Acta Cryst. (2009). E65, m1275 [ doi:10.1107/S1600536809039233 ]
The title compound, [Ni(C8H8NO2)2], is a centrosymmetric mononuclear nickel(II) complex. The NiII ion, lying on an inversion centre, is four-coordinated in a square-planar geometry by two phenolate O and two imine N atoms from two symmetry-related 2-iminomethyl-5-methoxyphenolate ligands. In the crystal, molecules are linked into corrugated layers parallel to (100) by N-H
O hydrogen bonds.
4-Methoxy-2-hydroxybenzaldehyde (0.2 mmol, 30.5 mg) and nickel(II) nitrate hexahydrate (0.1 mmol, 29.1 mg) were mixed in a methanol solution (20 ml) which contains small quantity of ammonia. The mixture was stirred at room temperature for 30 min to give a red solution. The solution was allowed to stand in air for 8 d, yielding red block-shaped crystals of the title complex. The absorption band indicative of the C═N double bond formation in the IR spectrum of the complex is at 1617 cm-1.
Atom H1 was located in a difference Fourier map and refined isotropically, with N-H distance restrained to 0.90 (1) Å and Uiso set at 0.08 Å2. Other H atoms were constrained to ideal geometries, with C-H = 0.93–0.96 Å and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C8).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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]](./ci2923fig1thm.gif)
| Fig. 1. The molecular structure of the title complex. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms are at the symmetry position (2-x, -y, 1-z). |
![[Figure 2]](./ci2923fig2thm.gif)
| Fig. 2. Packing diagram, viewed along the a axis. Hydrogen bonds are shown as dashed lines. |
| [Ni(C8H8NO2)2] | F(000) = 744 |
| Mr = 359.02 | Dx = 1.614 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1894 reflections |
| a = 7.5704 (16) Å | θ = 2.3–26.2° |
| b = 11.331 (2) Å | µ = 1.34 mm−1 |
| c = 17.227 (4) Å | T = 298 K |
| V = 1477.7 (5) Å3 | Block, red |
| Z = 4 | 0.18 × 0.17 × 0.17 mm |
| Bruker SMART CCD area-detector diffractometer | 1620 independent reflections |
| Radiation source: fine-focus sealed tube | 1122 reflections with I > 2σ(I) |
| graphite | Rint = 0.028 |
| ω scans | θmax = 27.0°, θmin = 2.4° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→6 |
| Tmin = 0.795, Tmax = 0.805 | k = −11→14 |
| 7939 measured reflections | l = −21→22 |
| 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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.384P] where P = (Fo2 + 2Fc2)/3 |
| 1620 reflections | (Δ/σ)max = 0.001 |
| 110 parameters | Δρmax = 0.28 e Å−3 |
| 1 restraint | Δρmin = −0.29 e Å−3 |
| [Ni(C8H8NO2)2] | V = 1477.7 (5) Å3 |
| Mr = 359.02 | Z = 4 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 7.5704 (16) Å | µ = 1.34 mm−1 |
| b = 11.331 (2) Å | T = 298 K |
| c = 17.227 (4) Å | 0.18 × 0.17 × 0.17 mm |
| Bruker SMART CCD area-detector diffractometer | 1620 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1122 reflections with I > 2σ(I) |
| Tmin = 0.795, Tmax = 0.805 | Rint = 0.028 |
| 7939 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.083 | Δρmax = 0.28 e Å−3 |
