Acta Cryst. (2009). E65, m1380 [ doi:10.1107/S1600536809041816 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
N)copper(II) chlorideIn the molecular structure of the title compound, [CuCl(C6H5NO)4]Cl, the CuII atom is coordinated by four N atoms of four pyridine-4-carboxaldehyde ligands and one chloride anion in a slightly distorted square-pyramidal coordination geometry. There is also a non-coordinating Cl- anion in the crystal structure. The CuII atom and both Cl atoms are situated on fourfold rotation axes. A weak C-H
Cl interaction is also present.
For the preparation of the title compound, a solution of CuCl2 × 2 H2O (0.08524 g, 0.5 mmol) in H2O(5 ml) was slowly added over a period of 2 h to a solution of L-Cysteic acid (0.094 g, 0.5 mmol), KOH (0.056 g, 1 mmol), pyridine-4-carboxaldehyde (0.06 ml, 0.6 mmol) and NaBH4 (0.03028 g, 0.8 mmol) in methanol (20 ml) resulting in a blue solution that was stirred for another 4 h at 298 K. Then, the solution was left to evaporate slowly at room temperature. After ten days, blue block crystals of the title compoound were obtained with a yield of 70%.
H atom bonded to C atom were positioned geometrically with the C—H distance of 0.9303 Å, and treated as riding atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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]](./im2137fig1thm.gif)
| Fig. 1. Ellipsoid plot (30% probability) of the title compound showing the numbering scheme. Dashed lines indicate hydrogen bonds. Symmetry code: 1# -x + 1/2, y + 1/2, z. |
![[Figure 2]](./im2137fig2thm.gif)
| Fig. 2. 2-D network, as viewed down the c axis. Dashed lines indicate hydrogen bonds. |
| [CuCl(C6H5NO)4]Cl | Dx = 1.490 Mg m−3 |
| Mr = 562.88 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, P4/n | Cell parameters from 1162 reflections |
| Hall symbol: -P 4a | θ = 2.6–25.1° |
| a = 10.5035 (3) Å | µ = 1.12 mm−1 |
| c = 11.3751 (6) Å | T = 296 K |
| V = 1254.94 (8) Å3 | Block, blue |
| Z = 2 | 0.38 × 0.21 × 0.18 mm |
| F(000) = 574 |
| Bruker SMART CCD area-detector diffractometer | 1126 independent reflections |
| Radiation source: fine-focus sealed tube | 1083 reflections with I > 2σ(I) |
| graphite | Rint = 0.017 |
| phi and ω scans | θmax = 25.1°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
| Tmin = 0.675, Tmax = 0.825 | k = −12→12 |
| 9150 measured reflections | l = −12→13 |
| 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.114 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.091P)2 + 0.4771P] where P = (Fo2 + 2Fc2)/3 |
| 1126 reflections | (Δ/σ)max < 0.001 |
| 82 parameters | Δρmax = 0.56 e Å−3 |
| 13 restraints | Δρmin = −0.48 e Å−3 |
| [CuCl(C6H5NO)4]Cl | Z = 2 |
| Mr = 562.88 | Mo Kα radiation |
| Tetragonal, P4/n | µ = 1.12 mm−1 |
