Acta Cryst. (2008). E64, m215 [ doi:10.1107/S1600536807056309 ]
The asymmetric unit of the title compound, [Ni(C7H4ClO2)2], contains one half-molecule. The NiII ion, lying on an inversion centre, is four-coordinated by O atoms of 5-chlorosalicylaldehydate ligands in a square-planar geometry.
For the preparation of the title compound, (I), 5-chlorosalicylaldehyde (15.7 mg, 0.1 mmol) and Ni(NO3)2.6(H2O) (29.0 mg, 0.1 mmol) were dissolved in methanol (10 ml). The mixture was stirred for 30 min at room temperature to give a clear brown solution. After allowing the resulting solution to stand in air for 11 d, brown block-shaped crystals of (I) were formed by slow evaporation of the solvent. The crystals were collected, washed with methanol and dried in a vacuum desiccator using anhydrous CaCl2 (yield; 54%). Elemental analysis; found C 45.42%, H2.16%; calc. for C14H8Cl2Ni O4: C 45.44, H 2.61%.
H atoms were positioned geometrically, with C—H = 0.93 Å, for aromatic H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXTL (Sheldrick, 1995).
![[Figure 1]](./hk2368fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| [Ni(C7H4ClO2)2] | F(000) = 372 |
| Mr = 369.81 | Dx = 1.739 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1788 reflections |
| a = 15.765 (3) Å | θ = 2.6–27.2° |
| b = 5.6921 (14) Å | µ = 1.76 mm−1 |
| c = 7.8869 (14) Å | T = 298 K |
| β = 93.896 (2)° | Block, brown |
| V = 706.1 (3) Å3 | 0.20 × 0.17 × 0.12 mm |
| Z = 2 |
| Bruker SMART CCD area-detector diffractometer | 1250 independent reflections |
| Radiation source: fine-focus sealed tube | 1056 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.019 |
| φ and ω scans | θmax = 25.0°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→15 |
| Tmin = 0.720, Tmax = 0.816 | k = −6→6 |
| 3455 measured reflections | l = −7→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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.093 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0455P)2 + 0.5565P] where P = (Fo2 + 2Fc2)/3 |
| 1250 reflections | (Δ/σ)max < 0.001 |
| 97 parameters | Δρmax = 0.55 e Å−3 |
| 0 restraints | Δρmin = −0.43 e Å−3 |
| [Ni(C7H4ClO2)2] | V = 706.1 (3) Å3 |
| Mr = 369.81 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 15.765 (3) Å | µ = 1.76 mm−1 |
| b = 5.6921 (14) Å | T = 298 K |
| c = 7.8869 (14) Å | 0.20 × 0.17 × 0.12 mm |
| β = 93.896 (2)° |
| Bruker SMART CCD area-detector diffractometer | 1250 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1056 reflections with I > 2σ(I) |
| Tmin = 0.720, Tmax = 0.816 | Rint = 0.019 |
| 3455 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.093 | Δρmax = 0.55 e Å−3 |
| S = 1.10 | Δρmin = −0.43 e Å−3 |
| 1250 reflections | Absolute structure: ? |
| 97 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 | ||
| Ni1 | 0.5000 | 0.0000 | 0.0000 | 0.0368 (2) | |
| Cl1 | 0.06478 (6) | 0.1508 (2) | 0.19360 (16) | 0.0813 (4) | |
| O1 | 0.45925 (17) | 0.2599 (5) | 0.1098 (3) | 0.0634 (7) | |
| O2 | 0.39686 (13) | −0.1524 (3) | −0.0165 (3) | 0.0434 (5) | |
| C1 | 0.3822 (2) | 0.3016 (5) | 0.1485 (4) | 0.0425 (7) | |
| H1 | 0.3714 | 0.4431 | 0.2018 | 0.051* | |
| C2 | 0.3126 (2) | 0.1431 (5) | 0.1141 (4) | 0.0398 (7) | |
| C3 | 0.32369 (19) | −0.0744 (6) | 0.0312 (4) | 0.0389 (7) | |
| C4 | 0.2507 (2) | −0.2141 (6) | −0.0042 (4) | 0.0465 (8) | |
| H4 | 0.2557 | −0.3559 | −0.0613 | 0.056* | |
| C5 | 0.1722 (2) | −0.1449 (6) | 0.0438 (5) | 0.0528 (9) | |
| H5 | 0.1250 | −0.2402 | 0.0197 | 0.063* | |
| C6 | 0.1633 (2) | 0.0666 (7) | 0.1281 (4) | 0.0497 (8) | |
| C7 | 0.2316 (2) | 0.2091 (6) | 0.1627 (4) | 0.0460 (8) | |
| H7 | 0.2248 | 0.3508 | 0.2189 | 0.055* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0449 (3) | 0.0309 (3) | 0.0342 (3) | −0.0012 (2) | 0.0001 (2) | −0.0031 (2) |
| Cl1 | 0.0502 (6) | 0.0935 (9) | 0.1021 (9) | 0.0018 (5) | 0.0186 (5) | −0.0168 (7) |
