Acta Cryst. (2009). E65, m1098 [ doi:10.1107/S1600536809031043 ]
The title compound, [Cu(C7H5ClNO)2]·2CH3OH, possesses crystallographic twofold symmetry, with the twofold axis passing through the central CuII ion. The metal centre is coordinated by two O atoms and two N atoms from two symmetry-related Schiff base ligands, forming a slightly distorted cis-CuN2O2 square-planar geometry. The complex molecules are linked via the solvent methanol molecules by O-H
O and N-HO hydrogen bonds, leading to the formation of chains along the b axis.
All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. 5-Chloro-2-hydroxybenzaldehyde (0.2 mmol, 31.32 mg), isopropylamine (0.2 mmol, 11.8 mg) and Cu(Ac)2 (0.1 mmol 18.2 mg) were dissolved in methanol (10 ml). The mixture was stirred at room temperature for 30 min and then filtered. The filtrate was allowed to stand in air for 7 d, after which time yellow block-shaped crystals of the title compound were formed by slow evaporation of the solvent.
H atoms attached to C and N atoms were placed in geometrically idealized positions (N-H = 0.86 Å and C-H = 0.93-0.96 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N). H atoms attached to O atoms (water) were located in difference Fourier maps and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(O).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ci2879fig1thm.gif)
| Fig. 1. The asymmetric unit of (I), showing 30% probability displacement ellipsoids. The dashed line indicates a hydrogen bond; symmetry code: (A) 1 -x, y, 3/2 - z. |
![[Figure 2]](./ci2879fig2thm.gif)
| Fig. 2. Part of the crystal packing of (I), viewed along the b axis. Hydrogen bonds are shown as dashed lines. |
| [Cu(C7H5ClNO)2]·2CH4O | F(000) = 892 |
| Mr = 436.76 | Dx = 1.626 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1362 reflections |
| a = 20.603 (2) Å | θ = 2.6–27.5° |
| b = 7.639 (1) Å | µ = 1.55 mm−1 |
| c = 14.6681 (15) Å | T = 298 K |
| β = 129.376 (2)° | Block, yellow |
| V = 1784.5 (3) Å3 | 0.15 × 0.11 × 0.08 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1568 independent reflections |
| Radiation source: fine-focus sealed tube | 1167 reflections with I > 2σ(I) |
| graphite | Rint = 0.048 |
| φ and ω scans | θmax = 25.0°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→20 |
| Tmin = 0.801, Tmax = 0.886 | k = −9→7 |
| 4502 measured reflections | l = −15→17 |
| 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.084 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0346P)2] where P = (Fo2 + 2Fc2)/3 |
| 1568 reflections | (Δ/σ)max = 0.001 |
| 114 parameters | Δρmax = 0.38 e Å−3 |
| 0 restraints | Δρmin = −0.26 e Å−3 |
| [Cu(C7H5ClNO)2]·2CH4O | V = 1784.5 (3) Å3 |
| Mr = 436.76 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 20.603 (2) Å | µ = 1.55 mm−1 |
| b = 7.639 (1) Å | T = 298 K |
| c = 14.6681 (15) Å | 0.15 × 0.11 × 0.08 mm |
| β = 129.376 (2)° |
| Bruker SMART CCD area-detector diffractometer | 1568 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1167 reflections with I > 2σ(I) |
| Tmin = 0.801, Tmax = 0.886 | Rint = 0.048 |
| 4502 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
| wR(F2) = 0.084 | Δρmax = 0.38 e Å−3 |
