anti-Chloroglyoxime, CGH(2), has been synthesized by chlorination of anti-glyoxime. The reaction of CGH(2) with thiophenol, 4-methyIthiophenol and 4-methoxythiophenol in ethanol between -5 degrees C and -10 degrees C gives unsymmetrical vic-dioximes, designated as thiophenologlyoxime [L(a)H(2)], 4-methylthiophenologlyoxime [L(b)H(2)] and 4-methoxythiophenologlyoxime [L(c)H(2)]. The Cu(II) and Ni(II) complexes of these ligands were prepared and are proposed to be square-planar, while the corresponding Co(II) complexes are proposed to be octahedral with water molecules as axial ligands. Structural assiguments are supported by H-1 NMR, IR and elemental analyses.