| S = 1.01 | Δρmin = −0.29 e Å−3 |
| 1620 reflections | Absolute structure: ? |
| 110 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 1.0000 | 0.0000 | 0.5000 | 0.03483 (14) | |
| O1 | 0.98642 (18) | 0.00398 (11) | 0.39332 (9) | 0.0407 (4) | |
| O2 | 0.8757 (2) | 0.14990 (13) | 0.13928 (8) | 0.0486 (4) | |
| N1 | 0.9039 (3) | 0.14925 (16) | 0.51213 (9) | 0.0422 (4) | |
| C1 | 0.8581 (3) | 0.19740 (17) | 0.37798 (11) | 0.0366 (5) | |
| C2 | 0.9275 (3) | 0.08998 (17) | 0.34895 (11) | 0.0352 (4) | |
| C3 | 0.9336 (3) | 0.07278 (17) | 0.26800 (11) | 0.0369 (5) | |
| H3 | 0.9783 | 0.0026 | 0.2480 | 0.044* | |
| C4 | 0.8738 (3) | 0.15895 (18) | 0.21830 (11) | 0.0380 (5) | |
| C5 | 0.8038 (3) | 0.26481 (18) | 0.24643 (12) | 0.0457 (5) | |
| H5 | 0.7634 | 0.3224 | 0.2123 | 0.055* | |
| C6 | 0.7956 (3) | 0.28230 (19) | 0.32452 (12) | 0.0426 (5) | |
| H6 | 0.7473 | 0.3522 | 0.3433 | 0.051* | |
| C7 | 0.8489 (3) | 0.22017 (18) | 0.45884 (12) | 0.0423 (5) | |
| H7 | 0.7997 | 0.2915 | 0.4746 | 0.051* | |
| C8 | 0.9403 (4) | 0.0435 (2) | 0.10637 (13) | 0.0547 (6) | |
| H8A | 1.0625 | 0.0338 | 0.1198 | 0.082* | |
| H8B | 0.9286 | 0.0467 | 0.0509 | 0.082* | |
| H8C | 0.8736 | −0.0220 | 0.1261 | 0.082* | |
| H1 | 0.897 (3) | 0.176 (2) | 0.5612 (8) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0469 (2) | 0.0262 (2) | 0.0314 (2) | 0.00123 (15) | −0.00135 (15) | −0.00138 (14) |
| O1 | 0.0622 (10) | 0.0268 (8) | 0.0330 (7) | 0.0072 (6) | −0.0022 (6) | 0.0002 (5) |
| O2 | 0.0658 (10) | 0.0432 (9) | 0.0367 (8) | 0.0046 (7) | −0.0027 (7) | 0.0072 (7) |
| N1 | 0.0578 (12) | 0.0320 (10) | 0.0367 (10) | 0.0037 (9) | −0.0006 (8) | −0.0044 (7) |
| C1 | 0.0413 (11) | 0.0290 (10) | 0.0395 (11) | −0.0004 (8) | −0.0032 (8) | −0.0019 (9) |
| C2 | 0.0384 (11) | 0.0289 (11) | 0.0382 (11) | −0.0038 (9) | −0.0029 (8) | 0.0015 (8) |
| C3 | 0.0442 (11) | 0.0284 (10) | 0.0381 (11) | 0.0001 (9) | 0.0005 (9) | −0.0001 (8) |
| C4 | 0.0402 (12) | 0.0361 (11) | 0.0378 (11) | −0.0045 (9) | −0.0036 (8) | 0.0045 (9) |
| C5 | 0.0532 (12) | 0.0351 (12) | 0.0488 (13) | 0.0023 (10) | −0.0072 (10) | 0.0107 (10) |
| C6 | 0.0499 (13) | 0.0279 (11) | 0.0500 (13) | 0.0058 (9) | −0.0032 (10) | 0.0007 (10) |
| C7 | 0.0516 (14) | 0.0281 (11) | 0.0472 (13) | 0.0038 (10) | −0.0018 (10) | −0.0050 (9) |
| C8 | 0.0743 (16) | 0.0515 (14) | 0.0382 (12) | 0.0055 (13) | −0.0010 (11) | 0.0029 (11) |
| Ni1—O1i | 1.8411 (16) | C2—C3 | 1.409 (3) |
| Ni1—O1 | 1.8411 (16) | C3—C4 | 1.375 (3) |
| Ni1—N1i | 1.8529 (18) | C3—H3 | 0.93 |
| Ni1—N1 | 1.8529 (18) | C4—C5 | 1.398 (3) |
| O1—C2 | 1.316 (2) | C5—C6 | 1.361 (3) |
| O2—C4 | 1.365 (2) | C5—H5 | 0.93 |
| O2—C8 | 1.419 (3) | C6—H6 | 0.93 |
| N1—C7 | 1.289 (3) | C7—H7 | 0.93 |
| N1—H1 | 0.901 (10) | C8—H8A | 0.96 |
| C1—C6 | 1.413 (3) | C8—H8B | 0.96 |
| C1—C2 | 1.417 (3) | C8—H8C | 0.96 |
| C1—C7 | 1.418 (3) | ||
| O1i—Ni1—O1 | 180 | C2—C3—H3 | 119.8 |
| O1i—Ni1—N1i | 93.92 (6) | O2—C4—C3 | 124.35 (19) |
| O1—Ni1—N1i | 86.08 (6) | O2—C4—C5 | 114.44 (18) |
| O1i—Ni1—N1 | 86.08 (6) | C3—C4—C5 | 121.21 (19) |
