As a result interaction AgNO3 and Cd(CH3COO)2 · 2H2O with 4,4’-(1,4-phenilenediisopropiliden)bisaniline (molar ratio of 1:1) in acetonitrile was synthesized coordination polymers [AgL1.5]NO3 (I), [CdL1,25(CH3CO2)2(H2O)] (II), L = NH2-C6H4-C(CH3)2-C6H4- C(CH3)2-C6H4-NH2, and structure I, II was determined. In the structure of I realized cationic polymeric chains [Ag(L)]+ ∞ due to bridging ligand L. Second crystallographically nonequivalent centrosymmetrical ligand L combines pairwise the chains to form infinite tapes along direction [010] (Fig. 1). Ag+ ion is coordinated to three nitrogen atoms of ligands L and has a distorted T-shaped coordination. Let us note that the ligands of such a type can have anti or syn conformation. Ligand L is known to have anti configuration in solid state. In the studied structure I, only centrosymmetrical ligand L, which is a bridge between a couple of chains, has anti orientation. The ligand L producing polymeric chains [Ag(L)]+ ∞ have syn orientation.figureFig. 1. Infinite tapes of cationic polymeric chains [Ag(L)]+ ∞ pairwise bound by centrosymmetrical ligands L. Noncoordinated NO3 - anions participate in N–H…O hydrogen bonds as proton acceptors. One oxygen atom has a weak contact with silver ion that leads to formation of 3D supramolecular ensemble. The structure II is built of discrete centrosymmetrical tetranuclear complexes [Сd4L5] due to three bridging and two terminal ligands L. Two crystallographically nonequivalent atoms Сd(1) and Cd(2) linked by bridging ligand N(2)…N(3), Cd(1) bonding by terminal ligand N(1)…N(5). Centrosymmetrical ligand N(4)…N(4a) combines such structural units to form tetranuclear complexes [Сd4L5]. Each of two ions Cd2+ are coordinated seven atoms: two nitrogen atoms of ligands, four oxygen atoms of two bidentate acetate groups and one molecule H2O (fig. 2). In the structure II only centrosymmetrical ligand N(4)…N(4a) has anti orientation. The bridging ligand N(2)…N(3) between Сd(1) and Cd(2) and terminal ligand N(1)…N(5) have syn orientation. Bidentate acetate groups coordinating cadmium atoms parFig. 2. Centrosymmetrical tetranuclear complexes [Сd4L5]. ticipate in N–H…O hydrogen bonds as proton acceptors and combine centrosymmetrical tetranuclear complexes [Сd4L5] in 3D supramolecular framework. Thus, the use of extended flexible ditopic ligands makes it possible to obtain coordination polymers whose structure contains unusual polymeric motifs, while bridging ligands producing bonds with metal ion may have differrent conformation in the same compound.