The reaction between a series of non mesogenic tetradentate salen-like Schiff bases and Zn(II) acetate gives rise to the formation of liquid cristalline complexes showing nematic and smectic phases stable over a quite large temperature range. A dimeric structural arrangement could favour the appearance of such type of mesophase in the case of 1,3-diaminopropane and 1,3-diamino-2,2-dimethylpropane bridges containing ligands while for the salen derivatives a monomeric solvent-induced pentacoordinated arrengement observed in solution and in the crystalline molecular structure, probably prevent the liquid crystalline behaviour.