Crystalline Nitridophosphates by Ammonothermal Synthesis

Nitridophosphates are a well-studied class of compounds with high structural diversity. However, their synthesis is quite challenging, particularly due to the limited thermal stability of starting materials like P₃ N₅ . Typically, it requires even high-pressure techniques (e.g. multianvil) in most cases. Herein, we establish the ammonothermal method as a versatile synthetic tool to access nitridophosphates with different degrees of condensation. α-Li₁₀ P₄ N₁₀ , β-Li₁₀ P₄ N₁₀ , Li₁₈ P₆ N₁₆ , Ca₂ PN₃ , SrP₈ N₁₄ , and LiPN₂ were synthesized in supercritical NH₃ at temperatures and pressures up to 1070 K and 200 MPa employing ammonobasic conditions. The products were analyzed by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and FTIR spectroscopy. Moreover, we established red phosphorus as a starting material for nitridophosphate synthesis instead of commonly used and not readily available precursors, such as P₃ N₅ . This opens a promising preparative access to the emerging compound class of nitridophosphates.