| a = 10.5035 (3) Å | T = 296 K |
| c = 11.3751 (6) Å | 0.38 × 0.21 × 0.18 mm |
| V = 1254.94 (8) Å3 |
| Bruker SMART CCD area-detector diffractometer | 1126 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1083 reflections with I > 2σ(I) |
| Tmin = 0.675, Tmax = 0.825 | Rint = 0.017 |
| 9150 measured reflections | θmax = 25.1° |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.114 | Δρmax = 0.56 e Å−3 |
| S = 1.03 | Δρmin = −0.48 e Å−3 |
| 1126 reflections | Absolute structure: ? |
| 82 parameters | Flack parameter: ? |
| 13 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 | 0.7500 | 0.7500 | 0.81702 (4) | 0.0289 (3) | |
| Cl1 | 0.7500 | 0.7500 | 1.03833 (9) | 0.0373 (3) | |
| C1 | 0.8616 (2) | 0.5010 (2) | 0.8824 (2) | 0.0376 (5) | |
| H1 | 0.8631 | 0.5372 | 0.9570 | 0.045* | |
| C2 | 0.9093 (3) | 0.3791 (2) | 0.8675 (2) | 0.0418 (6) | |
| H2 | 0.9404 | 0.3342 | 0.9319 | 0.050* | |
| C3 | 0.9109 (2) | 0.3241 (2) | 0.7569 (2) | 0.0342 (5) | |
| C4 | 0.8612 (3) | 0.3938 (2) | 0.6653 (2) | 0.0411 (6) | |
| H4 | 0.8601 | 0.3603 | 0.5896 | 0.049* | |
| C5 | 0.8132 (3) | 0.5140 (3) | 0.6867 (2) | 0.0422 (6) | |
| H5 | 0.7790 | 0.5593 | 0.6240 | 0.051* | |
| C6 | 0.9662 (3) | 0.1930 (2) | 0.7405 (3) | 0.0466 (6) | |
| H6 | 0.9939 | 0.1428 | 0.8027 | 0.056* | |
| N1 | 0.81319 (18) | 0.56845 (17) | 0.79272 (17) | 0.0320 (4) | |
| O1 | 0.9721 (2) | 0.1535 (2) | 0.6224 (2) | 0.0598 (6) | |
| Cl2 | 0.7500 | 0.7500 | 0.44844 (12) | 0.0562 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0261 (3) | 0.0261 (3) | 0.0344 (4) | 0.000 | 0.000 | 0.000 |
| Cl1 | 0.0410 (4) | 0.0410 (4) | 0.0299 (5) | 0.000 | 0.000 | 0.000 |
| C1 | 0.0418 (13) | 0.0357 (12) | 0.0354 (11) | 0.0033 (10) | −0.0029 (10) | −0.0013 (9) |
| C2 | 0.0487 (15) | 0.0378 (13) | 0.0390 (13) | 0.0075 (11) | −0.0068 (10) | 0.0066 (10) |
| C3 | 0.0288 (11) | 0.0306 (11) | 0.0434 (12) | −0.0011 (8) | 0.0001 (9) | 0.0016 (9) |
| C4 | 0.0485 (15) | 0.0372 (13) | 0.0377 (11) | 0.0062 (11) | −0.0016 (10) | −0.0031 (10) |
| C5 | 0.0527 (16) | 0.0355 (13) | 0.0385 (13) | 0.0079 (11) | −0.0074 (10) | 0.0039 (9) |
| C6 | 0.0514 (15) | 0.0348 (13) | 0.0536 (15) | 0.0105 (11) | −0.0040 (12) | −0.0009 (11) |
| N1 | 0.0314 (10) | 0.0282 (9) | 0.0364 (9) | 0.0000 (7) | −0.0003 (8) | 0.0025 (8) |
| O1 | 0.0654 (14) | 0.0500 (12) | 0.0642 (13) | 0.0141 (10) | −0.0063 (10) | −0.0171 (10) |
| Cl2 | 0.0619 (6) | 0.0619 (6) | 0.0448 (7) | 0.000 | 0.000 | 0.000 |
| Cu1—N1i | 2.0380 (19) | C2—H2 | 0.9300 |
| Cu1—N1 | 2.0380 (19) | C3—C4 | 1.377 (3) |
| Cu1—N1ii | 2.0380 (19) | C3—C6 | 1.506 (3) |
| Cu1—N1iii | 2.0380 (19) | C4—C5 | 1.381 (4) |
| Cu1—Cl1 | 2.5175 (11) | C4—H4 | 0.9300 |
| C1—N1 | 1.342 (3) | C5—N1 | 1.335 (3) |
| C1—C2 | 1.385 (4) | C5—H5 | 0.9300 |