| O1 | 0.0725 (18) | 0.0565 (15) | 0.0609 (16) | −0.0023 (13) | 0.0037 (13) | −0.0085 (13) |
| O2 | 0.0464 (12) | 0.0340 (11) | 0.0499 (13) | −0.0011 (9) | 0.0035 (10) | −0.0066 (10) |
| C1 | 0.0490 (19) | 0.0354 (16) | 0.0433 (18) | 0.0045 (14) | 0.0057 (14) | −0.0065 (14) |
| C2 | 0.0469 (17) | 0.0353 (17) | 0.0369 (16) | 0.0006 (13) | 0.0008 (13) | 0.0006 (13) |
| C3 | 0.0461 (18) | 0.0350 (15) | 0.0351 (16) | −0.0009 (13) | −0.0004 (13) | 0.0037 (13) |
| C4 | 0.054 (2) | 0.0388 (17) | 0.0462 (19) | −0.0042 (14) | 0.0003 (15) | −0.0023 (14) |
| C5 | 0.0481 (19) | 0.053 (2) | 0.056 (2) | −0.0091 (16) | 0.0002 (16) | 0.0002 (17) |
| C6 | 0.0443 (18) | 0.055 (2) | 0.050 (2) | 0.0024 (15) | 0.0048 (15) | 0.0025 (16) |
| C7 | 0.0518 (19) | 0.0422 (18) | 0.0441 (19) | 0.0056 (15) | 0.0046 (15) | −0.0015 (14) |
| Ni1—O2i | 1.840 (2) | C2—C7 | 1.408 (4) |
| Ni1—O2 | 1.840 (2) | C2—C3 | 1.417 (4) |
| Ni1—O1 | 1.851 (3) | C3—C4 | 1.411 (4) |
| Ni1—O1i | 1.851 (3) | C4—C5 | 1.376 (5) |
| Cl1—C6 | 1.738 (3) | C4—H4 | 0.9300 |
| O1—C1 | 1.294 (4) | C5—C6 | 1.387 (5) |
| O2—C3 | 1.315 (4) | C5—H5 | 0.9300 |
| C1—C2 | 1.433 (4) | C6—C7 | 1.361 (5) |
| C1—H1 | 0.9300 | C7—H7 | 0.9300 |
| O2i—Ni1—O2 | 180 | O2—C3—C2 | 124.5 (3) |
| O2i—Ni1—O1 | 85.60 (10) | C4—C3—C2 | 117.3 (3) |
| O2—Ni1—O1 | 94.40 (10) | C5—C4—C3 | 121.4 (3) |
| O2i—Ni1—O1i | 94.40 (10) | C5—C4—H4 | 119.3 |
| O2—Ni1—O1i | 85.60 (10) | C3—C4—H4 | 119.3 |
| O1—Ni1—O1i | 180 | C4—C5—C6 | 120.2 (3) |
| C1—O1—Ni1 | 128.2 (2) | C4—C5—H5 | 119.9 |
| C3—O2—Ni1 | 127.52 (19) | C6—C5—H5 | 119.9 |
| O1—C1—C2 | 124.0 (3) | C7—C6—C5 | 120.6 (3) |
| O1—C1—H1 | 118.0 | C7—C6—Cl1 | 119.1 (3) |
| C2—C1—H1 | 118.0 | C5—C6—Cl1 | 120.2 (3) |
| C7—C2—C3 | 120.1 (3) | C6—C7—C2 | 120.4 (3) |
| C7—C2—C1 | 118.5 (3) | C6—C7—H7 | 119.8 |
| C3—C2—C1 | 121.3 (3) | C2—C7—H7 | 119.8 |
| O2—C3—C4 | 118.2 (3) | ||
| O2i—Ni1—O1—C1 | 177.8 (3) | C7—C2—C3—C4 | 2.0 (4) |
| O2—Ni1—O1—C1 | −2.2 (3) | C1—C2—C3—C4 | −177.2 (3) |
| O1—Ni1—O2—C3 | 3.1 (3) | O2—C3—C4—C5 | 179.2 (3) |
| O1i—Ni1—O2—C3 | −176.9 (3) | C2—C3—C4—C5 | −1.7 (5) |
| Ni1—O1—C1—C2 | 1.5 (5) | C3—C4—C5—C6 | 0.4 (5) |
| O1—C1—C2—C7 | 179.9 (3) | C4—C5—C6—C7 | 0.6 (5) |
| O1—C1—C2—C3 | −0.8 (5) | C4—C5—C6—Cl1 | −178.4 (3) |
| Ni1—O2—C3—C4 | 175.5 (2) | C5—C6—C7—C2 | −0.3 (5) |
| Ni1—O2—C3—C2 | −3.5 (4) | Cl1—C6—C7—C2 | 178.7 (2) |
| C7—C2—C3—O2 | −178.9 (3) | C3—C2—C7—C6 | −1.1 (5) |
| C1—C2—C3—O2 | 1.9 (5) | C1—C2—C7—C6 | 178.1 (3) |
| Symmetry code: (i) −x+1, −y, −z. |
| Ni1—O2 | 1.840 (2) | Ni1—O1 | 1.851 (3) |
| O2i—Ni1—O2 | 180 | O2—Ni1—O1 | 94.40 (10) |
| O2i—Ni1—O1 | 85.60 (10) | O1—Ni1—O1i | 180 |
| Symmetry code: (i) −x+1, −y, −z. |
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
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Sheldrick, G. M. (1995). SHELXTL (Version 5.0). Siemens Analytical Instruments Inc, Madison, Wisconsin, USA.
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Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Veauthier, J. M., Cho, W.-S., Lynch, V. M. & Sessler, J. L. (2004). Inorg. Chem. 43, 1220–1228.
The design of multidentate ligands and their metallosupramolecular chemistry are of great interest in the last few years (Gavrilova & Bosnich, 2004; Boudalis et al., 2004; Veauthier et al., 2004). As an extension of our ongoing studies on the structural characterization of Schiff base compounds, we report herein the crystal structure of the title compound, (I).
The asymmetric unit of (I) contains one-half molecule (Fig. 1), in which the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). It is a mononuclear NiII complex being structurally similar to the Co(II) and Zn(II) complexes derived from other Schiff base ligands (Erxleben et al., 2001). The NiII ion is four-coordinated by symmetry-related O atoms of 5-chlorosalicylaldehydato ligands.