Crystal structure and composition of hiärneite, Ca2Zr4Mn3+SbTiO16, and constitution of the calzirtite group

Abstract

AbstractThe crystal structure of hiärneite has been refined from single-crystal X-ray diffraction data (λ = 0.71073 Å) on type material from Långban, Värmland, Sweden. The refinement converged to R1 = 0.046 based on 1073 reflections with F2 > 4σ(F2). The tetragonal unit cell, space group I41/acd, has the parameters a = 15.2344(6) Å and c = 10.0891(6) Å with Z = 8. The mineral is isostructural with calzirtite, ideally Ca2Zr5Ti2O16, with a structural topology derived from fluorite. In hiärneite, Mn3+ is ordered at a 4- to 8-fold coordinated site (with a distorted polyhedral coordination figure), without the atom splitting encountered at the corresponding Zr-dominated site of calzirtite. The end-member formula for hiärneite is established as Ca2Zr4Mn3+SbTiO16. The calzirtite group, with calzirtite, hiärneite and tazheranite (cubic ZrO2-x), has been approved by the IMA–CNMNC.