High‐Pressure Synthesis and Chemical Bonding of Mg ₃ BiN

The search for intermetallic compounds with elements providing strong spin–orbit coupling yields the new phase Mg 3 BiN adopting a cubic (anti‐)perovskite‐type crystal structure ( a = 4.4011(2) Å). Synthesis is performed at high‐pressure high‐temperature conditions in a Walker‐type large volume device (8 GPa, 1123−1273 K). The ternary compound is formed by reaction of Mg‐Bi mixtures with the crucible material boron nitride upon prolonged heating for 2 hours. The position of the nitride anion is identified by analysis of the spatial distribution of the electron localizability indicator in the metal matrix. The electron balance [Mg +2 ] 3 [Bi −3 ][N −3 ] indicates that the compound is electron‐precise in accordance with the Zintl concept, and the calculated electronic density of states indicates semiconducting properties.