High-Pressure Synthesis of Sc5 P12 N23 O3 and Ti5 P12 N24 O2 by Activation of the Binary Nitrides ScN and TiN with NH4 F.

Multinary transition metal nitrides and oxonitrides are a versatile and intriguing class of compounds. However, they have been investigated far less than pure oxides. The compounds Sc5 P12 N23 O3 and Ti5 P12 N24 O2 have now been synthesized from the binary nitrides ScN and TiN, respectively, by following a high-pressure high-temperature approach at 8 GPa and 1400 °C. NH4 F acts as a mineralizing agent that supports product formation and crystallization. The starting materials ScN and TiN are seemingly an uncommon choice because of their chemical inertness but, nevertheless, react under these conditions. Sc5 P12 N23 O3 and Ti5 P12 N24 O2 crystallize isotypically with Ti5 B12 O26 , consisting of solely vertex-sharing P(O/N)4 tetrahedra forming two independent interpenetrating diamond-like nets that host TM(O/N)6 (TM=Sc, Ti) octahedra. Ti5 P12 N24 O2 is a mixed-valence compound and shows ordering of Ti3+ and Ti4+ ions.