Acta Cryst. (2007). E63, m3065 [ doi:10.1107/S1600536807057881 ]
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N)zinc(II)In the title compound, [ZnCl2(C6H5NO)2], the ZnII atom lies on a mirror plane, and is coordinated by two N atoms from two pyridine-3-carbaldehyde ligands and two Cl ligands in a distorted tetrahedral geometry. The packing is governed by intermolecular C-H
O hydrogen-bonding interactions.
The title compound was prepared by the addition of ZnCl2 (1.0 mmol) to an ethanol solution (20 ml) of pyridine-3-carbalehyde (nicotinaldehyde, 2.0 mmol). The mixture was stirred at 80°C for 2 h and filtered. Colorless prismatic single crystals were obtained from the filtrate upon slow evaporation of the solvent over several days.
All H atoms on aromatic rings were placed in calculated positions (C—H = 0.93 Å) and were refined using a riding model with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).
![[Figure 1]](./zl2084fig1thm.gif)
| Fig. 1. The molecular structure of the title complex, showing 50% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the symmetry operator (x, 1.5 − y, z). |
![[Figure 2]](./zl2084fig2thm.gif)
| Fig. 2. Packing diagram of the title complex, viewed along the a axis. Dashed lines indicate the C—H···O hydrogen bonds. |
| [ZnCl2(C6H5NO)2] | F000 = 704 |
| Mr = 350.49 | Dx = 1.683 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 1650 reflections |
| a = 5.8445 (1) Å | θ = 1.4–28.0º |
| b = 19.2032 (3) Å | µ = 2.16 mm−1 |
| c = 12.3216 (2) Å | T = 296 (2) K |
| V = 1382.89 (4) Å3 | Prismatic, colourless |
| Z = 4 | 0.20 × 0.18 × 0.18 mm |
| Bruker APEXII area-detector diffractometer | 1639 independent reflections |
| Radiation source: fine-focus sealed tube | 1412 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.027 |
| T = 296(2) K | θmax = 27.5º |
| φ and ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
| Tmin = 0.659, Tmax = 0.682 | k = −24→23 |
| 11915 measured reflections | l = −14→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)] = 0.022 | H-atom parameters constrained |
| wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0316P)2 + 0.3618P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 1639 reflections | Δρmax = 0.24 e Å−3 |
| 91 parameters | Δρmin = −0.26 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [ZnCl2(C6H5NO)2] | V = 1382.89 (4) Å3 |
| Mr = 350.49 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα |
| a = 5.8445 (1) Å | µ = 2.16 mm−1 |
| b = 19.2032 (3) Å | T = 296 (2) K |
| c = 12.3216 (2) Å | 0.20 × 0.18 × 0.18 mm |
| Bruker APEXII area-detector diffractometer | 1639 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1412 reflections with I > 2σ(I) |
| Tmin = 0.659, Tmax = 0.682 | Rint = 0.027 |
| 11915 measured reflections |
| R[F2 > 2σ(F2)] = 0.022 | 91 parameters |
| wR(F2) = 0.061 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.24 e Å−3 |
| 1639 reflections | Δρmin = −0.26 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 | ||
| C1 | 0.4874 (3) | 0.65200 (8) | 0.05903 (13) | 0.0386 (4) | |
| H1 | 0.4698 | 0.6765 | 0.1236 | 0.046* | |
| C2 | 0.6525 (3) | 0.60094 (9) | 0.05413 (15) | 0.0420 (4) | |
| C3 | 0.6773 (3) | 0.56404 (9) | −0.04233 (17) | 0.0515 (5) | |
| H3 | 0.7865 | 0.5290 | −0.0483 | 0.062* | |
| C4 | 0.5380 (4) | 0.58012 (9) | −0.12864 (15) | 0.0516 (5) | |
| H4 | 0.5512 | 0.5560 | −0.1938 | 0.062* | |
| C5 | 0.3783 (3) | 0.63254 (9) | −0.11717 (14) | 0.0450 (4) | |
| H5 | 0.2860 | 0.6436 | −0.1762 | 0.054* | |
| C6 | 0.7926 (3) | 0.58667 (10) | 0.15072 (16) | 0.0542 (5) | |
| H6 | 0.7659 | 0.6133 | 0.2125 | 0.065* | |
| Cl1 | −0.12237 (11) | 0.7500 | −0.14568 (5) | 0.05127 (17) | |
| Cl2 | 0.00885 (11) | 0.7500 | 0.15928 (5) | 0.05020 (17) | |
| N1 | 0.3506 (2) | 0.66815 (7) | −0.02492 (11) | 0.0368 (3) | |
| O1 | 0.9395 (3) | 0.54290 (8) | 0.15522 (14) | 0.0800 (5) | |
