metal-organic compounds
Bis[(E)-4-bromo-2-(methoxyiminomethyl)phenolato-κ2N,O1]copper(II)
aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
*Correspondence e-mail: chailanqin@163.com
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 R22(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); Dong et al. (2007a, 2008). For related structures, see: Dong et al. (2007b, 2009). For the ligand synthesis, see: Wang et al. (2008); Zhao et al. (2009).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); 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) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809047989/hy2253sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809047989/hy2253Isup2.hkl
(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%.
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).
Data collection: SMART (Siemens, 1996); cell
SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Cu(C8H7BrNO2)2] | F(000) = 1020 |
Mr = 521.65 | Dx = 2.021 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1233 reflections |
a = 24.691 (3) Å | θ = 2.2–23.4° |
b = 3.8623 (5) Å | µ = 5.96 mm−1 |
c = 20.260 (2) Å | T = 298 K |
β = 117.453 (2)° | Needle-like, dark-brown |
V = 1714.4 (3) Å3 | 0.40 × 0.12 × 0.11 mm |
Z = 4 |
Siemens SMART 1000 CCD diffractometer | 1521 independent reflections |
Radiation source: fine-focus sealed tube | 1128 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→28 |
Tmin = 0.199, Tmax = 0.560 | k = −4→4 |
3981 measured reflections | l = −24→23 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0126P)2] where P = (Fo2 + 2Fc2)/3 |
1521 reflections | (Δ/σ)max < 0.001 |
116 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Cu(C8H7BrNO2)2] | V = 1714.4 (3) Å3 |
Mr = 521.65 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.691 (3) Å | µ = 5.96 mm−1 |
b = 3.8623 (5) Å | T = 298 K |
c = 20.260 (2) Å | 0.40 × 0.12 × 0.11 mm |
β = 117.453 (2)° |
Siemens SMART 1000 CCD diffractometer | 1521 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1128 reflections with I > 2σ(I) |
Tmin = 0.199, Tmax = 0.560 | Rint = 0.040 |
3981 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.54 e Å−3 |
1521 reflections | Δρmin = −0.40 e Å−3 |
116 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0478 (2) | |
Br1 | 0.169435 (18) | 0.60817 (11) | 0.35138 (2) | 0.04703 (16) | |
N1 | 0.46014 (14) | 0.4521 (8) | 0.56593 (15) | 0.0359 (8) | |
O1 | 0.48859 (12) | 0.2994 (7) | 0.63799 (13) | 0.0454 (7) | |
O2 | 0.43631 (11) | 0.8108 (7) | 0.43906 (13) | 0.0459 (8) | |
C1 | 0.54119 (19) | 0.4966 (11) | 0.6868 (2) | 0.0563 (13) | |
H1A | 0.5672 | 0.5306 | 0.6638 | 0.084* | |
H1B | 0.5632 | 0.3737 | 0.7328 | 0.084* | |
H1C | 0.5284 | 0.7173 | 0.6964 | 0.084* | |
C2 | 0.40218 (17) | 0.4722 (9) | 0.54291 (19) | 0.0353 (10) | |
H2 | 0.3870 | 0.3956 | 0.5747 | 0.042* | |
C3 | 0.35910 (16) | 0.6052 (9) | 0.47123 (18) | 0.0303 (9) | |
C4 | 0.37870 (17) | 0.7699 (10) | 0.42340 (19) | 0.0337 (10) | |
C5 | 0.33223 (17) | 0.9004 (10) | 0.35507 (19) | 0.0357 (10) | |
H5 | 0.3434 | 1.0184 | 0.3232 | 0.043* | |
C6 | 0.27127 (17) | 0.8574 (9) | 0.33473 (19) | 0.0358 (10) | |
H6 | 0.2418 | 0.9423 | 0.2894 | 0.043* | |
C7 | 0.25404 (16) | 0.6861 (9) | 0.3825 (2) | 0.0308 (9) | |
C8 | 0.29692 (16) | 0.5679 (9) | 0.45035 (19) | 0.0323 (9) | |
H8 | 0.2847 | 0.4628 | 0.4826 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0365 (4) | 0.0708 (6) | 0.0413 (4) | 0.0207 (4) | 0.0224 (4) | 0.0218 (4) |
Br1 | 0.0330 (3) | 0.0476 (3) | 0.0530 (3) | −0.0031 (2) | 0.0134 (2) | −0.0005 (2) |
N1 | 0.035 (2) | 0.044 (2) | 0.0273 (18) | 0.0067 (17) | 0.0131 (15) | 0.0089 (15) |
O1 | 0.0378 (17) | 0.057 (2) | 0.0334 (15) | 0.0074 (14) | 0.0095 (13) | 0.0140 (14) |
