Acta Cryst. (2009). E65, m1577 [ doi:10.1107/S1600536809046212 ]
The title complex, [Cu(C18H16Br2N2O4)(H2O)], lies on a crystallographic mirror plane with the CuII ion coordinated by two N atoms and two O atoms of a tetradentate Schiff base ligand and one O atom from a water ligand in a slightly distorted square-pyramidal environment. The mirror plane, which coincides with the Cu-Owater bond, imposes disorder of the atoms of the ethylene group. In the crystal structure, intermolecular O-H
O hydrogen bonds link complex molecules into extended chains along [100].
Condensation of ethyl diamine and 5-bromo-3-methoxyl-2-hydroxy-benzaldehyde with the ratio 1:2 in ethanol gave the Schiff base ligand. The title compound was synthesized by treatment Cu(ClO4)2.6H2O and the schiff-base ligand (1:1, molar ratio) in methanol. After the mixture was stirred for for about 30 min at room temperature, it was filtered and the filtrate was allowed to partial evaporate in air for one week to produce crystals suitable for X-ray diffraction with a yield about 52%.
H atoms were included using the HFIX command in SHELXL-97 (Sheldrick, 2008), with C—H = 0.96 and 0.93 Å; O—H = 0.82Å and were allowed for as riding atoms with Uiso(H) = 1.5Ueq(Cmethyl) and (Uiso(H) = 1.2Ueq(C,O).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./lh2938fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. All H-atoms are omitted for clarity. Only one disorder component is shown with open bonds [symmetry code (A): (x, -y+1/2, z). |
| [Cu(C18H16Br2N2O4)(H2O)] | F(000) = 1116 |
| Mr = 565.70 | Dx = 1.926 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 2580 reflections |
| a = 8.7299 (13) Å | θ = 2.9–26.7° |
| b = 27.968 (4) Å | µ = 5.25 mm−1 |
| c = 7.9900 (12) Å | T = 293 K |
| V = 1950.8 (5) Å3 | Block, blue |
| Z = 4 | 0.23 × 0.20 × 0.18 mm |
| Bruker APEXII CCD diffractometer | 1759 independent reflections |
| Radiation source: fine-focus sealed tube | 1498 reflections with I > 2σ(I) |
| graphite | Rint = 0.034 |
| φ and ω scans | θmax = 25.0°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→10 |
| Tmin = 0.378, Tmax = 0.452 | k = −33→27 |
| 8970 measured reflections | l = −8→9 |
| 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.138 | H-atom parameters constrained |
| S = 1.13 | w = 1/[σ2(Fo2) + (0.0394P)2 + 13.8845P] where P = (Fo2 + 2Fc2)/3 |
| 1759 reflections | (Δ/σ)max = 0.001 |
| 140 parameters | Δρmax = 1.48 e Å−3 |
| 1 restraint | Δρmin = −1.01 e Å−3 |
| [Cu(C18H16Br2N2O4)(H2O)] | V = 1950.8 (5) Å3 |
| Mr = 565.70 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 8.7299 (13) Å | µ = 5.25 mm−1 |
| b = 27.968 (4) Å | T = 293 K |
| c = 7.9900 (12) Å | 0.23 × 0.20 × 0.18 mm |
| Bruker APEXII CCD diffractometer | 1759 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1498 reflections with I > 2σ(I) |
| Tmin = 0.378, Tmax = 0.452 | Rint = 0.034 |
| 8970 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.0394P)2 + 13.8845P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.138 | Δρmax = 1.48 e Å−3 |
| S = 1.13 | Δρmin = −1.01 e Å−3 |
| 1759 reflections | Absolute structure: ? |
| 140 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
| H-atom parameters constrained |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Br1 | 0.28985 (13) | 0.50680 (3) | −0.14560 (14) | 0.0802 (4) | |
