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Ten years have passed since the description of the perovskite topost-perovskite transition in MgSiO3 and its' impact on the mineralogy andrheology of the D" region at the base of the Earth's mantle. Much work hasexplored the mechanisms operating during this transformation and theirinfluence on seismic response. In parallel, calculations in ABX3 systems haveidentified potential structures for a denser post-post-perovskite phaseoccurring at higher pressures. However, experiments have yet to elucidate anyhigher pressure form, beyond the CaIrO3-type. Here we describe the structuresand transformations that lead to the crystallisation of a post-post-perovskiteof Sb2S3-type in a GdFeO3-type fluoroperovskite at high pressure conditions.The use of single-crystal techniques gives unique access to the relativecrystallographic orientations of all polymorphs. We use this information toextend this description to include other calculated and observed forms that arecompetitive in ABX3 and A2X3 stoichiometries (e.g. Sb2S3, a-Gd2S3, Be3N2) andprovide substantial information on inter-relationships between thesestructures, which is critical to the interpretation of transition mechanisms,predicting transition sequences, to the expression of directional properties inthose transformed structures when assessing their suitability to modelling e.g.their rheological response in deep-Earth and exoplanet interiors.

Observation of the Sb2S3-type post-post-GdFeO3-perovskite: A model structure for high density ABX3 and A2X3 phases