SrP3 N5 NH: A Framework-Type Imidonitridophosphate Featuring Structure-Directing Hydrogen Bonds

Abstract

Nitridophosphates and imidonitridophosphates show intriguing structural diversity, including unprecedented structure types. Highly condensed strontium imidonitridophosphate SrP₃ N₅ NH has been synthesized at 8 GPa and 1100 °C using a high-pressure high-temperature approach starting from stoichiometric amounts of Sr(N₃ )₂ , P₃ N₅ and NH₄ Cl. Herein, NH₄ Cl was used as a hydrogen source and as a precursor for in situ formation of SrCl₂ , which acts as mineralizer and facilitates growth of single-crystals with a diameter of ≤30 μm. SrP₃ N₅ NH (P2₁ /c (no. 14), a=5.01774(2), b=8.16912(4), c=12.70193(5) Å, β=101.7848(3)°, Z=4) adopts an unprecedented network structure, represented by the point symbol (3.4.5.6.7² )(3.4.5.7² .8)(3.6.7³ .8). This unique three nodal P/N(H) network is stabilized by moderately strong hydrogen bonds causing a structure-directing effect, which has not yet been reported for imidonitridophosphates.

Keywords: NMR spectroscopy; high-pressure chemistry; high-temperature chemistry; hydrogen bonds; imidonitridophosphates.