| Cu1 | 0.43677 (12) | 0.2500 | 0.01791 (14) | 0.0336 (3) | |
| O1 | 0.2831 (5) | 0.29928 (14) | 0.0459 (6) | 0.0394 (11) | |
| O2 | 0.0393 (5) | 0.35017 (16) | 0.0910 (7) | 0.0492 (12) | |
| O3 | 0.5275 (7) | 0.2500 | 0.2889 (8) | 0.0446 (16) | |
| H3A | 0.5656 | 0.2746 | 0.3257 | 0.067* | |
| N1 | 0.5856 (6) | 0.2962 (2) | −0.0675 (8) | 0.0515 (16) | |
| C1 | 0.4226 (7) | 0.3656 (2) | −0.0697 (8) | 0.0385 (15) | |
| C2 | 0.2929 (7) | 0.3439 (2) | 0.0005 (8) | 0.0334 (13) | |
| C3 | 0.1626 (7) | 0.3736 (2) | 0.0235 (8) | 0.0387 (15) | |
| C4 | 0.1622 (8) | 0.4211 (2) | −0.0169 (9) | 0.0436 (16) | |
| H4 | 0.0754 | 0.4397 | 0.0006 | 0.052* | |
| C5 | 0.2941 (9) | 0.4410 (2) | −0.0848 (9) | 0.0472 (17) | |
| C6 | 0.4200 (9) | 0.4150 (2) | −0.1124 (9) | 0.0484 (18) | |
| H6 | 0.5062 | 0.4291 | −0.1596 | 0.058* | |
| C7 | 0.5621 (8) | 0.3402 (2) | −0.1013 (9) | 0.0460 (17) | |
| H7 | 0.6421 | 0.3571 | −0.1505 | 0.055* | |
| C8 | −0.0958 (9) | 0.3769 (3) | 0.1200 (10) | 0.058 (2) | |
| H8A | −0.0753 | 0.4015 | 0.2011 | 0.087* | |
| H8B | −0.1746 | 0.3561 | 0.1615 | 0.087* | |
| H8C | −0.1290 | 0.3913 | 0.0172 | 0.087* | |
| C9 | 0.7175 (16) | 0.2701 (7) | −0.147 (2) | 0.054 (5) | 0.50 |
| H9A | 0.6948 | 0.2643 | −0.2645 | 0.065* | 0.50 |
| H9B | 0.8089 | 0.2897 | −0.1413 | 0.065* | 0.50 |
| C9A | 0.7457 (13) | 0.2236 (7) | −0.061 (3) | 0.052 (5) | 0.50 |
| H9A1 | 0.7812 | 0.2280 | 0.0527 | 0.063* | 0.50 |
| H9A2 | 0.8177 | 0.2037 | −0.1222 | 0.063* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.1002 (8) | 0.0319 (4) | 0.1084 (8) | 0.0054 (4) | 0.0121 (6) | 0.0259 (4) |
| Cu1 | 0.0301 (5) | 0.0275 (5) | 0.0433 (6) | 0.000 | 0.0040 (5) | 0.000 |
| O1 | 0.038 (2) | 0.024 (2) | 0.056 (3) | 0.0025 (18) | 0.006 (2) | 0.010 (2) |
| O2 | 0.038 (3) | 0.034 (2) | 0.076 (3) | 0.006 (2) | 0.014 (2) | 0.007 (2) |
| O3 | 0.053 (4) | 0.032 (3) | 0.049 (4) | 0.000 | −0.011 (3) | 0.000 |
| N1 | 0.035 (3) | 0.044 (3) | 0.076 (4) | 0.000 (3) | 0.013 (3) | 0.020 (3) |
| C1 | 0.041 (4) | 0.037 (4) | 0.038 (3) | −0.002 (3) | 0.001 (3) | 0.008 (3) |
| C2 | 0.039 (3) | 0.026 (3) | 0.035 (3) | 0.000 (3) | 0.000 (3) | 0.002 (3) |
| C3 | 0.041 (3) | 0.035 (3) | 0.040 (3) | −0.002 (3) | −0.001 (3) | 0.002 (3) |
| C4 | 0.049 (4) | 0.030 (3) | 0.051 (4) | 0.005 (3) | −0.004 (3) | 0.007 (3) |
| C5 | 0.065 (5) | 0.029 (3) | 0.048 (4) | −0.001 (3) | −0.005 (4) | 0.005 (3) |
| C6 | 0.054 (4) | 0.039 (4) | 0.052 (4) | −0.004 (3) | 0.000 (4) | 0.009 (3) |
| C7 | 0.038 (4) | 0.043 (4) | 0.057 (4) | −0.005 (3) | 0.008 (3) | 0.013 (3) |
| C8 | 0.052 (5) | 0.053 (5) | 0.069 (5) | 0.015 (4) | 0.011 (4) | 0.009 (4) |
| C9 | 0.031 (8) | 0.053 (9) | 0.078 (14) | −0.001 (7) | 0.009 (9) | 0.021 (10) |
| C9A | 0.023 (8) | 0.067 (11) | 0.066 (13) | 0.004 (7) | −0.006 (8) | −0.011 (11) |
| Br1—C5 | 1.903 (7) | C2—C3 | 1.420 (9) |
| Cu1—O1i | 1.937 (4) | C3—C4 | 1.367 (9) |
| Cu1—O1 | 1.937 (4) | C4—C5 | 1.389 (10) |
| Cu1—N1 | 1.954 (5) | C4—H4 | 0.9300 |
| Cu1—N1i | 1.954 (5) | C5—C6 | 1.338 (10) |
| Cu1—O3 | 2.305 (6) | C6—H6 | 0.9300 |
| O1—C2 | 1.303 (7) | C7—H7 | 0.9300 |
| O2—C3 | 1.371 (8) | C8—H8A | 0.9600 |
| O2—C8 | 1.416 (8) | C8—H8B | 0.9600 |
| O3—H3A | 0.8188 | C8—H8C | 0.9600 |
