Schiff bases o-vanilidene-1-aminobenzene (HL1) and o-vanilidene-2-methyl-1-aminobenzene (HL2) lead to the formation of mono- and bis-[(Cl)Zn(L1)] (1), [(Cl)Zn(L2)] (2), [(Cl)Hg(L1)] (3), [(Cl)Hg(L2)] (4), [Zn(L1)2] (5), [Zn(L2)2] (6), [Hg(L1)2] (7), and [Hg(L2)2] (8) complexes by reactions of zinc(II) and mercury(II) chlorides in different mole ratio(s). Complexes 1–8 have been characterized by elemental analyses (Zn, Hg, C, H, Cl, and N), melting point and spectral (IR, 1H-NMR), PXRD, molar conductivity measurement, and TGA. Conductivity measurements suggest non-electrolytes. Structural compositions have been assigned by mass spectral studies. Four-coordinate geometry may be assigned to these complexes tentatively. Structural study reveals that in 1–4 two metal centers are held together by two bridged (μ2-Cl) chlorides, whereas 5–8 contain two bidentate Schiff-base ligands around one metal-producing monomers.