Structure of the high-temperature phase of caesium nitrate - the importance of high-resolution data

Acta Crystallogr B Struct Sci Cryst Eng Mater. 2022 Apr 1;78(Pt 2):140-152. doi: 10.1107/S2052520622001135. Epub 2022 Mar 10.

Abstract

A single-crystal structure determination of the cubic phase of CsNO3 based on data collected at 439 K up to sinθmax/λ = 0.995000 Å-1, i.e. to an unprecedentedly high-θ value, is reported. The structure has been refined in Pm3m (Z = 1). Analysis of the difference electron-density maps revealed that the most appropriate model is the twelve-orientation model with the Cs, N, O1 and O2 atoms situated on the Wyckoff positions 1a, 6f, 6f and 24l, respectively, rather than the eight-orientation aragonite model with the Cs, N and O atoms situated on the Wyckoff positions 1a, 8g and 24m, respectively. Both models, however, show close similarities if the large anisotropic displacement parameters of the O atoms in the eight-orientation aragonite model are taken into account. The reason for this is shown to lie in the smeared electron density around the positions of the disordered [NO3]- anion.

Keywords: alkali nitrates; difference electron-density maps; eight-orientation aragonite model; positional disorder; twelve-orientation model.