Dinuclear versus trinuclear complex formation in zinc(II) benzoate/pyridyl oxime chemistry depending on the position of the oxime group

The initial employment of pyridine-3-carbaldehyde oxime, (3-py)C(H)NOH, and pyridine-4-carbaldehyde oxime, (4-py)C(H)NOH, in zinc(II) carboxylate chemistry is reported. The syntheses, crystal structures and IR characterization are described for [Zn3(O2CPh)6{(3-py)C(H)NOH}2] (1) and [Zn2(O2CPh)4{(4-py)C(H)NOH}2] (2). The trinuclear molecule of 1 has a linear structure, with one monoatomically bridging η1:η2:μ and two syn, syn-η1:η1:μ benzoate groups spanning each pair of ZnII ions; the terminal metal ions are each capped by one (3-py)C(H)NOH ligand coordinating through its pyridyl nitrogen. Complex 2 exhibits a dinuclear paddle–wheel structure with a Zn···Zn distance of 2.990(2) Å; each ZnII ion has a square pyramidal geometry with four carboxylate oxygens in the basal plane and the pyridyl nitrogen of one monodentate (4-py)C(H)NOH ligand at the apex. Both complexes form 1D architectures by virtue of hydrogen bonding interactions involving the free oxime group as donor and the oxime nitrogen (1) or carboxylate oxygens (2) as acceptors. IR data are discussed in terms of the known structures and coordination modes of the ligands.

The reaction of Zn(O2CPh)2·2H2O and 3-pyridinealdoxime, (3-py)C(H)NOH, in MeCN gives a trinuclear cluster containing the [Zn3(η1:η1:μ-Ο2CPh)4(η1:η2:μ-Ο2CPh)2]0 core, while an analogous reaction with the isomeric 4-pyridinealdoxime, (4-py)C(H)NOH, yields the dinuclear, paddle-wheel complex [Zn2(η1:η1:μ-Ο2CPh)4{(4-py)C(H)NOH}2].Figure optionsDownload as PowerPoint slide