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Acta Cryst. (2007). E63, m2564    [ doi:10.1107/S1600536807044996 ]

Bis{2-[(3,5-dibromo-2-oxidophenyl)methylamino]ethanol-[kappa]3O,N,O'}nickel(II)

S.-H. Zhang, H.-H. Zou, M.-H. Zeng and H. Liang

Abstract top

In the title centrosymmetric complex, [Ni(C9H10Br2NO2)2], the NiII ion is chelated by two 2-[(3,5-dibromo-2-oxidophenyl)methylamino]ethanol ligands in a slightly distorted octahedral geometry. In the crystal structure, intermolecular O-H...O hydrogen bonds connect molecules into one-dimensional chains, and there are short intermolecular Br...Br contacts of 3.592 (1) Å.

Comment top

Halogens have a ubiquitous presence in both inorganic and organic chemisry, serving as mondentate or bridging ligands for a wide variety of d-block, f-block, and main group metals as well as being common substituents in a large number of organic compounds. Most frequently they lie at the periphery of molecules. The resultant steric accessibility has the potential to make halogenated compounds an attractive target for use in supramolecular chemistry and crystal engineering wherein the halogen atoms are directly involved in forming intermolecular interactions. Indeed interest in packing arrangements of halogenated compounds goes back many years to what was called the "chloro effect", wherein the presence of chloro substituents on aromatic compounds frequently resulted in stacking arrangements with a resultant short(ca 4 Å) crystallographic axis (Cohen, et al., 1964, Desiraju, 1989). Herein, we chose LH, to construct a new mononuclear nickel coordination complex Ni(L)2 {LH = [(3,5-dibromo-2-oxidophenyl)methyleneamino]ethanol}.

The molecular structure of the tile complex is shown in Fig. 1. The NiII atom, which lies on a crystallographic inversion center, is coordinated by four O atoms and two N atoms from two difference tridentate L− ligands, to furnish a slightly distorted octahedral geometry as defined by the bond lengths and angles in Table 1.

All other bond distances and angles are within the normal ranges (Allen et al., 1987). In the crystal structure close Br···Br contacts of 3.592 (1)Å are observed (Fiorenzo, et al., 2005, Zaman, et al., 2004, Jagarlapudi & Gautam, 1986) (Fig.2).

Related literature top

For a related structure, see: Zhang et al. (2007). For related literature, see: Allen et al. (1987); Cohen et al. (1964); Desiraju (1989); Fiorenzo et al. (2005); Jagarlapudi & Gautam (1986); Zaman et al. (2004); Zhang et al. (2007).

Experimental top

A solution of (2 mmol, 0.120 g) 2-Amino-ethanol and (2 mmol, 0.112 g) caustic potash in distilled water was added slowly to a solution of (2 mmol, 0.562 g) 3,5-Dibromo-2-hydroxy-benzaldehyde in methanol. The mixture was stirred for 30 min at room temperature, then added to solid (2 mmol, 0.076 g) sodium borohydride and stirred 2 h; the yellow solution become colourless. Then this mixture was slowly added to a solution of (1 mmol, 0.291 g) nickel nitrate in distilled water. The mixture was stirred for 4 h at room temperature and filtration and the filtrate was left to stand at room temperature. The green block single crystals suitable for X-ray diffration were obtained in a yield of 66%(base on nickel nitrate). analysis found(%):C, 30.52; H, 2.96; N, 3.93; C18H20Br4N2NiO4 requires (%):C, 30.59; H, 2.85; N, 3.96.

