Acta Cryst. (2008). E64, m828 [ doi:10.1107/S1600536808014748 ]
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2N,N')(pyridine-2-carbaldehyde oxime-2N,N')copper(II)In the title compound, [Cu(C6H5N2O)Cl(C6H6N2O)], the Cu atom is coordinated by one neutral and one deprotonated pyridine-2-carboxaldehyde oxime (pco) ligand, resulting in the formation of two five-membered CuN2C2 rings. Together with the additional coordinating chloride anion, the coordination polyhedron of copper is best described as a distorted square-pyramid, the distortion parameter being 0.288. The two organic ligands are linked by an intramolecular O-H
O hydrogen bond.
A methanolic solution (15 ml) containing pco (0.1 mmol, 0.012 g) was added to an methanolic solution (10 ml) containing CuCl2 × 2 H2O (0.1 mmol, 0.017 g). After stirring for 2 h, the solution was filtered. Dark green needle-like crystals suitable for single-crystal X-ray diffraction were obtained by evaporating the resulting filtrate in air for several days (yield 65.6% based on the ligand).
H atoms were placed geometrically and allowed to ride during refinement with C—H = 0.93–0.96 Å and O—H = 0.82 Å with Uiso(H) = 1.2 or 1.5Ueq(C or O).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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]](./im2064fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 50% probability level. |
| [Cu(C6H5N2O)Cl(C6H6N2O)] | F000 = 1384 |
| Mr = 342.24 | Dx = 1.730 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2343 reflections |
| a = 16.686 (2) Å | θ = 2.4–26.6º |
| b = 12.064 (2) Å | µ = 1.87 mm−1 |
| c = 13.805 (1) Å | T = 293 (2) K |
| β = 109.02 (1)º | Block, dark green |
| V = 2627.3 (5) Å3 | 0.22 × 0.18 × 0.15 mm |
| Z = 8 |
| Bruker SMART CCD area-detector diffractometer | 2318 independent reflections |
| Radiation source: fine-focus sealed tube | 1788 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| T = 293(2) K | θmax = 25.0º |
| φ and ω scans | θmin = 2.1º |
| Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008) | h = −14→19 |
| Tmin = 0.488, Tmax = 0.594 | k = −14→13 |
| 6487 measured reflections | l = −16→16 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.065P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 2318 reflections | Δρmax = 0.40 e Å−3 |
| 181 parameters | Δρmin = −0.39 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Cu(C6H5N2O)Cl(C6H6N2O)] | V = 2627.3 (5) Å3 |
| Mr = 342.24 | Z = 8 |
| Monoclinic, C2/c | Mo Kα |
| a = 16.686 (2) Å | µ = 1.87 mm−1 |
| b = 12.064 (2) Å | T = 293 (2) K |
| c = 13.805 (1) Å | 0.22 × 0.18 × 0.15 mm |
| β = 109.02 (1)º |
| Bruker SMART CCD area-detector diffractometer | 2318 independent reflections |
| Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008) | 1788 reflections with I > 2σ(I) |
| Tmin = 0.488, Tmax = 0.594 | Rint = 0.034 |
| 6487 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 181 parameters |
| wR(F2) = 0.110 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.40 e Å−3 |
| 2318 reflections | Δρmin = −0.39 e Å−3 |
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 | 0.45583 (2) | 0.75857 (3) | 0.08754 (3) | 0.03490 (18) | |
| Cl1 | 0.39133 (6) | 0.74459 (6) | −0.09737 (7) | 0.0452 (3) | |
| N2 | 0.39301 (17) | 0.8985 (2) | 0.1014 (2) | 0.0365 (6) | |
| N3 | 0.53622 (18) | 0.6345 (2) | 0.0978 (2) | 0.0432 (7) | |