O2 | 0.0311 (17) | 0.064 (2) | 0.0454 (16) | 0.0148 (15) | 0.0198 (13) | 0.0245 (14) |
C1 | 0.057 (3) | 0.060 (3) | 0.037 (2) | 0.003 (2) | 0.009 (2) | −0.001 (2) |
C2 | 0.038 (3) | 0.036 (3) | 0.036 (2) | 0.001 (2) | 0.020 (2) | 0.0039 (18) |
C3 | 0.034 (2) | 0.032 (2) | 0.026 (2) | 0.0051 (19) | 0.0140 (18) | 0.0016 (19) |
C4 | 0.034 (2) | 0.037 (2) | 0.030 (2) | 0.007 (2) | 0.015 (2) | 0.0004 (19) |
C5 | 0.043 (3) | 0.036 (2) | 0.033 (2) | 0.008 (2) | 0.0216 (19) | 0.004 (2) |
C6 | 0.036 (3) | 0.038 (3) | 0.027 (2) | 0.009 (2) | 0.0097 (19) | 0.003 (2) |
C7 | 0.031 (2) | 0.024 (2) | 0.036 (2) | 0.0008 (18) | 0.0148 (19) | −0.0039 (18) |
C8 | 0.039 (2) | 0.032 (2) | 0.034 (2) | 0.000 (2) | 0.0224 (19) | 0.0001 (19) |
Cu1—O2 | 1.910 (2) | C2—H2 | 0.9300 |
Cu1—N1 | 2.000 (3) | C3—C8 | 1.399 (5) |
Br1—C7 | 1.907 (4) | C3—C4 | 1.418 (5) |
N1—C2 | 1.287 (4) | C4—C5 | 1.422 (5) |
N1—O1 | 1.424 (3) | C5—C6 | 1.375 (5) |
O1—C1 | 1.435 (4) | C5—H5 | 0.9300 |
O2—C4 | 1.316 (4) | C6—C7 | 1.391 (5) |
C1—H1A | 0.9600 | C6—H6 | 0.9300 |
C1—H1B | 0.9600 | C7—C8 | 1.370 (5) |
C1—H1C | 0.9600 | C8—H8 | 0.9300 |
C2—C3 | 1.442 (5) | ||
O2i—Cu1—O2 | 180.000 (2) | C3—C2—H2 | 117.7 |
O2i—Cu1—N1 | 91.27 (11) | C8—C3—C4 | 120.8 (3) |
O2—Cu1—N1 | 88.73 (11) | C8—C3—C2 | 117.7 (3) |
O2i—Cu1—N1i | 88.73 (11) | C4—C3—C2 | 121.5 (3) |
O2—Cu1—N1i | 91.27 (11) | O2—C4—C3 | 124.1 (3) |
N1—Cu1—N1i | 180.000 (1) | O2—C4—C5 | 119.3 (3) |
C2—N1—O1 | 109.7 (3) | C3—C4—C5 | 116.6 (3) |
C2—N1—Cu1 | 124.0 (2) | C6—C5—C4 | 122.0 (4) |
O1—N1—Cu1 | 124.1 (2) | C6—C5—H5 | 119.0 |
N1—O1—C1 | 110.4 (3) | C4—C5—H5 | 119.0 |
C4—O2—Cu1 | 123.8 (2) | C5—C6—C7 | 119.5 (3) |
O1—C1—H1A | 109.5 | C5—C6—H6 | 120.2 |
O1—C1—H1B | 109.5 | C7—C6—H6 | 120.2 |
H1A—C1—H1B | 109.5 | C8—C7—C6 | 120.9 (4) |
O1—C1—H1C | 109.5 | C8—C7—Br1 | 120.0 (3) |
H1A—C1—H1C | 109.5 | C6—C7—Br1 | 119.0 (3) |
H1B—C1—H1C | 109.5 | C7—C8—C3 | 120.1 (3) |
N1—C2—C3 | 124.5 (3) | C7—C8—H8 | 120.0 |
N1—C2—H2 | 117.7 | C3—C8—H8 | 120.0 |
O2i—Cu1—N1—C2 | −148.5 (3) | C8—C3—C4—O2 | −179.3 (3) |
O2—Cu1—N1—C2 | 31.5 (3) | C2—C3—C4—O2 | 1.1 (6) |
O2i—Cu1—N1—O1 | 13.2 (3) | C8—C3—C4—C5 | 1.5 (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—C6 | 178.2 (3) |
Cu1—N1—O1—C1 | 63.0 (3) | C3—C4—C5—C6 | −2.6 (5) |
N1—Cu1—O2—C4 | −38.8 (3) | C4—C5—C6—C7 | 1.0 (6) |
N1i—Cu1—O2—C4 | 141.2 (3) | C5—C6—C7—C8 | 1.8 (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—C8 | 171.7 (3) | Br1—C7—C8—C3 | 175.9 (3) |
N1—C2—C3—C4 | −8.6 (6) | C4—C3—C8—C7 | 1.1 (5) |
Cu1—O2—C4—C3 | 29.8 (5) | C2—C3—C8—C7 | −179.2 (3) |
Cu1—O2—C4—C5 | −151.0 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1C···O1ii | 0.96 | 2.52 | 3.328 (5) | 142 |
Symmetry code: (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H7BrNO2)2] |
Mr | 521.65 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 24.691 (3), 3.8623 (5), 20.260 (2) |
β (°) | 117.453 (2) |
V (Å3) | 1714.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.96 |
Crystal size (mm) | 0.40 × 0.12 × 0.11 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.199, 0.560 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3981, 1521, 1128 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.053, 1.04 |
No. of reflections | 1521 |
No. of parameters | 116 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.40 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1C···O1i | 0.96 | 2.52 | 3.328 (5) | 142 |
Symmetry code: (i) x, y+1, z. |
Acknowledgements
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.
References
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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.
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).