The importance of intramolecular hydrogen bonds for structural stabilization. [Triphenyl-tetrazolium] [tetraphenyldichalcogenoimidodiphosphinates], [Ph3CN4][Ph2P(X)NP(Y)Ph2].

[Display omitted] In order to know the capacity of the tetrazolium cation [Ph 3 CN 4 ]+ to act as a stabilizing influence in the presence of bulky anions and facilitator to obtain suitable crystals for single-crystal X-ray diffraction studies, four new compounds [Ph 3 CN 4 ] [Ph 2 P(X)NP(Y)Ph 2 ] [X = Y = O (1); X = Y = S (2); X = Y = Se (3); X = S, Y = Se (4)] were synthesized. The compounds were characterized by elemental analysis, IR, FAB+ mass spectrometry, 1H, 13C, and 31P NMR spectroscopy, and the corresponding single-crystal X-ray structural determinations were acquired. In the four compounds, the neighboring [Ph 3 CN 4 ]+ and [Ph 2 P(X)NP(Y)Ph 2 ]- ions are linked by electrostatic interactions, and thus supramolecular polymer chains are generated. To explain the energetic implications of the structural deformations, the interactions and the stabilizer hydrogen bonds, a study was carried out through the Density Functional Theory (DFT). [ABSTRACT FROM AUTHOR]