| O1—Ni1—N1 | 93.92 (6) | C6—C5—C4 | 119.00 (19) |
| N1i—Ni1—N1 | 180 | C6—C5—H5 | 120.5 |
| C2—O1—Ni1 | 128.08 (13) | C4—C5—H5 | 120.5 |
| C4—O2—C8 | 117.75 (16) | C5—C6—C1 | 121.97 (19) |
| C7—N1—Ni1 | 127.97 (15) | C5—C6—H6 | 119.0 |
| C7—N1—H1 | 116.0 (17) | C1—C6—H6 | 119.0 |
| Ni1—N1—H1 | 116.0 (17) | N1—C7—C1 | 124.78 (19) |
| C6—C1—C2 | 118.63 (18) | N1—C7—H7 | 117.6 |
| C6—C1—C7 | 119.98 (18) | C1—C7—H7 | 117.6 |
| C2—C1—C7 | 121.40 (18) | O2—C8—H8A | 109.5 |
| O1—C2—C3 | 117.48 (18) | O2—C8—H8B | 109.5 |
| O1—C2—C1 | 123.82 (17) | H8A—C8—H8B | 109.5 |
| C3—C2—C1 | 118.69 (18) | O2—C8—H8C | 109.5 |
| C4—C3—C2 | 120.50 (19) | H8A—C8—H8C | 109.5 |
| C4—C3—H3 | 119.8 | H8B—C8—H8C | 109.5 |
| Symmetry codes: (i) −x+2, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O2ii | 0.90 (1) | 2.39 (2) | 3.166 (2) | 144 (2) |
| Symmetry codes: (ii) x, −y+1/2, z+1/2. |
| Ni1—O1 | 1.8411 (16) | Ni1—N1 | 1.8529 (18) |
| O1i—Ni1—O1 | 180 | O1—Ni1—N1 | 93.92 (6) |
| O1—Ni1—N1i | 86.08 (6) | N1i—Ni1—N1 | 180 |
| Symmetry codes: (i) −x+2, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O2ii | 0.90 (1) | 2.39 (2) | 3.166 (2) | 144 (2) |
| Symmetry codes: (ii) x, −y+1/2, z+1/2. |
Financial support from the Jiaying University research fund is gratefully acknowledged.
Angulo, I. M., Bouwman, E., Lutz, M., Mul, W. P. & Spek, A. L. (2001). Inorg. Chem. 40, 2073–2082.
Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Costes, J.-P., Dahan, F. & Laurent, J.-P. (1994). Inorg. Chem. 33, 2738–2742.
Dey, S. K., Mondal, N., El Fallah, M. S., Vicente, R., Escuer, A., Solans, X., Font-Bardia, M., Matsushita, T., Gramlich, V. & Mitra, S. (2004). Inorg. Chem. 43, 2427–2434.
Edison, S. E., Krause Bauer, J. A. & Baldwin, M. J. (2004). Acta Cryst. E60, m1930–m1932.
Kamenar, B., Kaitner, B., Stefanović, A. & Waters, T. N. (1990). Acta Cryst. C46, 1627–1631.
Ramadevi, P., Kumaresan, S. & Muir, K. W. (2005). Acta Cryst. E61, m1749–m1751.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Suh, M. P., Oh, K. Y., Lee, J. W. & Bae, Y. Y. (1996). J. Am. Chem. Soc. 118, 777–783.
Tang, C. (2009). Acta Cryst. E65, m317.
Nickel(II) complexes play an important role in both bioinorganic chemistry and coordination chemistry (Suh et al., 1996; Dey et al., 2004; Angulo et al., 2001; Ramadevi et al., 2005; Edison et al., 2004). Recently, the author has reported a nickel(II) complex (Tang, 2009). As a continuation of this work, the title mononuclear nickel(II) complex (Fig. 1), is reported in this paper.
The title complex is a centrosymmetric mononuclear nickel(II) complex. The NiII ion, lying on the inversion centre, is four-coordinated in a square-planar geometry, with two phenolate O and two imine N atoms from two 2-(iminomethyl)-5-methoxyphenolate ligands. The coordination bond lengths (Table 1) are comparable to those observed in related complexes (Kamenar et al., 1990; Costes et al., 1994).
In the crytal structure, molecules are linked through intermolecular N—H···O hydrogen bonds (Table 2), forming zigzag layers parallel to the (100) [Fig.2].