Compounds with a `stuffed' anti-bixbyite-type structure, analysed in terms of the Zintl–Klemm and coordination-defect concepts

Abstract

The bixbyite structure (Mn2O3) (Ia\bar 3) is often described as a distorted face-centered cubic (f.c.c.) array of Mn atoms, with O atoms occupying 3/4 of the tetrahedral holes. The empty M 4 tetrahedra are centred at 16c. In anti-bixbyite structures (Mg3N2), cation vacancies are centred in empty N4 tetrahedra. If 16 hypothetical atoms were located at this site they would form the structure of γ-Si. This means that anti-bixbyite structures are ideally prepared to accommodate Si(Ge) atoms at these holes. Several compounds (Li3AlN2 and Li3ScN2) fully satisfy this expectation. They are really anti-bixbyites `stuffed' with Al(Sc). The presence of these atoms in 16c is illuminated in the light of the extended Zintl–Klemm concept (EZKC) [Vegas & García-Baonza (2007). Acta Cryst. B63, 339–345], from which a compound would be the result of `multiple resonance' pseudo-structures, emerging from electron transfers between any species pair (like or unlike atoms, cations or anions). The coordination-defect (CD) concept [Bevan & Martin (2008). J. Solid State Chem. 181, 2250–2259] is also consistent with the EZKC description of the pseudo-structures. A more profound insight into crystal structures is gained if one is not restricted to the contemplation of classical anions and cations in their conventional oxidation states.