A series of six-membered Cu-I true heterocycles was prepared by reactions of Cu(PPh3)(2)NO3 with deprotonated R2P(S)-NH-C(O)R' (R' = (CH2)(3)CH3, C6H5, C6H4F, C6H4Cl; R = Ph, OPh) ligands. The synthesized compounds were characterized by P-31 NMR spectroscopy and single crystal X-ray diffraction. According to quantum chemical calculations, most of the true Cu-I heterocycles with the P-N-C ligands should be tetrahedral. However, an exceptional trigonal complex was observed upon crystallization.