Crystal structures of novel tetrakis(diethylammonium) and tetra(piperidinium) salts of 1,2,3,4-tetramercapto-1,2,3,4-tetrathioxotetraphosphetane are determined by single crystal X-ray diffraction. It is found that the substitution of the piperidinium cation for the diethylammonium one results in a change in the nature of charge distribution in crystals of the compounds, but the nature of supramolecular structures originating from intermolecular hydrogen bonding is preserved. Stoichiometry of the composition and phosphorus-containing anions turn out to be identical in both cases.