High‐pressure and high‐temperature synthesis of crystalline Sb<sub>3</sub>N<sub>5</sub>
Matteo Ceppatelli, Manuel Serrano‐Ruiz, Marta Morana, Kamil F. Dziubek, Demetrio Scelta, Gastón Garbarino, Tomasz Porȩba, Mohamed Mézouar, Roberto Bini, Maurizio Peruzzini
Abstract
Abstract A chemical reaction between Sb and N 2 was induced under high‐pressure (32–35 GPa) and high‐temperature (1600–2200 K) conditions, generated by a laser heated diamond anvil cell. The reaction product was identified by single crystal synchrotron X‐ray diffraction at 35 GPa and room temperature as crystalline antimony nitride with Sb 3 N 5 stoichiometry and structure belonging to orthorhombic space group Cmc 2 1 . Only Sb−N bonds are present in the covalent bonding framework, with two types of Sb atoms respectively forming SbN 6 distorted octahedra and trigonal prisms and three types of N atoms forming NSb 4 distorted tetrahedra and NSb 3 trigonal pyramids. Taking into account two longer Sb−N distances, the SbN 6 trigonal prisms can be depicted as SbN 8 square antiprisms and the NSb 3 trigonal pyramids as NSb 4 distorted tetrahedra. The Sb 3 N 5 structure can be described as an ordered stacking in the bc plane of bi‐ layers of SbN 6 octahedra alternated to monolayers of SbN 6 trigonal prisms (SbN 8 square antiprisms). The discovery of Sb 3 N 5 finally represents the long sought‐after experimental evidence for Sb to form a crystalline nitride, providing new insights about fundamental aspects of pnictogens chemistry and opening new perspectives for the high‐pressure chemistry of pnictogen nitrides and the synthesis of an entire class of new materials.