Structural Influence of Lone Pairs in GeP(2)N(4), a Germanium(II) Nitridophosphate

Owing to their widespread properties, nitridophosphates are of high interest in current research. Explorative high‐pressure high‐temperature investigations yielded various compounds with stoichiometry MP(2)N(4) (M=Be, Ca, Sr, Ba, Mn, Cd), which are discussed as ultra‐hard or luminescent materials, when doped with Eu(2+). Herein, we report the first germanium nitridophosphate, GeP(2)N(4), synthesized from Ge(3)N(4) and P(3)N(5) at 6 GPa and 800 °C. The structure was determined by single‐crystal X‐ray diffraction and further characterized by energy‐dispersive X‐ray spectroscopy, density functional theory calculations, IR and NMR spectroscopy. The highly condensed network of PN(4)‐tetrahedra shows a strong structural divergence to other MP(2)N(4) compounds, which is attributed to the stereochemical influence of the lone pair of Ge(2+). Thus, the formal exchange of alkaline earth cations with Ge(2+) may open access to various compounds with literature‐known stoichiometry, however, new structures and properties.