Xue Mei-Xiang, Liu Shi-Xiong
Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002, People's Republic of China.
Acta Crystallogr C. 2008 May;64(Pt 5):m190-3. doi: 10.1107/S0108270108006240. Epub 2008 Apr 9.
In the two title complexes of cinnamaldehyde salicyloylhydrazone [or 2-hydroxy-N'-(3-phenylprop-2-enylidene)benzohydrazide], [Ni(C(16)H(13)N(2)O(2))(2)(CH(4)O)(2)], (I), and [Ni(C(16)H(13)N(2)O(2))(2)(C(5)H(5)N)(2)], (II), the Ni(II) atoms lie on crystallographic inversion centres and have distorted octahedral geometries. The equatorial plane is defined by two carbonyl O atoms and two hydrazine N atoms of two bidentate trans-oriented salicyloylhydrazone ligands. The axial positions are occupied by two O atoms from two coordinated methanol molecules in (I) and by two N atoms from two coordinated pyridine molecules in (II). There is an extended chain structure in (I) resulting from intermolecular O-H...O hydrogen bonds between coordinated methanol molecules and phenol O atoms, while (II) comprises discrete molecules. Complex (I) also exhibits weak pi-pi stacking interactions, and intramolecular O-H...N hydrogen bonds are present in both (I) and (II). The salicyloylhydrazone ligands in (I) and (II) are coordinated to the metal atom through the carbohydrazide O and N(2) atoms, not via the phenol O atom. We have established a link between the reagents used and the nuclearity of the complex formed: the ligand produced by condensation between salicylhydrazide and an aldehyde leads to mononuclear complexes, while replacing the aldehyde in the reaction by a ketone leads to multinuclear complexes.
在肉桂醛水杨酰腙[或2-羟基-N'-(3-苯基丙-2-亚基)苯甲酰肼]的两个标题配合物[Ni(C₁₆H₁₃N₂O₂)₂(CH₄O)₂],(I),和[Ni(C₁₆H₁₃N₂O₂)₂(C₅H₅N)₂],(II)中,Ni(II)原子位于晶体学反演中心,具有扭曲的八面体几何构型。赤道平面由两个双齿反式取向的水杨酰腙配体的两个羰基O原子和两个肼基N原子定义。轴向位置在(I)中由两个配位甲醇分子的两个O原子占据,在(II)中由两个配位吡啶分子的两个N原子占据。(I)中存在由配位甲醇分子和酚O原子之间的分子间O-H...O氢键导致的扩展链结构,而(II)由离散分子组成。配合物(I)还表现出弱的π-π堆积相互作用,并且(I)和(II)中均存在分子内O-H...N氢键。(I)和(II)中的水杨酰腙配体通过酰肼O和N₂原子与金属原子配位,而不是通过酚O原子。我们已经建立了所用试剂与形成的配合物的核数之间的联系:水杨酰肼与醛缩合产生的配体导致单核配合物,而在反应中用酮代替醛则导致多核配合物。