| S = 1.05 | Δρmin = −0.26 e Å−3 |
| 1568 reflections | Absolute structure: ? |
| 114 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.5000 | 0.17304 (7) | 0.7500 | 0.0365 (2) | |
| Cl1 | 0.11369 (5) | 0.33974 (13) | 0.15757 (7) | 0.0592 (3) | |
| N1 | 0.41857 (15) | −0.0028 (3) | 0.6418 (2) | 0.0413 (7) | |
| H1 | 0.4297 | −0.1088 | 0.6674 | 0.050* | |
| O1 | 0.43140 (12) | 0.3587 (2) | 0.64243 (18) | 0.0417 (6) | |
| O2 | 0.41114 (18) | 0.6573 (3) | 0.7355 (2) | 0.0727 (8) | |
| H2 | 0.4284 | 0.5693 | 0.7249 | 0.109* | |
| C1 | 0.3505 (2) | 0.0205 (4) | 0.5374 (3) | 0.0407 (8) | |
| H1A | 0.3177 | −0.0776 | 0.4964 | 0.049* | |
| C2 | 0.32026 (18) | 0.1865 (4) | 0.4774 (3) | 0.0342 (7) | |
| C3 | 0.36158 (18) | 0.3465 (4) | 0.5328 (3) | 0.0343 (7) | |
| C4 | 0.32418 (18) | 0.5002 (4) | 0.4667 (3) | 0.0414 (8) | |
| H4 | 0.3504 | 0.6069 | 0.5010 | 0.050* | |
| C5 | 0.25007 (19) | 0.4981 (5) | 0.3530 (3) | 0.0439 (8) | |
| H5 | 0.2269 | 0.6020 | 0.3110 | 0.053* | |
| C6 | 0.21020 (18) | 0.3407 (4) | 0.3012 (3) | 0.0408 (8) | |
| C7 | 0.24355 (19) | 0.1877 (4) | 0.3604 (3) | 0.0411 (8) | |
| H7 | 0.2159 | 0.0829 | 0.3240 | 0.049* | |
| C20 | 0.4423 (2) | 0.6610 (5) | 0.8525 (3) | 0.0618 (10) | |
| H20A | 0.5025 | 0.6544 | 0.9048 | 0.093* | |
| H20B | 0.4204 | 0.5632 | 0.8665 | 0.093* | |
| H20C | 0.4254 | 0.7680 | 0.8666 | 0.093* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0396 (3) | 0.0265 (3) | 0.0406 (3) | 0.000 | 0.0241 (3) | 0.000 |
| Cl1 | 0.0508 (5) | 0.0672 (7) | 0.0368 (5) | 0.0024 (5) | 0.0170 (4) | −0.0017 (4) |
| N1 | 0.0480 (16) | 0.0252 (14) | 0.0447 (16) | −0.0017 (13) | 0.0266 (14) | −0.0018 (12) |
| O1 | 0.0385 (12) | 0.0252 (12) | 0.0398 (13) | −0.0011 (9) | 0.0147 (11) | 0.0018 (9) |
| O2 | 0.118 (2) | 0.0396 (15) | 0.0717 (19) | 0.0145 (15) | 0.0654 (18) | 0.0053 (13) |
| C1 | 0.0474 (19) | 0.0295 (17) | 0.049 (2) | −0.0093 (15) | 0.0324 (18) | −0.0109 (15) |
| C2 | 0.0352 (16) | 0.0332 (17) | 0.0381 (17) | 0.0000 (15) | 0.0251 (15) | −0.0016 (14) |
| C3 | 0.0362 (17) | 0.0296 (18) | 0.0398 (18) | 0.0007 (14) | 0.0253 (16) | 0.0008 (14) |
| C4 | 0.0429 (18) | 0.0338 (18) | 0.0427 (19) | −0.0015 (15) | 0.0248 (16) | 0.0013 (15) |
| C5 | 0.050 (2) | 0.0404 (19) | 0.045 (2) | 0.0080 (17) | 0.0314 (17) | 0.0103 (16) |
| C6 | 0.0379 (18) | 0.050 (2) | 0.0327 (17) | 0.0020 (16) | 0.0214 (15) | −0.0004 (15) |
| C7 | 0.0457 (19) | 0.0416 (19) | 0.0409 (19) | −0.0048 (17) | 0.0299 (17) | −0.0087 (16) |
| C20 | 0.068 (3) | 0.054 (2) | 0.062 (3) | 0.002 (2) | 0.040 (2) | −0.001 (2) |
| Cu1—O1i | 1.9152 (19) | C2—C3 | 1.414 (4) |
| Cu1—O1 | 1.9152 (19) | C2—C7 | 1.415 (4) |
| Cu1—N1 | 1.939 (2) | C3—C4 | 1.402 (4) |
| Cu1—N1i | 1.939 (2) | C4—C5 | 1.372 (4) |
| Cl1—C6 | 1.754 (3) | C4—H4 | 0.93 |
| N1—C1 | 1.272 (4) | C5—C6 | 1.380 (4) |
| N1—H1 | 0.86 | C5—H5 | 0.93 |
| O1—C3 | 1.315 (3) | C6—C7 | 1.355 (4) |
| O2—C20 | 1.400 (4) | C7—H7 | 0.93 |
| O2—H2 | 0.82 | C20—H20A | 0.96 |
| C1—C2 | 1.440 (4) | C20—H20B | 0.96 |
| C1—H1A | 0.93 | C20—H20C | 0.96 |
| O1i—Cu1—O1 | 84.48 (12) | C4—C3—C2 | 117.4 (3) |
| O1i—Cu1—N1 | 172.02 (10) | C5—C4—C3 | 122.0 (3) |
| O1—Cu1—N1 | 92.03 (9) | C5—C4—H4 | 119.0 |
