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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1599.
Published online 2009 November 18. doi:  10.1107/S1600536809047989
PMCID: PMC2971867

Bis[(E)-4-bromo-2-(methoxy­imino­meth­yl)phenolato-κ2 N,O 1]copper(II)

Abstract

In the title centrosymmetric mononuclear copper(II) complex, [Cu(C8H7BrNO2)2], the CuII atom, lying on an inversion centre, is four-coordinated in a trans-CuN2O2 square-planar geometry by two phenolate O atoms and two oxime N atoms from two symmetry-related N,O-bidentate oxime-type ligands. Inter­molecular C—H(...)O hydrogen bonds link neighbouring mol­ecules into a one-dimensional supra­molecular structure with an R 2 2(14) ring motif. This structure is further stabilized by π–π stacking inter­actions between adjacent benzene rings [centroid–centroid distance = 3.862 (1) Å].

Related literature

For general background to oxime compounds, see: Chaudhuri (2003 [triangle]); Dong et al. (2007a [triangle], 2008 [triangle]). For related structures, see: Dong et al. (2007b [triangle], 2009 [triangle]). For the ligand synthesis, see: Wang et al. (2008 [triangle]); Zhao et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1599-scheme1.jpg

Experimental

Crystal data

  • [Cu(C8H7BrNO2)2]
  • M r = 521.65
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1599-efi1.jpg
  • a = 24.691 (3) Å
  • b = 3.8623 (5) Å
  • c = 20.260 (2) Å
  • β = 117.453 (2)°
  • V = 1714.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 5.96 mm−1
  • T = 298 K
  • 0.40 × 0.12 × 0.11 mm

Data collection

  • Siemens SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.199, T max = 0.560
  • 3981 measured reflections
  • 1521 independent reflections
  • 1128 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.053
  • S = 1.04
  • 1521 reflections
  • 116 parameters
  • H-atom parameters constrained
  • Δρmax = 0.54 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047989/hy2253sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047989/hy2253Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Foundation of the Education Department of Gansu Province (0904–11) and the ‘Jing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University, which are gratefully acknowledged.

supplementary crystallographic information

Comment

Oximes are a traditional class of chelating ligands widely used in coordination and analytical chemistry and extraction metallurgy (Chaudhuri, 2003; Dong et al., 2007a,b, 2008, 2009). We report here the title mononuclear copper(II) complex with an oxime-type ligand.

The molecular structure of the title compound is shown in Fig. 1. The CuII ion, lying on an inversion centre is four-coordinated in a trans-CuN2O2 square-planar geometry, with two phenolate O atoms and two oxime N atoms from two N,O-bidentate oxime-type ligands. Bond lengths and angles are within normal ranges (Table 1). The Cu—O and Cu—N bond lengths are 1.910 (2) Å and 2.000 (3) Å, respectively, which are slightly longer than those observed in a similar Schiff base copper(II) complex [the mean bond lengths of Cu—O and Cu—N are 1.894 (2) and 1.990 (3) Å] (Dong et al., 2009).

In the crystal structure, intermolecular C1—H1C···O1 hydrogen bonds link neighbouring molecules into a one-dimensional supramolecular structure, with an R22(14) ring motif (Table 2 and Fig. 2). The one-dimensional structure is further stabilized by weak π–π stacking interactions between the adjacent benzene rings [centroid–centroid distance = 3.862 (1) Å] (Fig. 2).

Experimental

(E)-5-Bromo-2-hydroxybenzaldehyde O-methyl oxime (HL) was synthesized according to an analogous method in literature (Wang et al., 2008; Zhao et al., 2009). A blue solution of copper(II) acetate monohydrate (1.7 mg, 0.008 mmol) in methanol (4 ml) was added dropwise to a solution of HL (4.1 mg, 0.016 mmol) in methanol (5 ml) at room temperature. The colour of the mixing solution turned to yellow immediately then turned to brown slowly. The mixture was allowed to stand at room temperature for several days. With evaporating of the solvent, dark-brown needle-like single crystals suitable for X-ray crystallographic analysis were obtained (yield 49.3%). IR: ν(C═N) 1607, ν(Ar—O) 1243, ν(Cu—N) 447, ν(Cu—O) 422 cm-1. Analysis, calculated for C16H14Br2CuN2O4: C 39.30, H 3.32, Cu 11.51, N 5.13%; found: C 39.21, H 3.39, Cu 11.64, N 4.85%.

