Crystalline compounds based on Cd(II) complex units provide not only novel structures, but also interesting luminescence properties. Herein we present our results on crystal design, synthesis and X-ray single crystal investigation for complex formation between cadmium(II) salts, classic dioximes and linear bifunctional bipyridyl ligands. The Cd(II) oxime chemistry is poorly eIn the similar in structure binuclear molecules each Cd(II) cation is hexacoordinated into a shape of a square bipyramid in the N3O3 -environment. Its basal plane is defined by a bidentate NioxH2 molecule and two monodentate acetate/formate anions, the water molecule and the bidentate bpy/bpetha ligand occupy the apical sites, bpy/bpetha being coordinated to the symmetry-related metal atom in a bridge function. Interaction in the system CdSO4+ NioxH2/ mgH2 + bpy in the molar ratio 1:2:2 resulted in the dioxime-free 1D coordination polymer with the monomeric unit [Cd(bpy)(SO4).(H2O)3].2H2O (a) in the case of mgH2, and the 1D polymer of the composition {[Cd2(NioxH2)(SO4)(bpy)](NioxH2)(H2O)3}n (b). The Xray diffraction shows that each Cd(II) ion (b) binds one two-coordinate NioxH2 molecule, two twocoordinate sulfato-anions as basal ligands and two bpy molecules as axial ligands with the formation of a square bipyramidal N4O2-coordination core. In concern with the sulfate anions NioxH2 formulate the robust extended binuclear metal platform. An another dioxime free 1D coordination polymer was obtained as a result of interaction in the system Cd(CH3COO)2+bpetha+dphH2, in the similar molar ratio. The cadmium atom is heptacoordinated and has a pentagon bipyramidal N2O5-environment; one water molecule occupies the basal positions around the Cd(II) along with four atoms from the bidentate acetato ligands, and two nitrogen atoms from trans-bpetha ligand occupy the apical positions. The luminescent properties of all novel compounds are in progress.xplored, particularly in the field of classic dioximes. To fill this gap, we intended to synthesize multinuclear and polymeric coordination compounds starting from the Cd(II) halides, formates, acetates, or sulfates, classic dioximes (mgH2= methylglyoxime, dphH2= diphenylglyoxime, NioxH2 =1,2-cyclohexanedionedioxime), and potentially bridging bipyridyl ligands (bpy= 4,4’bipyridyl, bpetha= 1,2-bis(4-pyridyl)ethane). Thus, three novel 0D and three 1D Cd(II) mixed-ligand coordination compounds were obtained. The schematic diagram is presented bellow.formula