A series of Zn(II), Cd(II), Co(II), Co(III) and Mn(III) complexes with the Schiff base [(CH3)2NCH2CH2NCHC 6H3(OH)(OMe)], LH, derived from 2-dimethylaminoethylamine and o-vanillin, has been synthesised and structures of all the products have been established by X-ray crystallography. In the cases of zinc and cadmium, dimeric complexes [Zn(LH)2(NCS)] [Zn2(L)( 1,1-CH3COO)(NCS)3] (1), [Cd2(L) 2(Cl)2] (2) and [Cd2(L)2(NCS) 2] (3), and for cobalt and manganese, monomeric complexes [Co(LH)2(NCS)]2 [Co(NCS)4] (4), [Co(LH) 2(NCS)]ClO4 (5), [Co(L)(N3)(o-vanillinate)] ·0.5MeOH (6) and [Mn(LH)2(MeOH)2](ClO 4)3 (7), are formed with various terminal ligands. All the complexes have been characterised by elemental analysis and IR spectra. UV-Vis and NMR spectroscopy, magnetic, and electrochemical studies, were also carried out where feasible. The Schiff base functions as a bi-, tri- or tetra-dentate chelating agent and coordinates via the protonated or deprotonated phenolic oxygen, amine and imine nitrogens, and only in case of 1 with the methoxy oxygen atoms, to the metal ion leading to the formation of mono- or bi-metallic complexes. © The Royal Society of Chemistry 2006.