High‐pressure and high‐temperature synthesis of crystalline Sb3N5

• Published in: Angewandte Chemie International Edition 2024-03, Vol.63 (11), p.e202319278-n/a
• Main Authors: Ceppatelli, Matteo, Serrano‐Ruiz, Manuel, Morana, Marta, Dziubek, Kamil, Scelta, Demetrio, Garbarino, Gaston, Poręba, Tomasz, Mezouar, Mohamed, Bini, Roberto, Peruzzini, Maurizio
• Format: Article
• Language: English
• Subjects: Antimony; Chemical reactions; Chemical synthesis; Diamond anvil cells; Laser beam heating; Nitrides; Prisms; Pyramids; Reaction products; Room temperature; Single crystals; Stoichiometry; Tetrahedra
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202319278

A chemical reaction between Sb and N2 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 Sb3N5 stoichiometry and structure belonging to orthorhombic space group Cmc21. Only Sb−N bonds are present in the covalent bonding framework, with two types of Sb atoms respectively forming SbN6 distorted octahedra and trigonal prisms and three types of N atoms forming NSb4 distorted tetrahedra and NSb3 trigonal pyramids. Taking into account two longer Sb−N distances, the SbN6 trigonal prisms can be depicted as SbN8 square antiprisms and the NSb3 trigonal pyramids as NSb4 distorted tetrahedra. The Sb3N5 structure can be described as an ordered stacking in the bc plane of bi‐ layers of SbN6 octahedra alternated to monolayers of SbN6 trigonal prisms (SbN8 square antiprisms). The discovery of Sb3N5 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. Crystalline Sb3N5 has been synthesized from the high‐pressure and high‐temperature chemical reaction of antimony and nitrogen in a laser heated diamond anvil cell. The Cmc21 structure of Sb3N5, determined by single crystal synchrotron X‐ray diffraction, contains two types Sb atoms in octahedral and trigonal prismatic (square antiprismatic) coordination, respectively forming alternated double‐ and mono‐layers stacked in the bc plane.