High-Pressure Synthesis, Crystal Structure, and Characterization of Zn2PN3 - A New catena-Polynitridophosphate

Phase-pure zinc catena-polynitridophosphate Zn2PN3 was synthesized by means of high-pressure high-temperature conditions (1200 degrees C, 8 GPa) starting from Zn3N2 and P3N5 utilizing a multianvil assembly. It was obtained as a colorless, microcrystalline powder. The crystal structure of Zn2PN3 (Cmc2(1), no. 36, a = 937.847(6), b = 547.696(4), c = 492.396(3) pm, Z = 4, R-p = 0.0110, wR(p) = 0.0141) has been refined from powder X-ray diffraction data by the Rietveld method using the atomic parameters of isotypic Mg2PN3 as starting values. Interconnected by N-coordinated Zn2+ ions, the catena-polynitridophosphate chain anions run parallel [001] with a chain periodicity P = 2 and a stretching factor f(s) = 0.88. FT-IR and Raman spectra of Zn2PN3 were recorded and relevant bands were assigned. The solid-state P-31 MAS NMR spectrum yielded a single resonance at delta = 42.8. In addition an account of the thermal behavior of Zn2PN3 is given.