High-pressure structural behavior of ingersonite, Ca3Mn2+Sb5+4O14: An in-situ single-crystal X-ray study
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Pier Francesco Zanazzi
,
Laura Chelazzi
Abstract
An in-situ, high-pressure, single-crystal X-ray diffraction study has been carried out at room temperature up to 7.42 GPa on a crystal of ingersonite, ideally Ca3Mn2+Sb5+4O14, from the type material. Ingersonite is isostructural with the synthetic weberite-3T polytype and related to the pyrochlore structure-type. Owing to the P range investigated and the quality of data, a second-order Birch- Murnaghan Equation of State (EoS) is the best approximation to describe the ingersonite volume evolution with P. The refined EoS parameters are V0 = 810.6(1) Å3 and K0 = 154.5(2.4) GPa. The behavior of ingersonite with pressure is almost isotropic and the decrease of the unit-cell volume is mainly due to the kinking of the polyhedra rather than their volume decrease. The overall mean distances are quite constant, indicating virtually no compressibility of both the A and B polyhedra in the P range investigated. However, some geometrical changes in the pyrochlore-like AB3 layer can be observed and compared with those observed in synthetic pyrochlore compounds. The largest change is observed for the z atomic coordinate of the O2 atom. Using an anion-centered polyhedral description, O2 is the only O atom that is asymmetrically located in an octahedral interstice, this feature being the most remarkable difference between the structure of ingersonite (i.e., weberite-3T type, space group P3121) and that of zirconolite-3T (pyrochlore structure type, space group P3121), where all the O atoms occupy the tetrahedral interstices of a cubic A2B2 array. With the increase of pressure, the O2 atom migrates from the A4B2 octahedral cavity toward the adjacent AB3 tetrahedral cavity, suggesting that a transition from weberite-3T to zirconolite-3T structure type could occur at pressures higher than 11 GPa.
© 2015 by Walter de Gruyter Berlin/Boston
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