Refinement top

All hydrogen atoms were positioned geometrically and refined with a riding model, with C—H = 0.97 (CH2) or 0.93 Å(aromatic ring); Uiso(H) = 1.2 Ueq(C) and O—H = 0.82 Å; N—H =0.91Å with Uiso(H) = 1.5 Ueq(O,N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure showing 30% probability displacement ellipsoids for non-H atoms. hydrogen atoms have been omitted. symmetry codes: (i) 2 − x, 1 − y, −z.
[Figure 2] Fig. 2. Part of the crystal structure showing short Br···Br contacts as dashed lines.
Bis{2-[(3,5-Dibromo-2-oxidophenyl)methylamino]ethanol- κ3O,N,O'}nickel(II) top
Crystal data top
[Ni(C9H10Br2NO2)2]F000 = 684
Mr = 706.71Dx = 2.292 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4304 reflections
a = 4.865 (3) Åθ = 2.2–25.6º
b = 10.481 (6) ŵ = 8.78 mm−1
c = 20.103 (11) ÅT = 293 (2) K
β = 92.539 (10)ºBlock, green
V = 1024.0 (10) Å30.26 × 0.23 × 0.23 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		1880 independent reflections
Radiation source: fine-focus sealed tube1136 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.075
T = 293(2) Kθmax = 25.6º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −5→5
Tmin = 0.209, Tmax = 0.237k = −12→12
4304 measured reflectionsl = −11→24
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-atom parameters constrained
wR(F2) = 0.187  w = 1/[σ2(Fo2) + (0.0856P)2 + 3.284P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1880 reflectionsΔρmax = 1.19 e Å−3
133 parametersΔρmin = −1.60 e Å−3
24 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C9H10Br2NO2)2]V = 1024.0 (10) Å3
Mr = 706.71Z = 2
Monoclinic, P21/nMo Kα
a = 4.865 (3) ŵ = 8.78 mm−1
b = 10.481 (6) ÅT = 293 (2) K
c = 20.103 (11) Å0.26 × 0.23 × 0.23 mm
β = 92.539 (10)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		1880 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1136 reflections with I > 2σ(I)
Tmin = 0.209, Tmax = 0.237Rint = 0.075
4304 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06524 restraints
wR(F2) = 0.187H-atom parameters constrained
S = 1.09Δρmax = 1.19 e Å−3
1880 reflectionsΔρmin = −1.60 e Å−3
133 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
xyzUiso*/Ueq
Br11.4009 (3)0.32819 (14)0.20719 (6)0.0319 (4)
Br20.6079 (3)−0.05668 (14)0.16826 (7)0.0377 (5)
C11.144 (2)0.2727 (11)0.0800 (6)0.019 (3)
C21.166 (2)0.2414 (11)0.1475 (6)0.019 (3)
C31.007 (3)0.1406 (11)0.1737 (6)0.026 (3)
H31.02720.11850.21850.031*
C40.817 (2)0.0745 (12)0.1308 (6)0.026 (3)
C50.804 (2)0.1025 (12)0.0650 (7)0.027 (3)
H50.68700.05550.03660.033*
C60.963 (3)0.2010 (13)0.0384 (6)0.027 (3)
C70.959 (3)0.2210 (12)−0.0352 (5)0.024 (3)
H7A0.84970.1547−0.05720.029*
H7B1.14510.2149−0.05050.029*
C80.888 (2)0.3775 (14)−0.1243 (6)0.030 (3)
H8A0.76560.4453−0.13990.036*
H8B0.84780.3022−0.15110.036*
C91.198 (2)0.4193 (14)−0.1325 (7)0.033 (3)
H9A1.31760.3453−0.13150.040*
H9B1.21680.4637−0.17430.040*
N10.8410 (19)0.3495 (8)−0.0538 (5)0.019 (2)
H10.66880.3377−0.03900.029*
Ni11.00000.50000.00000.0174 (5)
O11.2618 (14)0.3738 (8)0.0547 (4)0.0190 (18)
O21.2670 (15)0.5024 (9)−0.0774 (4)0.0230 (19)
H21.27560.5794−0.08410.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0260 (7)0.0401 (9)0.0286 (7)−0.0054 (6)−0.0083 (5)0.0021 (6)
