Combination of Ambient and High‐Temperature Beryllium Nitride Motifs in W₂Be₄N₅ and W₄Be₈N₉

Abstract Compounds of transition metals and beryllium have a wide range of applications, from everyday tools to high tech applications. Remarkably, no single ternary beryllium nitride with a transition metal is known. Here, we report on the synthesis and properties of the first transition metal nitridoberyllates, namely W 2 Be 4 N 5 and W 4 Be 8 N 9 . Both compounds were synthesized in a high‐temperature high‐pressure approach from Be 3 N 2 and W, using azide generated N 2 as an oxidizing agent. The crystal structures, consisting of alternating layers of WN 6 trigonal prisms and BeN 4 tetrahedra, were elucidated by single‐crystal X‐ray diffraction (sc‐XRD). The separating nitridoberyllate layers show either ambient temperature (α‐Be 3 N 2 type) or high temperature (β‐Be 3 N 2 type) motifs. W 2 Be 4 N 5 was further corroborated by infrared (IR), nuclear magnetic resonance (NMR) and UV/Vis spectroscopy and vibrating sample magnetometry (VSM) measurements. The latter revealed a mixed valence with an intermediate oxidation state of 3.5 for the W atoms. Both, the synthesis of the first transition metal nitridoberyllates and the synthesis approach using elemental W pave the way to a new field of nitride chemistry.