Phase transitions in compounds with the Ca3Ga2Ge4O14 structure

Possible structural changes described by the group-subgroup relationships in the Ca3Ga2Ge4O14-type structure (sp. gr. P321) are considered. The most probable phase transitions seem to be those accompanied by lowering of the symmetry to the maximal non-isomorphic subgroups P3 and C2. It is shown that only destructive phase transitions accompanied by symmetry rise up to the minimal non-isomorphic supergroups for the given structure type can take place. The change of the trigonal symmetry to monoclinic is revealed in La3SbZn3Ge2O14, whose crystal structure is refined as a derivative structure of the Ca3Ga2Ge4O14 structure type within the sp. gr. A2 (C2). At ∼250°C, La3SbZn3Ge2O14 undergoes a reversible phase transition accompanied by symmetry rise, A2 ⇄ P321. Similar phase transitions, P321 ⇄ A2, are also observed in La3Nb0.5Ga5.5O14 and La3Ta0.5Ga5.5O14 under the hydrostatic pressures 12.4(3) and 11.7(3) GPa, respectively. The mechanisms of compression and phase transition are based on the anisotropic compressibility of a layer structure. With the attainment of the critical stress level in the structure, the elevated compressibility in the (ab) plane gives rise to a phase transition accompanied by the loss of the threefold axis. Attempts to reveal low-temperature phase transitions in a number of representatives of the langasite family have failed.