The first heterospin compounds based on bis(1,1,1,3,5,5,5 heptafluoro 4 iminopent 2 ene 2 aminato)copper(II) (CuL2) and nitronyl nitroxide radicals, 2 R 4,4,5,5 tetramethyl 4,5 dihydro 1H imidazole 3 oxide 1 oxyls (NIT R, where R = H, Me, Ph, and 1 methyl pyrazol 4 yl), were synthesized and structurally characterized. An important peculiarity of the structure of synthesized solid phases is the formation of a supramolecular structure due to hydrogen bonds between the oxygen atoms of the nitronyl nitroxide fragments of NIT R and the hydrogen atoms of the NH groups of CuL2