.002 (7)−0.015 (7)−0.016 (6)
C120.099 (8)0.057 (6)0.090 (7)0.001 (6)−0.004 (6)−0.021 (5)
C130.070 (6)0.044 (5)0.057 (5)0.003 (4)0.010 (4)−0.001 (4)
O10.080 (4)0.038 (3)0.062 (3)0.016 (3)−0.009 (3)−0.005 (3)
N20.067 (5)0.041 (4)0.065 (4)0.015 (4)0.006 (4)−0.004 (3)
Geometric parameters (Å, °) top
Ni1—N11.957 (6)C5—C71.480 (11)
Ni1—N1i1.957 (6)C6—O11.276 (9)
Ni1—O11.984 (6)C7—N21.333 (10)
Ni1—O1i1.984 (6)C8—C91.378 (11)
Br1—C11.902 (9)C8—C131.413 (11)
Br2—C31.913 (8)C9—C101.379 (12)
N1—C71.340 (9)C9—H90.93
N1—C81.359 (10)C10—C111.378 (14)
C1—C21.329 (11)C10—H100.93
C1—C61.442 (12)C11—C121.385 (15)
C2—C31.400 (12)C11—H110.93
C2—H20.93C12—C131.367 (12)
C3—C41.338 (13)C12—H120.93
C4—C51.385 (11)C13—N21.421 (11)
C4—H40.93N2—H2A0.86 (3)
C5—C61.419 (11)
N1—Ni1—N1i117.8 (4)C5—C6—C1113.3 (7)
N1—Ni1—O194.4 (2)N2—C7—N1110.3 (7)
N1i—Ni1—O1116.8 (2)N2—C7—C5122.9 (7)
N1—Ni1—O1i116.8 (2)N1—C7—C5126.7 (7)
N1i—Ni1—O1i94.4 (2)N1—C8—C9133.1 (8)
O1—Ni1—O1i118.7 (3)N1—C8—C13109.3 (7)
C7—N1—C8108.0 (6)C9—C8—C13117.5 (8)
C7—N1—Ni1122.7 (5)C8—C9—C10118.9 (9)
C8—N1—Ni1128.8 (5)C8—C9—H9120.6
C2—C1—C6125.0 (8)C10—C9—H9120.6
C2—C1—Br1117.9 (7)C11—C10—C9121.4 (10)
C6—C1—Br1117.0 (6)C11—C10—H10119.3
C1—C2—C3118.5 (8)C9—C10—H10119.3
C1—C2—H2120.8C10—C11—C12122.1 (10)
C3—C2—H2120.8C10—C11—H11119.0
C4—C3—C2120.2 (8)C12—C11—H11119.0
C4—C3—Br2121.0 (7)C13—C12—C11115.1 (9)
C2—C3—Br2118.8 (7)C13—C12—H12122.5
C3—C4—C5122.0 (8)C11—C12—H12122.5
C3—C4—H4119.0C12—C13—C8124.9 (9)
C5—C4—H4119.0C12—C13—N2131.6 (9)
C4—C5—C6120.9 (8)C8—C13—N2103.4 (7)
C4—C5—C7117.5 (7)C6—O1—Ni1125.3 (5)
C6—C5—C7121.6 (7)C7—N2—C13108.9 (7)
O1—C6—C5127.4 (8)C7—N2—H2A145 (8)
O1—C6—C1119.3 (7)C13—N2—H2A106 (8)
N1i—Ni1—N1—C7−137.8 (6)C6—C5—C7—N2−177.9 (7)
O1—Ni1—N1—C7−14.4 (6)C4—C5—C7—N1179.3 (7)
O1i—Ni1—N1—C7110.9 (6)C6—C5—C7—N1−1.4 (11)
N1i—Ni1—N1—C851.4 (6)C7—N1—C8—C9−179.7 (9)
O1—Ni1—N1—C8174.9 (6)Ni1—N1—C8—C9−7.9 (13)
O1i—Ni1—N1—C8−59.8 (7)C7—N1—C8—C13−2.3 (8)
C6—C1—C2—C3−2.4 (15)Ni1—N1—C8—C13169.5 (5)
Br1—C1—C2—C3−178.2 (7)N1—C8—C9—C10178.0 (9)
C1—C2—C3—C41.1 (14)C13—C8—C9—C100.8 (12)
C1—C2—C3—Br2−179.9 (7)C8—C9—C10—C113.0 (15)
C2—C3—C4—C5−1.2 (14)C9—C10—C11—C12−3.9 (17)
Br2—C3—C4—C5179.8 (6)C10—C11—C12—C130.8 (16)
C3—C4—C5—C62.5 (13)C11—C12—C13—C83.3 (15)
C3—C4—C5—C7−178.2 (8)C11—C12—C13—N2177.0 (9)
C4—C5—C6—O1178.4 (8)N1—C8—C13—C12178.1 (8)
C7—C5—C6—O1−0.9 (13)C9—C8—C13—C12−4.1 (13)
C4—C5—C6—C1−3.3 (11)N1—C8—C13—N22.9 (8)
C7—C5—C6—C1177.4 (7)C9—C8—C13—N2−179.3 (7)
C2—C1—C6—O1−178.1 (9)C5—C6—O1—Ni1−7.4 (11)
Br1—C1—C6—O1−2.3 (10)C1—C6—O1—Ni1174.4 (6)
C2—C1—C6—C53.4 (13)N1—Ni1—O1—C612.9 (6)
Br1—C1—C6—C5179.2 (6)N1i—Ni1—O1—C6137.1 (6)
C8—N1—C7—N20.7 (8)O1i—Ni1—O1—C6−111.0 (6)
Ni1—N1—C7—N2−171.7 (5)N1—C7—N2—C131.1 (8)
C8—N1—C7—C5−176.1 (7)C5—C7—N2—C13178.1 (7)
Ni1—N1—C7—C511.5 (10)C12—C13—N2—C7−177.1 (9)
C4—C5—C7—N22.8 (11)C8—C13—N2—C7−2.4 (8)
Symmetry codes: (i) −x+2, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br1ii0.86 (3)2.74 (7)3.464 (7)143 (9)
N2—H2A···O1ii0.86 (3)2.11 (8)2.811 (9)138 (9)
Symmetry codes: (ii) x, y+1/2, −z.
Table 1
Selected geometric parameters (Å, °) top
Ni1—N11.957 (6)Ni1—O11.984 (6)
N1—Ni1—N1i117.8 (4)N1—Ni1—O1i116.8 (2)
N1—Ni1—O194.4 (2)O1—Ni1—O1i118.7 (3)
Symmetry codes: (i) −x+2, −y+1/2, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br1ii0.86 (3)2.74 (7)3.464 (7)143 (9)
N2—H2A···O1ii0.86 (3)2.11 (8)2.811 (9)138 (9)
Symmetry codes: (ii) x, y+1/2, −z.
Acknowledgements top

This work was supported by the Sichuan Province Education Department, Sichuan, China (grant No. 2006 A110).

references
References top

Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Elzbieta, C., Zygmunt, E. & Romuald, K. (1964). Diss. Pharm. 15, 369–378.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wang, J., Bei, F.-L. & Ma, W.-X. (2003). Chin. J. Inorg. Chem. 19, 609–612.