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New CaCrO3−δ superstructure phases (δ = 0.33, 0.4, and 0.5) have been discovered through ‘soft’ low temperature reduction of the perovskite CaCrO3 made at ‘hard’ high pressure–temperature conditions. Their structures form a related series based on stacking of octahedral and tetrahedral chromium oxide layers.

Graphical abstract: Hard–soft synthesis of a new series of vacancy-ordered perovskites, CaCrO3−δ

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