| N4 | 0.39418 (17) | 0.6311 (2) | 0.1352 (2) | 0.0386 (7) | |
| O2 | 0.60997 (16) | 0.6484 (2) | 0.0801 (2) | 0.0594 (7) | |
| C1 | 0.3107 (2) | 0.9115 (3) | 0.0892 (3) | 0.0445 (9) | |
| H1A | 0.2761 | 0.8491 | 0.0764 | 0.053* | |
| N1 | 0.54953 (17) | 0.8713 (2) | 0.1156 (2) | 0.0431 (7) | |
| C11 | 0.4316 (2) | 0.5328 (3) | 0.1314 (3) | 0.0427 (9) | |
| C5 | 0.4419 (2) | 0.9892 (3) | 0.1166 (3) | 0.0433 (8) | |
| O1 | 0.63020 (15) | 0.8491 (3) | 0.1224 (2) | 0.0666 (8) | |
| H1B | 0.6346 | 0.7834 | 0.1100 | 0.100* | |
| C2 | 0.2750 (3) | 1.0126 (4) | 0.0946 (3) | 0.0585 (11) | |
| H2A | 0.2177 | 1.0187 | 0.0866 | 0.070* | |
| C9 | 0.3236 (3) | 0.4362 (4) | 0.1762 (3) | 0.0647 (12) | |
| H9A | 0.3002 | 0.3707 | 0.1903 | 0.078* | |
| C7 | 0.3232 (2) | 0.6295 (3) | 0.1599 (3) | 0.0457 (9) | |
| H7A | 0.2973 | 0.6968 | 0.1638 | 0.055* | |
| C12 | 0.5115 (2) | 0.5390 (3) | 0.1109 (3) | 0.0463 (9) | |
| H12A | 0.5426 | 0.4760 | 0.1076 | 0.056* | |
| C6 | 0.5299 (2) | 0.9703 (3) | 0.1257 (3) | 0.0483 (9) | |
| H6A | 0.5692 | 1.0276 | 0.1381 | 0.058* | |
| C10 | 0.3975 (3) | 0.4349 (3) | 0.1509 (3) | 0.0579 (11) | |
| H10A | 0.4239 | 0.3680 | 0.1471 | 0.069* | |
| C8 | 0.2865 (3) | 0.5352 (4) | 0.1798 (3) | 0.0593 (11) | |
| H8A | 0.2365 | 0.5388 | 0.1957 | 0.071* | |
| C4 | 0.4094 (3) | 1.0927 (3) | 0.1215 (3) | 0.0636 (12) | |
| H4A | 0.4440 | 1.1550 | 0.1313 | 0.076* | |
| C3 | 0.3253 (3) | 1.1034 (3) | 0.1118 (4) | 0.0718 (13) | |
| H3A | 0.3029 | 1.1729 | 0.1171 | 0.086* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0277 (3) | 0.0340 (3) | 0.0441 (3) | 0.00547 (15) | 0.0132 (2) | −0.00158 (17) |
| Cl1 | 0.0482 (6) | 0.0432 (5) | 0.0407 (5) | 0.0035 (4) | 0.0094 (4) | −0.0023 (4) |
| N2 | 0.0355 (16) | 0.0317 (15) | 0.0418 (16) | 0.0041 (12) | 0.0118 (13) | −0.0026 (12) |
| N3 | 0.0398 (17) | 0.0480 (19) | 0.0432 (17) | 0.0156 (14) | 0.0152 (14) | 0.0003 (14) |
| N4 | 0.0385 (16) | 0.0366 (16) | 0.0392 (16) | 0.0031 (12) | 0.0107 (13) | 0.0023 (12) |
| O2 | 0.0440 (16) | 0.0712 (19) | 0.0731 (19) | 0.0207 (14) | 0.0327 (14) | 0.0047 (15) |
| C1 | 0.040 (2) | 0.044 (2) | 0.049 (2) | 0.0096 (16) | 0.0142 (17) | 0.0009 (16) |
| N1 | 0.0286 (16) | 0.0516 (19) | 0.0505 (18) | −0.0040 (13) | 0.0147 (14) | −0.0005 (14) |
| C11 | 0.052 (2) | 0.0372 (19) | 0.032 (2) | 0.0057 (16) | 0.0044 (17) | −0.0001 (15) |
| C5 | 0.052 (2) | 0.038 (2) | 0.040 (2) | 0.0022 (16) | 0.0157 (18) | −0.0024 (16) |
| O1 | 0.0326 (15) | 0.077 (2) | 0.092 (2) | −0.0025 (13) | 0.0241 (15) | −0.0042 (17) |
| C2 | 0.051 (2) | 0.066 (3) | 0.059 (3) | 0.029 (2) | 0.019 (2) | 0.002 (2) |
| C9 | 0.069 (3) | 0.058 (3) | 0.058 (3) | −0.024 (2) | 0.009 (2) | 0.009 (2) |
| C7 | 0.041 (2) | 0.051 (2) | 0.047 (2) | −0.0006 (17) | 0.0166 (17) | 0.0022 (17) |
| C12 | 0.052 (2) | 0.044 (2) | 0.040 (2) | 0.0195 (18) | 0.0113 (18) | −0.0006 (17) |
| C6 | 0.045 (2) | 0.045 (2) | 0.056 (2) | −0.0115 (17) | 0.0177 (18) | −0.0050 (18) |
| C10 | 0.071 (3) | 0.036 (2) | 0.053 (2) | −0.0020 (19) | 0.002 (2) | 0.0001 (18) |
| C8 | 0.052 (3) | 0.067 (3) | 0.057 (3) | −0.014 (2) | 0.016 (2) | 0.006 (2) |
| C4 | 0.080 (3) | 0.031 (2) | 0.079 (3) | 0.0027 (19) | 0.025 (3) | −0.0044 (19) |
| C3 | 0.088 (4) | 0.044 (3) | 0.084 (3) | 0.033 (2) | 0.029 (3) | −0.004 (2) |
| Cu1—N3 | 1.984 (3) | C5—C4 | 1.371 (5) |
| Cu1—N1 | 2.012 (3) | C5—C6 | 1.451 (5) |
