In the result of the interaction between the [Co(dH)2(N3)(sam)] structural block (dH - dimethylglyoxime monoanion, sam - sulfanilamide) with bridging ligands (dpp – 4,4- trimethylenedipyridine and L – 4N-(4-4-[(E)-1-(4-pyridyl)methylideneamino] phenethylphenyl)-4- pyridylmethamine in a 2:1 molar ratio have been obtained [Co2(dH)4(N3)2(dpp)] (1) and [Co2(dH)4 (N3)2(L)] (2) binuclear complexes. Monocrystals have been obtained in the methanoldimethylformamide media, and the X-ray study has established the crystallization of these compounds in the tricilinic P-1 and monoclinic P21/c space groups, respective. The crystal structure determination has confirmed the sam substitution from the initial structural block through bridging ligands and the formation of the binuclear complex compounds (Fig. 1 and Fig. 2) as in the case of using [Co(dH)2Cl(H2O)] as structural blocks [1]. In the both compounds the Co(III) coordination polyhedron consists of N6 donor atoms, four nitrogen atoms belonging to the two DH- residues coordinated in chelating mode, one from N3 - anion, and the remaing N atoms come from dpp or L ligands with bridging function. Fig. 1. The molecular structure of the binuclear complex compound 1. Fig. 2. The molecular structure of the binuclear complex compound 2. The mode of packing compunds in crystals depended on the dimensionality of the ligand with bridging function.