| O1i—Cu1—N1i | 92.03 (9) | C3—C4—H4 | 119.0 |
| O1—Cu1—N1i | 172.02 (10) | C4—C5—C6 | 119.6 (3) |
| N1—Cu1—N1i | 92.31 (15) | C4—C5—H5 | 120.2 |
| C1—N1—Cu1 | 127.5 (2) | C6—C5—H5 | 120.2 |
| C1—N1—H1 | 116.2 | C7—C6—C5 | 121.1 (3) |
| Cu1—N1—H1 | 116.2 | C7—C6—Cl1 | 119.6 (3) |
| C3—O1—Cu1 | 128.18 (18) | C5—C6—Cl1 | 119.3 (2) |
| C20—O2—H2 | 109.5 | C6—C7—C2 | 120.3 (3) |
| N1—C1—C2 | 125.3 (3) | C6—C7—H7 | 119.8 |
| N1—C1—H1A | 117.3 | C2—C7—H7 | 119.8 |
| C2—C1—H1A | 117.3 | O2—C20—H20A | 109.5 |
| C3—C2—C7 | 119.6 (3) | O2—C20—H20B | 109.5 |
| C3—C2—C1 | 122.7 (3) | H20A—C20—H20B | 109.5 |
| C7—C2—C1 | 117.6 (3) | O2—C20—H20C | 109.5 |
| O1—C3—C4 | 118.8 (3) | H20A—C20—H20C | 109.5 |
| O1—C3—C2 | 123.8 (3) | H20B—C20—H20C | 109.5 |
| O1—Cu1—N1—C1 | 4.2 (3) | C7—C2—C3—C4 | −1.0 (4) |
| N1i—Cu1—N1—C1 | −169.1 (3) | C1—C2—C3—C4 | −177.5 (3) |
| O1i—Cu1—O1—C3 | 179.9 (3) | O1—C3—C4—C5 | −178.1 (3) |
| N1—Cu1—O1—C3 | −7.3 (3) | C2—C3—C4—C5 | 0.5 (5) |
| Cu1—N1—C1—C2 | 0.4 (5) | C3—C4—C5—C6 | 0.4 (5) |
| N1—C1—C2—C3 | −4.3 (5) | C4—C5—C6—C7 | −0.8 (5) |
| N1—C1—C2—C7 | 179.2 (3) | C4—C5—C6—Cl1 | 177.9 (2) |
| Cu1—O1—C3—C4 | −175.7 (2) | C5—C6—C7—C2 | 0.3 (5) |
| Cu1—O1—C3—C2 | 5.8 (4) | Cl1—C6—C7—C2 | −178.4 (2) |
| C7—C2—C3—O1 | 177.5 (3) | C3—C2—C7—C6 | 0.7 (5) |
| C1—C2—C3—O1 | 1.1 (5) | C1—C2—C7—C6 | 177.3 (3) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1 | 0.82 | 2.04 | 2.822 (3) | 160 |
| N1—H1···O2ii | 0.86 | 2.20 | 2.986 (4) | 153 |
| Symmetry codes: (ii) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1 | 0.82 | 2.04 | 2.822 (3) | 160 |
| N1—H1···O2i | 0.86 | 2.20 | 2.986 (4) | 153 |
| Symmetry codes: (i) x, y−1, z. |
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The syntheses of copper(II) complexes with Schiff base have been reported for their applications in the design and construction of new magnetic materials (Erxleben & Schumache, 2001; Stewart et al., 1961). Some of these complexes also inhibit the cellular proteasome activity (Adsule et al., 2006). As an extension of the work on structural characterization of mononuclear copper(II) complexes, the crystal structure of the title compound is reported.
Complex (I) is a mononuclear copper(II) compound. The central CuII atom is coordinated by two O atoms and two N atoms of the two Schiff base ligands to form a slightly distorted square-planar geometry, with angles subtended at the copper(II) atoms in the range 84.48 (12)°–172.02 (10)°. The Cu—O and Cu—N bond lengths are 1.915 (2) Å and 1.939 (2) Å, respectively, which are a little longer than the corresponding value of 1.842 (3) Å and 1.837 (3) Å observed in a similar Schiff base copper(II) complex (Li & Zhang, 2004).
Intermolecular O—H···O and N—H···O hydrogen bonds involving atoms O1 and N1 from the Schiff base and O2 from the methanol (Table 1) link the molecules to form chains along the b axis. From Fig. 2, it can be seen that benzene rings from neighbouring complexes are parallel but the distance between their centroids is 3.852 (2) Å, which is longer than the distance (3.4 Å) between neighbouring base pairs in DNA (Wei et al., 2004), indicating no π···π packing interactions.