The reaction of zinc chloride with 2-benzylideneamino-5-methylphenol (LH), a bidentate Schiff base, in 1 : 1 molar ratio in the presence of triethylamine gives the ionic complex [Et3NH](+)[LZnCl2](-) (I). The reaction between the zinc salt (chloride or acetate) and LH in 1 : 2 ratio results in complete displacement of the zinc salt anions to give bis-o-iminophenolate ZnL2 (II), which exists in the crystalline state as the (ZnL2)(2) dimer formed via mu-bridging oxygen atoms of two out of the four o-iminophenolate ligands. The molecular structure of ligand LH and complexes I and (II center dot CDCl3)(2) was established by X-ray diffraction (CIF files CCDC nos. 2052647 (LH), 2052645 (I), 2052646 (II center dot CDCl3)(2)).