The reactions of formazanes with transition metal ions can give coordination compounds of different nature and structures, namely, mono-and binuclear complexes, complexes with different surrounding of a central atom and configuration. The reason for such a variety lies in a high flexibility of formazanes, their capability to act as bi-, tri-, or tetradentate ligands with allowance for the substituents [1].Formazanes and their compounds are widely used in chemistry, in particular, as analytical reagents. The polymeric ionites modified with formazanes significantly improve the ionite selectivity toward the adsorbed metal ions [2].The goal of this work was to study the Cu(II) complexes with hetarylformazanes ( HF ) in solutions, modified AN-18 anionite, and in polycrystals. The following ligands were used in this work:The authors of [3][4][5] used the NMR and X-ray diffraction methods to study the Ni(II), Co(II), and Cd(II) complexes with hetarylformazanes containing substituents R 1 , R 2 , and R 3 that were different from those we used. They established that the complexes under study had octahedral structure (coordination number 6) with the N 1 and N 4 atoms of the formazane fragment and the N 6 atom of heterocycle participating in coordination with a metal.A significant broadening of lines in the NMR spectrum of the Cu(II) complexes due to the spin paramagnetism effect does not make it possible to use the NMR method in order to study the structure of the Cu(II) complexes with formazanes. Therefore, we used the Abstract -The Cu(II) complexes with hetarylformazanes (HF) formed in solutions, polycrystals, and AN-18 polymeric ionite modified with HF were studied by EPR method and were found to have almost identical structures. The configuration of the Cu 2+ coordination surrounding (square-planar or pseudotetrahedral) is specified by the substituents at N 1 in formazane fragments. Complexes with coordination unit Cu(4N) were formed mainly, when the ligands were taken in excess, while in the case of the ligand deficiency and with the coordinating OH group in benzene ring, the complexes with the Cu(3NO) coordination unit were formed. The covalence of in-plane metal-ligand σ -bond was found to be affected by the substituents. The formation of binuclear copper complexes in solutions and polycrystals was established in the case of deficiency of the ligand with SO 3 H substituent in benzene ring.

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