The use of 6-methylpyridine-2-carbaldehydeoxime ligand (6-mepaoH), in nickel(II) chemistry has been investigated and three new clusters isolated in mild conditions. Depending on the nature of the metal starting salts and the reaction conditions, the NiII/6-mepaoH system has provided access to the complexes [Ni6(O2CPh)6(6-mepao)6] (1), [Ni6(O2CMe)6(6-mepao)6] (2) and [Ni5(3-Cl-BzO)4(6-mepao)4(6-mepaoH)2(N3)2] (3), where 3-Cl-BzO− is the 3-chlorobenzoate anion. Compounds 1 and 2 are two new members of the [Ni6(O2C-R)(oximato)6] family of hexanuclear complexes whereas 3 exhibits an unusual irregular bowtie topology including end-on azido bridges. The structures of the three compounds have been determined by single-crystal X-ray crystallography. Variable-temperature dc magnetic susceptibility studies were carried out for 1–3. The data indicate antiferromagnetic exchange for complexes 1 and 2 and ferrimagnetic interaction for complex 3.
