Four complexes [Ni(DMA)2(H2O)4]Cl2·2Н2О, [Ni(DMF)2(H2O)4]Cl2·2Н2О, [Ni(DMA)6][NiCl4], [Ni(DMF)2 (H2O)2Cl2] were isolated from the ternary aqueous-organic salt systems containing nickel chloride and N , N dimethylacetamide-water and N , N -dimethylformamide-water binary solvents. The obtained complexes were studied by single crystal X-ray diffraction method. The formation of hydrogen bonds between the water molecules of the nickel ion's solvate sphere, chlorine ions, and free water molecules located in the cavity of the crystal structure was found.