Interaction of zinc or cadmium formate or acetate with 1,2-cyclohexanedionedioxime (NioxH(2)) and 4,4'-bipyridine (bpy) resulted in similar binuclear coordination compounds of the general formula [M-2(NioxH(2))(2)(X)(4)(H2O)(2)(bpy)], where M = Cd and X = HCOO- for 1; M = Zn, Cd and X = CH3COO- for 2 and 3, respectively. When the corresponding sulfate salts were used as precursors in the synthesis, a dioxime-containing one-dimensional (I D) coordination polymer with the chemical formula [Cd(NioxH(2))(SO4)center dot(bpy)](NioxH(2))center dot(H2O)(3) (4) was obtained with Cd. All compounds were characterized by X-ray diffraction and spectroscopic techniques, and the thermogravimetric data are presented solely for compound 4. The experimental results demonstrate the successful strategy of using "metal oxime" building blocks in order to design new multinuclear complexes. The study has shown that the geometry and size of the corresponding anions together with their coordinating and hydrogen-bonding properties are essential in determining the Final structures.