Some phosphazenium chloride salts of the type [R3PNH 2]+Cl-, where R = phenyl, p-chlorophenyl and morpholino, were synthesized by the reaction of the corresponding phosphiniminocyclotrithiazene compounds (R3PNS3N 3) with diphenyldichlorosilane in acetonitrile. All the products were characterized by analytical and spectroscopic data. The single crystal X-ray structure of [Ph3PNH2]+Cl- was reinvestigated with one mole of water molecule in the crystal lattice, showing an intermolecular hydrogen bonding. © Taylor & Francis Group, LLC.