| Zn1 | 0.12503 (4) | 0.7500 | −0.01246 (2) | 0.03558 (10) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0421 (9) | 0.0379 (9) | 0.0360 (8) | 0.0006 (7) | −0.0002 (7) | −0.0014 (6) |
| C2 | 0.0414 (9) | 0.0367 (8) | 0.0479 (9) | 0.0022 (7) | 0.0022 (7) | 0.0041 (7) |
| C3 | 0.0547 (11) | 0.0388 (9) | 0.0610 (11) | 0.0089 (8) | 0.0137 (9) | −0.0008 (8) |
| C4 | 0.0683 (12) | 0.0435 (10) | 0.0429 (10) | 0.0012 (9) | 0.0087 (9) | −0.0087 (8) |
| C5 | 0.0541 (11) | 0.0441 (9) | 0.0369 (8) | −0.0041 (8) | −0.0010 (7) | −0.0015 (7) |
| C6 | 0.0513 (11) | 0.0511 (11) | 0.0601 (11) | 0.0052 (9) | −0.0048 (9) | 0.0071 (9) |
| Cl1 | 0.0436 (4) | 0.0672 (4) | 0.0430 (3) | 0.000 | −0.0112 (3) | 0.000 |
| Cl2 | 0.0504 (4) | 0.0647 (4) | 0.0355 (3) | 0.000 | 0.0057 (3) | 0.000 |
| N1 | 0.0385 (7) | 0.0361 (7) | 0.0359 (7) | 0.0005 (6) | 0.0002 (5) | −0.0009 (5) |
| O1 | 0.0728 (10) | 0.0789 (11) | 0.0884 (12) | 0.0346 (9) | −0.0138 (9) | 0.0078 (9) |
| Zn1 | 0.03358 (17) | 0.03874 (16) | 0.03444 (15) | 0.000 | −0.00213 (10) | 0.000 |
| C1—N1 | 1.344 (2) | C5—N1 | 1.336 (2) |
| C1—C2 | 1.377 (2) | C5—H5 | 0.9300 |
| C1—H1 | 0.9300 | C6—O1 | 1.203 (2) |
| C2—C3 | 1.391 (3) | C6—H6 | 0.9300 |
| C2—C6 | 1.471 (3) | Cl1—Zn1 | 2.1876 (7) |
| C3—C4 | 1.374 (3) | Cl2—Zn1 | 2.2223 (6) |
| C3—H3 | 0.9300 | N1—Zn1 | 2.0571 (14) |
| C4—C5 | 1.380 (3) | Zn1—N1i | 2.0571 (14) |
| C4—H4 | 0.9300 | ||
| N1—C1—C2 | 123.20 (15) | C4—C5—H5 | 118.6 |
| N1—C1—H1 | 118.4 | O1—C6—C2 | 124.41 (19) |
| C2—C1—H1 | 118.4 | O1—C6—H6 | 117.8 |
| C1—C2—C3 | 118.24 (17) | C2—C6—H6 | 117.8 |
| C1—C2—C6 | 119.17 (17) | C5—N1—C1 | 117.67 (15) |
| C3—C2—C6 | 122.58 (17) | C5—N1—Zn1 | 122.16 (12) |
| C4—C3—C2 | 119.00 (17) | C1—N1—Zn1 | 120.02 (11) |
| C4—C3—H3 | 120.5 | N1i—Zn1—N1 | 99.65 (8) |
| C2—C3—H3 | 120.5 | N1i—Zn1—Cl1 | 111.56 (4) |
| C3—C4—C5 | 119.03 (17) | N1—Zn1—Cl1 | 111.56 (4) |
| C3—C4—H4 | 120.5 | N1i—Zn1—Cl2 | 105.48 (4) |
| C5—C4—H4 | 120.5 | N1—Zn1—Cl2 | 105.48 (4) |
| N1—C5—C4 | 122.85 (17) | Cl1—Zn1—Cl2 | 120.83 (3) |
| N1—C5—H5 | 118.6 |
| Symmetry codes: (i) x, −y+3/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···O1ii | 0.93 | 2.49 | 3.342 (2) | 152 |
| C4—H4···O1iii | 0.93 | 2.66 | 3.562 (2) | 164 |
| Symmetry codes: (ii) −x+2, −y+1, −z; (iii) −x+3/2, −y+1, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···O1i | 0.93 | 2.49 | 3.342 (2) | 152 |
| C4—H4···O1ii | 0.93 | 2.66 | 3.562 (2) | 164 |
| Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, −y+1, z−1/2. |
The authors acknowledge South China Normal University for supporting this work.
Bruker (2004). APEX2, SMART and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
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Lynton, H. & Sears, M. C. (1971). Can. J. Chem. 49, 3418–3424.
Qin, J., Su, N., Dai, C., Yang, C., Liu, D., Day, M. W., Wu, B. & Chen, C. (1999). Polyhedron, 18, 3461–3464.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
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Coordination compounds of the type ZnL2Cl2 (L = 2-NH2py, 4-CNpy, 4-CH3py, 4-CH3COpy,3-NH2COpy, etc (py = pyridine)) have been previously prepared and studied by several groups (Qin et al., 1999; Steffen & Palenik, 1977; Lynton & Sears, 1971; Ide et al., 2002). In this paper, we report the crystal structure of the new mononuclear zinc complex Zn(3-CHOpy)2Cl2 (where 3-CHOpy is 3-pyridinecarboxaldehyde or nicotinaldehyde).
As illustrated in Fig. 1, the ZnII centre lies on a symmetry plane, defined by the zinc atom and the two chlorine atoms. The zinc center is coordinated to two N atoms from two 3-pyridinecarboxaldehyde ligands and two Cl atoms, and displays a distorted tetrahedral geometry. In the packing, C—H···O hydrogen bonding interactions (Table 1) stabilize the structural components (Fig. 2).