Directed synthesis of dianiline- (DAnH2) and disulfanilamideglyoximes (DSamH2) has been accomplished by condensation of dichloroglyoxime with aniline or sulfanilamide in 1:2 molar ratio, as well as their corresponding Co(III), Ni(II) and Cu(II) coordinative compounds. Composition, structure and some properties of dioximes and complexes have been established by using elemental analysis, UV-Vis, IR and NMR- spectroscopies. Dioxime coordination at the central atom and structure of complexes depends on pH of reaction medium: at pH=5-6 - bis- dioximates, whilst at pH=2 – tris-dioximines are obtained. In the case of the corresponding tris-dioximines increment of the functional groups number in dioxime fragments, which can form intermolecular hydrogen bonds, leads to the augment of the stability of complexes.