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.96 (CH3) and 0.93 Å (CH) and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted. [Symmetry code: (i) 1-x, 1-y, 1-z.]
Fig. 2.
Packing diagram for the title compound, showing the one-dimensional supramolecular structure formed by intermolecular C—H···O hydrogen bonds (dashed lines) and π–π stacking interactions (dashed lines). ...

Crystal data

[Cu(C8H7BrNO2)2]F(000) = 1020
Mr = 521.65Dx = 2.021 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1233 reflections
a = 24.691 (3) Åθ = 2.2–23.4°
b = 3.8623 (5) ŵ = 5.96 mm1
c = 20.260 (2) ÅT = 298 K
β = 117.453 (2)°Needle-like, dark-brown
V = 1714.4 (3) Å30.40 × 0.12 × 0.11 mm
Z = 4

Data collection

Siemens SMART 1000 CCD diffractometer1521 independent reflections
Radiation source: fine-focus sealed tube1128 reflections with I > 2σ(I)
graphiteRint = 0.040
[var phi] and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −21→28
Tmin = 0.199, Tmax = 0.560k = −4→4
3981 measured reflectionsl = −24→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0126P)2] where P = (Fo2 + 2Fc2)/3
1521 reflections(Δ/σ)max < 0.001
116 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = −0.40 e Å3

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

xyzUiso*/Ueq
Cu10.50000.50000.50000.0478 (2)
Br10.169435 (18)0.60817 (11)0.35138 (2)0.04703 (16)
N10.46014 (14)0.4521 (8)0.56593 (15)0.0359 (8)
O10.48859 (12)0.2994 (7)0.63799 (13)0.0454 (7)
O20.43631 (11)0.8108 (7)0.43906 (13)0.0459 (8)
C10.54119 (19)0.4966 (11)0.6868 (2)0.0563 (13)
H1A0.56720.53060.66380.084*
H1B0.56320.37370.73280.084*
H1C0.52840.71730.69640.084*
C20.40218 (17)0.4722 (9)0.54291 (19)0.0353 (10)
H20.38700.39560.57470.042*
C30.35910 (16)0.6052 (9)0.47123 (18)0.0303 (9)
C40.37870 (17)0.7699 (10)0.42340 (19)0.0337 (10)
C50.33223 (17)0.9004 (10)0.35507 (19)0.0357 (10)
H50.34341.01840.32320.043*
C60.27127 (17)0.8574 (9)0.33473 (19)0.0358 (10)
H60.24180.94230.28940.043*
C70.25404 (16)0.6861 (9)0.3825 (2)0.0308 (9)
C80.29692 (16)0.5679 (9)0.45035 (19)0.0323 (9)
H80.28470.46280.48260.039*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0365 (4)0.0708 (6)0.0413 (4)0.0207 (4)0.0224 (4)0.0218 (4)
Br10.0330 (3)0.0476 (3)0.0530 (3)−0.0031 (2)0.0134 (2)−0.0005 (2)
N10.035 (2)0.044 (2)0.0273 (18)0.0067 (17)0.0131 (15)0.0089 (15)
O10.0378 (17)0.057 (2)0.0334 (15)0.0074 (14)0.0095 (13)0.0140 (14)
O20.0311 (17)0.064 (2)0.0454 (16)0.0148 (15)0.0198 (13)0.0245 (14)
C10.057 (3)0.060 (3)0.037 (2)0.003 (2)0.009 (2)−0.001 (2)
C20.038 (3)0.036 (3)0.036 (2)0.001 (2)0.020 (2)0.0039 (18)
C30.034 (2)0.032 (2)0.026 (2)0.0051 (19)0.0140 (18)0.0016 (19)
C40.034 (2)0.037 (2)0.030 (2)0.007 (2)0.015 (2)0.0004 (19)
C50.043 (3)0.036 (2)0.033 (2)0.008 (2)0.0216 (19)0.004 (2)
C60.036 (3)0.038 (3)0.027 (2)0.009 (2)0.0097 (19)0.003 (2)
C70.031 (2)0.024 (2)0.036 (2)0.0008 (18)0.0148 (19)−0.0039 (18)
C80.039 (2)0.032 (2)0.034 (2)0.000 (2)0.0224 (19)0.0001 (19)

