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Recent optical and differential scanning calorimetry measurements indicate phase transitions in leonite-type compounds at low temperatures. The crystal structures of these phases, i.e., leonite, K 2 Mg(SO 4 ) 2 ⋅4H 2 O, “Mn-leonite”, K 2 Mn(SO 4 ) 2 ⋅4H 2 O, and mereiterite, K 2 Fe(SO 4 )2⋅4H 2 O, have been determined at low temperatures. The leonite structure (space group C2/m at room temperature) is composed of sulfate tetrahedra and MeO 6  octahedra which are interconnected by K cations and hydrogen bonds of the H 2 O molecules. Previous structure investigations at room temperature have shown that one of the sulfate groups is disordered. Refinements of single-crystal X-ray data at ambient and low temperatures indicate that the dynamic disorder in leonite and “Mn-leonite” is “frozen” in two steps and thus results in two new, ordered structures at low temperatures. In mereiterite only one transition from the dynamically disordered to the ordered structure is observed.

The crystal structures of the low-temperature phases of leonite-type compounds, K 2 Me(SO 4 ) 2 ·4H 2 O (Me 2+ = Mg, Mn, Fe)