ChemInform Abstract: High‐Pressure Synthesis and Structural Investigation of H₃P₈O₈N₉: A New Phosphorus(V) Oxonitride Imide with an Interrupted Framework Structure.

Abstract

Structure. -The title compound is synthesized in three steps. First a mixture of PO(NH2)3 and NH4Cl in a molar ratio of 1:3 is prepared from excess NH3 and POCl3 (-78°C, 2 h, 100% yield). In the second step, the obtained mixture is heated in a NH3 flow at 300 and 620°C for 5 and 12 h, resp., leading to the formation of the precursor PO 0.88 N 1.24 H 0.56 (26% yield). In the last step, the precursor is treated in a multianvil assembly under 12 GPa at 750°C for 30 min (yield given in g). H3P8O8N9 crystallizes in the monoclinic space group C2/c with Z = 4 (powder XRD). It exhibits a highly condensed, three-dimensional, but interrupted network composed of all-side vertex-sharing (Q 4 ) and only threefold-linking (Q 3 ) P(O,N) 4 tetrahedra in a Q 4 /Q 3 ratio of 3:1. The title compound is further characterized by 1 H and 31 P MAS NMR spectroscopy. -(SEDLMAIER, S. J.; CELINSKI, V. R.; SCHMEDT AUF DER GUENNE, J.; SCHNICK*, W.; Chem. Eur. J. 18 (2012) 14, 4358-4366, http://dx.