Geometric parameters (Å, °)

Cu1—O21.910 (2)C2—H20.9300
Cu1—N12.000 (3)C3—C81.399 (5)
Br1—C71.907 (4)C3—C41.418 (5)
N1—C21.287 (4)C4—C51.422 (5)
N1—O11.424 (3)C5—C61.375 (5)
O1—C11.435 (4)C5—H50.9300
O2—C41.316 (4)C6—C71.391 (5)
C1—H1A0.9600C6—H60.9300
C1—H1B0.9600C7—C81.370 (5)
C1—H1C0.9600C8—H80.9300
C2—C31.442 (5)
O2i—Cu1—O2180.000 (2)C3—C2—H2117.7
O2i—Cu1—N191.27 (11)C8—C3—C4120.8 (3)
O2—Cu1—N188.73 (11)C8—C3—C2117.7 (3)
O2i—Cu1—N1i88.73 (11)C4—C3—C2121.5 (3)
O2—Cu1—N1i91.27 (11)O2—C4—C3124.1 (3)
N1—Cu1—N1i180.000 (1)O2—C4—C5119.3 (3)
C2—N1—O1109.7 (3)C3—C4—C5116.6 (3)
C2—N1—Cu1124.0 (2)C6—C5—C4122.0 (4)
O1—N1—Cu1124.1 (2)C6—C5—H5119.0
N1—O1—C1110.4 (3)C4—C5—H5119.0
C4—O2—Cu1123.8 (2)C5—C6—C7119.5 (3)
O1—C1—H1A109.5C5—C6—H6120.2
O1—C1—H1B109.5C7—C6—H6120.2
H1A—C1—H1B109.5C8—C7—C6120.9 (4)
O1—C1—H1C109.5C8—C7—Br1120.0 (3)
H1A—C1—H1C109.5C6—C7—Br1119.0 (3)
H1B—C1—H1C109.5C7—C8—C3120.1 (3)
N1—C2—C3124.5 (3)C7—C8—H8120.0
N1—C2—H2117.7C3—C8—H8120.0
O2i—Cu1—N1—C2−148.5 (3)C8—C3—C4—O2−179.3 (3)
O2—Cu1—N1—C231.5 (3)C2—C3—C4—O21.1 (6)
O2i—Cu1—N1—O113.2 (3)C8—C3—C4—C51.5 (5)
O2—Cu1—N1—O1−166.8 (3)C2—C3—C4—C5−178.1 (3)
C2—N1—O1—C1−133.0 (3)O2—C4—C5—C6178.2 (3)
Cu1—N1—O1—C163.0 (3)C3—C4—C5—C6−2.6 (5)
N1—Cu1—O2—C4−38.8 (3)C4—C5—C6—C71.0 (6)
N1i—Cu1—O2—C4141.2 (3)C5—C6—C7—C81.8 (5)
O1—N1—C2—C3−178.3 (3)C5—C6—C7—Br1−176.9 (3)
Cu1—N1—C2—C3−14.3 (5)C6—C7—C8—C3−2.8 (5)
N1—C2—C3—C8171.7 (3)Br1—C7—C8—C3175.9 (3)
N1—C2—C3—C4−8.6 (6)C4—C3—C8—C71.1 (5)
Cu1—O2—C4—C329.8 (5)C2—C3—C8—C7−179.2 (3)
Cu1—O2—C4—C5−151.0 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1C···O1ii0.962.523.328 (5)142

Symmetry codes: (ii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2253).

References

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