CsCoO2, featuring a two-dimensional layered architecture of edge- and vertex-linked CoO4 tetrahedra, is subjected to a temperature-driven reversible second-order phase transformation (α → β) at 100 K, which corresponds to a structural relaxation with concurrent tilting and breathing modes of edge-sharing CoO4 tetrahedra. In the present investigation, it was found that pressure induces a phase transition, which encompasses a dramatic change in the connectivity of the tetrahedra. At 923 K and 2 GPa, β-CsCoO2 undergoes a first-order phase transition to a new quenchable high-pressure polymorph, γ-CsCoO2. It is built up of a three-dimensional cristobalite-type network of vertex-sharing CoO4 tetrahedra. According to a Rietveld refinement of high-resolution powder diffraction data, the new high-pressure polymorph γ-CsCoO2 crystallizes in the tetragonal space group I41/amd:2 (Z = 4) with the lattice constants a = 5.8711 (1) and c = 8.3214 (2) Å, corresponding to a shrinkage in volume by 5.7% compared with the ambient-temperature and atmospheric pressure β-CsCoO2 polymorph. The pressure-induced transition (β → γ) is reversible; γ-CsCoO2 stays metastable under ambient conditions, but transforms back to the β-CsCoO2 structure upon heating to 573 K. The transformation pathway revealed is remarkable in that it is topotactic, as is demonstrated through a clean displacive transformation track between the two phases that employs the symmetry of their common subgroup Pb21
a (alternative setting of space group No. 29 that matches the conventional β-phase cell).
