Correlated proton disorder in the crystal structure of the double hydroxide perovskite CuSn(OH)$_6$

TL;DR

This study reveals the crystal structure of CuSn(OH)$_6$, a frustrated magnetic double perovskite hydroxide, showing correlated proton disorder constrained by ice rules, and how pressure influences proton ordering.

Contribution

The paper provides the first crystal structure model of CuSn(OH)$_6$ with correlated proton disorder and demonstrates pressure-induced proton-ordering transitions.

Findings

Proposed an orthorhombic structure with correlated proton disorder constrained by ice rules.

Pressure suppresses proton disorder through proton-ordering transitions.

Structural distortions partially relieve magnetic and protonic frustration.

Abstract

CuSn(OH)$_6$ is a quantum spin system from the family of magnetic double perovskite hydroxides, having a frustrated magnetic sublattice. It is also known as the natural mineral mushistonite, whose crystal structure has remained elusive for decades. Here we employ x-ray and neutron powder diffraction to solve the crystal structure of CuSn(OH)$_6$ and propose a structure model in the orthorhombic space group $Pnnn$ with correlated proton disorder. The occupation of the hydrogen sites in the structure is constrained by ``ice rules'' similar to those known for water ice. The resulting frustration of the hydrogen bonding network is likely to have a complex and interesting interplay with the strong magnetic frustration expected in the face-centred magnetic sublattice. Structural distortions, which are quite pronounced in Cu$^{2+}$ compounds due to the Jahn-Teller effect, partially alleviate both types of frustration. We also show that hydrostatic pressure tends to suppress proton disorder through a sequence of proton-ordering transitions, as some of the split hydrogen sites merge already at 1.75 GPa while others show a tendency toward possible merging at higher pressures.