Copper scandium zirconium phosphate: occupancy of theM1 andM2 sites in the temperature range 100–300 K

Abstract

The title compound, with nominal formula Cu(2)ScZr(PO(4))(3), has a beige coloration and displays fast Cu(+) cation conduction at elevated temperatures. It adopts a NASICON-type structure in the space group R3c. The examined crystal was an obverse-reverse twin with approximately equal twin components. The [Sc(III)Zr(IV)(PO(4))(3)](2-) framework is composed of corner-sharing Sc/ZrO(6) octahedra and PO(4) tetrahedra. The Sc and Zr atoms are disordered on one atomic site on a crystallographic threefold axis. The P atom of the phosphate group lies on a crystallographic twofold axis. Nonframework Cu(+) cations occupy three positions. Two of the Cu(+) positions generate an approximately circular distribution around a site of 3 symmetry, referred to as the M1 site in the NASICON-type structure. The other Cu(+) position is situated close to the twofold symmetric M2 site, displaced into a position with a distorted square-based pyramidal coordination geometry. The structure has been determined at 100, 200 and 300 K. Changes in the refined site-occupancy factors of the Cu(+) positions suggest increased mobility of Cu(+) around the circular orbit close to the M1 site at room temperature, but no movement into or out of the M2 site. Free refinement of the Cu site-occupancy factors suggests that the formula of the crystal is Cu(1.92(1))ScZr(PO(4))(3), which is consistent with the low-level presence of Cu(2+) exclusively in the M2 site.