Br20.0267 (8)0.0384 (9)0.0481 (9)−0.0097 (7)0.0023 (6)0.0112 (7)
C10.014 (6)0.016 (6)0.026 (7)−0.002 (5)0.000 (5)−0.006 (5)
C20.016 (6)0.015 (7)0.027 (7)0.004 (5)−0.003 (5)0.004 (5)
C30.028 (7)0.023 (8)0.026 (7)−0.001 (6)−0.004 (5)0.002 (6)
C40.009 (5)0.033 (7)0.036 (6)−0.001 (5)0.001 (5)0.000 (5)
C50.019 (7)0.018 (7)0.044 (8)−0.002 (5)−0.011 (6)−0.001 (6)
C60.019 (7)0.041 (9)0.021 (6)−0.009 (6)0.001 (5)−0.003 (6)
C70.034 (8)0.022 (7)0.017 (6)−0.009 (6)−0.002 (5)0.002 (5)
C80.022 (7)0.046 (9)0.022 (7)−0.002 (6)−0.007 (5)0.001 (6)
C90.015 (6)0.044 (7)0.041 (6)−0.007 (5)0.003 (5)−0.009 (6)
N10.018 (5)0.015 (6)0.025 (5)0.003 (4)0.002 (4)0.007 (4)
Ni10.0071 (10)0.0236 (13)0.0214 (11)−0.0016 (9)−0.0012 (8)−0.0003 (10)
O10.004 (4)0.016 (4)0.037 (4)−0.003 (3)−0.006 (3)0.003 (4)
O20.005 (4)0.031 (4)0.033 (4)−0.005 (3)0.001 (3)−0.009 (4)
Geometric parameters (Å, °) top
Br1—C21.859 (12)C8—N11.475 (15)
Br2—C41.888 (13)C8—C91.586 (17)
C1—O11.319 (13)C8—H8A0.9700
C1—C21.395 (16)C8—H8B0.9700
C1—C61.403 (16)C9—O21.436 (15)
C2—C31.425 (16)C9—H9A0.9700
C3—C41.415 (17)C9—H9B0.9700
C3—H30.9300N1—Ni12.045 (9)
C4—C51.354 (17)N1—H10.9099
C5—C61.409 (18)Ni1—N1i2.045 (9)
C5—H50.9300Ni1—O2i2.071 (8)
C6—C71.495 (15)Ni1—O22.071 (8)
C7—N11.505 (15)Ni1—O12.111 (7)
C7—H7A0.9700Ni1—O1i2.111 (7)
C7—H7B0.9700O2—H20.8200
O1—C1—C2123.2 (10)O2—C9—H9A110.5
O1—C1—C6118.2 (10)C8—C9—H9A110.5
C2—C1—C6118.2 (11)O2—C9—H9B110.5
C1—C2—C3121.0 (11)C8—C9—H9B110.5
C1—C2—Br1122.2 (9)H9A—C9—H9B108.7
C3—C2—Br1116.9 (8)C8—N1—C7110.0 (9)
C4—C3—C2119.1 (11)C8—N1—Ni1106.5 (7)
C4—C3—H3120.4C7—N1—Ni1115.3 (7)
C2—C3—H3120.4C8—N1—H1121.7
C5—C4—C3119.4 (11)C7—N1—H198.3
C5—C4—Br2123.0 (10)Ni1—N1—H1105.3
C3—C4—Br2117.5 (9)N1i—Ni1—N1180
C4—C5—C6121.8 (12)N1i—Ni1—O2i81.2 (3)
C4—C5—H5119.1N1—Ni1—O2i98.8 (3)
C6—C5—H5119.1N1i—Ni1—O298.8 (3)
C1—C6—C5120.4 (11)N1—Ni1—O281.2 (3)
C1—C6—C7119.6 (11)O2i—Ni1—O2180
C5—C6—C7119.7 (11)N1i—Ni1—O190.1 (3)
C6—C7—N1111.1 (10)N1—Ni1—O189.9 (3)
C6—C7—H7A109.4O2i—Ni1—O189.2 (3)
N1—C7—H7A109.4O2—Ni1—O190.8 (3)
C6—C7—H7B109.4N1i—Ni1—O1i89.9 (3)
N1—C7—H7B109.4N1—Ni1—O1i90.1 (3)
H7A—C7—H7B108.0O2i—Ni1—O1i90.8 (3)
N1—C8—C9110.0 (10)O2—Ni1—O1i89.2 (3)
N1—C8—H8A109.7O1—Ni1—O1i180
C9—C8—H8A109.7C1—O1—Ni1116.2 (6)
N1—C8—H8B109.7C9—O2—Ni1116.0 (7)
C9—C8—H8B109.7C9—O2—H2118.8
H8A—C8—H8B108.2Ni1—O2—H2100.0
O2—C9—C8106.2 (10)
Symmetry codes: (i) −x+2, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.822.352.656 (10)103
Symmetry codes: (ii) −x+3, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
N1—Ni12.045 (9)Ni1—O12.111 (7)
Ni1—O22.071 (8)
N1i—Ni1—N1180O2—Ni1—O190.8 (3)
N1—Ni1—O2i98.8 (3)N1—Ni1—O1i90.1 (3)
N1—Ni1—O281.2 (3)O2—Ni1—O1i89.2 (3)
O2i—Ni1—O2180O1—Ni1—O1i180
N1—Ni1—O189.9 (3)
Symmetry codes: (i) −x+2, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.822.352.656 (10)103
Symmetry codes: (ii) −x+3, −y+1, −z.
Acknowledgements top

We acknowledge financial support by the NSFC (No. 20561001).

references
References top

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Fiorenzo, Z., Lee, B. & Paul, S. (2005). J. Am. Chem. Soc. 127, 5979–5989.

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