The novel complexing process in the Ni(II)- hydrazinomethanethioamide- buthanedione-2,3 triple system proceeding under water-ethanol solution and in nickel(II) hexacyanoferrate(II) gelatin-immobilized matrix systems, has been studied. It has been shown that self-assembly (template synthesis) of supramolecular macrocyclic Ni(II) coordination compound with novel chelating ligand 4,5-dimethyl-1,8-dimercapto-2,3,6,7-tetraazaoctatetraen-1,3,5,7-diamine-1,8 with (NSSN) coordination of donor atoms to metal ion, occurs under both such conditions. Hydrazinomethanethioamide and buthanedione-2,3 act as ligsons in this process.