| N1—C7 | 1.277 (9) | C9—C9A | 1.491 (19) |
| N1—C9Ai | 1.504 (10) | C9—H9A | 0.9700 |
| N1—C9 | 1.505 (10) | C9—H9B | 0.9700 |
| C1—C2 | 1.402 (9) | C9A—N1i | 1.504 (10) |
| C1—C6 | 1.421 (9) | C9A—H9A1 | 0.9700 |
| C1—C7 | 1.433 (10) | C9A—H9A2 | 0.9700 |
| O1i—Cu1—O1 | 90.8 (2) | C5—C4—H4 | 120.6 |
| O1i—Cu1—N1 | 166.2 (3) | C6—C5—C4 | 121.8 (6) |
| O1—Cu1—N1 | 91.8 (2) | C6—C5—Br1 | 120.1 (6) |
| O1i—Cu1—N1i | 91.8 (2) | C4—C5—Br1 | 118.1 (5) |
| O1—Cu1—N1i | 166.2 (3) | C5—C6—C1 | 120.2 (7) |
| N1—Cu1—N1i | 82.7 (4) | C5—C6—H6 | 119.9 |
| O1i—Cu1—O3 | 97.45 (18) | C1—C6—H6 | 119.9 |
| O1—Cu1—O3 | 97.45 (18) | N1—C7—C1 | 125.3 (6) |
| N1—Cu1—O3 | 95.7 (2) | N1—C7—H7 | 117.4 |
| N1i—Cu1—O3 | 95.7 (2) | C1—C7—H7 | 117.4 |
| C2—O1—Cu1 | 127.2 (4) | O2—C8—H8A | 109.5 |
| C3—O2—C8 | 117.8 (5) | O2—C8—H8B | 109.5 |
| Cu1—O3—H3A | 118.5 | H8A—C8—H8B | 109.5 |
| C7—N1—C9Ai | 120.7 (10) | O2—C8—H8C | 109.5 |
| C7—N1—C9 | 120.0 (9) | H8A—C8—H8C | 109.5 |
| C7—N1—Cu1 | 127.2 (5) | H8B—C8—H8C | 109.5 |
| C9Ai—N1—Cu1 | 111.3 (9) | C9A—C9—N1 | 110.7 (14) |
| C9—N1—Cu1 | 109.7 (8) | C9A—C9—H9A | 109.5 |
| C2—C1—C6 | 120.2 (6) | N1—C9—H9A | 109.5 |
| C2—C1—C7 | 122.8 (6) | C9A—C9—H9B | 109.5 |
| C6—C1—C7 | 117.0 (6) | N1—C9—H9B | 109.5 |
| O1—C2—C1 | 125.4 (6) | H9A—C9—H9B | 108.1 |
| O1—C2—C3 | 118.1 (6) | C9—C9A—N1i | 98.7 (12) |
| C1—C2—C3 | 116.5 (6) | C9—C9A—H9A1 | 112.0 |
| C4—C3—O2 | 123.7 (6) | N1i—C9A—H9A1 | 112.0 |
| C4—C3—C2 | 122.6 (6) | C9—C9A—H9A2 | 112.0 |
| O2—C3—C2 | 113.7 (5) | N1i—C9A—H9A2 | 112.0 |
| C3—C4—C5 | 118.7 (7) | H9A1—C9A—H9A2 | 109.7 |
| C3—C4—H4 | 120.6 |
| Symmetry codes: (i) x, −y+1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···O2ii | 0.82 | 2.23 | 2.963 (5) | 150 |
| O3—H3A···O1ii | 0.82 | 2.27 | 2.936 (7) | 139 |
| Symmetry codes: (ii) x+1/2, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···O2i | 0.82 | 2.23 | 2.963 (5) | 150 |
| O3—H3A···O1i | 0.82 | 2.27 | 2.936 (7) | 139 |
| Symmetry codes: (i) x+1/2, y, −z+1/2. |
This work was funded by a research grant from the Shanxi Datong University Foundation of Shanxi Province of the People's Republic of China (grant No. 2008 K1). We also thank Huazhong Normal University for supporting this study.
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Schiff-bases can readily form stable complexes with most transition metals, in which some may exhibit interesting properties (Yu et al., 2007; Ghosh et al., 2006; Singh et al., 2007; Nayka et al., 2006). Here, we report a Cu(II) complex based on the tetradentate Schiff-base ligand N,N'-ethylenebis(5-bromo-3-methoxysalicylaldimine.
The molecular structure of the title compound is shown in Fig. 1. The complex lies on a crystallographic mirror plane with the CuII ion coordinated in a slightly distorted square-pyramidal environment. The basal plane is occupied by two N atoms and two O atoms of the Schiff-base ligand, and the apical site is occupied by the O atom of the coordinated water molecule. The CuII ion is displaced towards the Cu—Owater bond from the plane formed by the two N atoms and two O atoms by 0.224 (4) Å. The Cu—N and Cu—O bond lengths are consistent with the corresponding distances found in other Cu Schiff base complexes (Nathan, et al., 2003; Saha, et al., 2007; Xing, 2009).