| C1—H1 | 0.9300 | C6—O1 | 1.407 (4) |
| C2—C3 | 1.384 (4) | C6—H6 | 0.9300 |
| N1i—Cu1—N1 | 88.946 (16) | C4—C3—C2 | 117.5 (2) |
| N1i—Cu1—N1ii | 164.41 (11) | C4—C3—C6 | 122.6 (2) |
| N1—Cu1—N1ii | 88.946 (16) | C2—C3—C6 | 119.9 (2) |
| N1i—Cu1—N1iii | 88.946 (15) | C3—C4—C5 | 119.4 (2) |
| N1—Cu1—N1iii | 164.41 (11) | C3—C4—H4 | 120.3 |
| N1ii—Cu1—N1iii | 88.946 (16) | C5—C4—H4 | 120.3 |
| N1i—Cu1—Cl1 | 97.79 (6) | N1—C5—C4 | 123.4 (2) |
| N1—Cu1—Cl1 | 97.79 (6) | N1—C5—H5 | 118.3 |
| N1ii—Cu1—Cl1 | 97.79 (6) | C4—C5—H5 | 118.3 |
| N1iii—Cu1—Cl1 | 97.79 (6) | O1—C6—C3 | 113.9 (2) |
| N1—C1—C2 | 122.2 (2) | O1—C6—H6 | 123.0 |
| N1—C1—H1 | 118.9 | C3—C6—H6 | 123.0 |
| C2—C1—H1 | 118.9 | C5—N1—C1 | 117.4 (2) |
| C3—C2—C1 | 120.1 (2) | C5—N1—Cu1 | 121.56 (16) |
| C3—C2—H2 | 120.0 | C1—N1—Cu1 | 120.97 (16) |
| C1—C2—H2 | 120.0 |
| Symmetry codes: (i) y, −x+3/2, z; (ii) −y+3/2, x, z; (iii) −x+3/2, −y+3/2, z. |
This work was funded by the Guangxi Science Foundation of the Guangxi Zhuang Autonomous Region of the People's Republic of China (grant No. 0731053).
Briand, G. G., Smith, A. D., Schatte, G., Rossini, A. J. & Schurko, R. W. (2007). Inorg. Chem. 46, 8625–8637.
Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Choi, Y.-Y. & Wong, W.-T. (1999). J. Organomet. Chem. 573, 189–201.
Rivera, A. V. & Sheldrick, G. M. (1977). Acta Cryst. B33, 154–155.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sie, W.-S., Lee, G.-H., Tsai, K. Y.-D., Chang, I.-J. & Shiu, K. B. (2008). J. Mol. Struct. 890, 198–202.
Only one structurally characterized coordination compound with pyridine-4- carboxaldehyde acting as the ligand has been reported up to now. In that article, pyridine-4-carboxaldehyde and CoBr2 form [CoBr2(C5H4N-CHO)4] (Rivera et al. 1977). This compound is highly related to the title compound. In addition, three crystal structures with pyridine-4-carboxaldehyde acting as independent components were reported (Choi et al. 1999; Briand et al. 2007; Sie et al. 2008).
In the cation of the title compound [CuCl(OCHC5H4N)4]Cl, the CuII centre is coordinated to four N atoms from four pyridine-4-carboxaldehyde ligands and one chloro ligand. Cu exhibits a slightly distorted square-pyramidal coordination geometry. Another non-coordinating chloride anion is observed in the crystal structure. The [CuCl(C5H4N-CHO)4]+ ion has a perfect C4 symmetry with the direction of the C4 axis being collinear with the Cu1—Cl1 direction. Cu1, Cl1 and Cl2 are all situated on the same crystallographic 4-fold rotoinversion axis. In the cation therefore all Cu—N bond lengths and angles are equivalent.
Several donor CH functions and the chloride acceptor groups participate in the observed hydrogen bonding pattern forming a two-dimensional network in the ab plane (Fig. 2)