| Cu1—N2 | 2.029 (3) | O1—H1B | 0.8200 |
| Cu1—N4 | 2.072 (3) | C2—C3 | 1.352 (6) |
| Cu1—Cl1 | 2.4316 (10) | C2—H2A | 0.9300 |
| N2—C1 | 1.338 (4) | C9—C8 | 1.354 (6) |
| N2—C5 | 1.340 (4) | C9—C10 | 1.385 (6) |
| N3—C12 | 1.256 (5) | C9—H9A | 0.9300 |
| N3—O2 | 1.341 (3) | C7—C8 | 1.361 (5) |
| N4—C7 | 1.335 (4) | C7—H7A | 0.9300 |
| N4—C11 | 1.350 (4) | C12—H12A | 0.9300 |
| C1—C2 | 1.370 (5) | C6—H6A | 0.9300 |
| C1—H1A | 0.9300 | C10—H10A | 0.9300 |
| N1—C6 | 1.258 (4) | C8—H8A | 0.9300 |
| N1—O1 | 1.345 (3) | C4—C3 | 1.371 (6) |
| C11—C10 | 1.375 (5) | C4—H4A | 0.9300 |
| C11—C12 | 1.453 (5) | C3—H3A | 0.9300 |
| N3—Cu1—N1 | 91.79 (14) | C4—C5—C6 | 123.0 (4) |
| N3—Cu1—N2 | 168.29 (12) | N1—O1—H1B | 109.5 |
| N1—Cu1—N2 | 79.19 (11) | C3—C2—C1 | 118.4 (4) |
| N3—Cu1—N4 | 79.15 (12) | C3—C2—H2A | 120.8 |
| N1—Cu1—N4 | 151.07 (12) | C1—C2—H2A | 120.8 |
| N2—Cu1—N4 | 105.21 (11) | C8—C9—C10 | 118.3 (4) |
| N3—Cu1—Cl1 | 94.60 (9) | C8—C9—H9A | 120.9 |
| N1—Cu1—Cl1 | 107.40 (9) | C10—C9—H9A | 120.9 |
| N2—Cu1—Cl1 | 95.22 (8) | N4—C7—C8 | 124.0 (4) |
| N4—Cu1—Cl1 | 100.71 (8) | N4—C7—H7A | 118.0 |
| C1—N2—C5 | 118.1 (3) | C8—C7—H7A | 118.0 |
| C1—N2—Cu1 | 128.8 (2) | N3—C12—C11 | 116.1 (3) |
| C5—N2—Cu1 | 112.8 (2) | N3—C12—H12A | 121.9 |
| C12—N3—O2 | 120.3 (3) | C11—C12—H12A | 121.9 |
| C12—N3—Cu1 | 117.1 (2) | N1—C6—C5 | 115.7 (3) |
| O2—N3—Cu1 | 122.1 (2) | N1—C6—H6A | 122.2 |
| C7—N4—C11 | 117.2 (3) | C5—C6—H6A | 122.2 |
| C7—N4—Cu1 | 131.7 (2) | C11—C10—C9 | 119.9 (4) |
| C11—N4—Cu1 | 110.9 (2) | C11—C10—H10A | 120.0 |
| N2—C1—C2 | 122.9 (4) | C9—C10—H10A | 120.0 |
| N2—C1—H1A | 118.5 | C9—C8—C7 | 119.2 (4) |
| C2—C1—H1A | 118.5 | C9—C8—H8A | 120.4 |
| C6—N1—O1 | 118.2 (3) | C7—C8—H8A | 120.4 |
| C6—N1—Cu1 | 116.6 (2) | C5—C4—C3 | 119.3 (4) |
| O1—N1—Cu1 | 125.2 (2) | C5—C4—H4A | 120.4 |
| N4—C11—C10 | 121.4 (4) | C3—C4—H4A | 120.4 |
| N4—C11—C12 | 115.3 (3) | C2—C3—C4 | 119.8 (4) |
| C10—C11—C12 | 123.2 (3) | C2—C3—H3A | 120.1 |
| N2—C5—C4 | 121.4 (4) | C4—C3—H3A | 120.1 |
| N2—C5—C6 | 115.6 (3) |
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Pyridine-2-carbaldehyde oxime ligands usually bind to metals in a bidentate fashion, either chelating one metal center or bridging two metals. Their complexes find application in diverse areas such as functional supramolecular design, magnetic materials and catalysis (Korpi et al., 2005; Pearse et al., 1989; Afrati et al., 2005; Stamatatos et al., 2006). The title compound is a new copper complex from the reaction of CuCl2 with pyridine-2-carbaldehyde oxime (pco). The compound consists of two N,N-chelating ligands and one chloride anion. The two pco ligands are coordinated to copper to form two five-membered CuC2N2 rings. The copper atom adopts a distorted 4 + 1 square-pyramidal coordination mode with the distortion parameter being 0.288 (Addison et al., 1984) and the angles around copper ion ranging from 79.07 (1)° for N3—Cu1—N4 to 168.37 (1)° for N2—Cu1—N3. From the viewpoint of charge balance, it is presumed there exists one deprotonated and one protonated oxime ligand with a strong intramolecular hydrogen bond between the OH group and the negatively charged oxygen of the other ligand (O1···O2 = 2.488 Å) which would also give an explanation for the rather unusal cis-arrangement of the ligands (Scheme 1, Figure 1. ).