Crystal structures of γ-, β- and α-Sr2B2O5 polymorphs resulting from the γ ↔ (at 565 K) β ↔ (at 637 K) α′ ↔ (at 651 K) α sequence of reversible first-order phase transitions are studied by high-temperature single-crystal X-ray diffraction, high-temperature X-ray powder diffraction, differential scanning calorimetry and impedance spectroscopy. Out of these phases, the structure of γ-Sr2B2O5 was already known whereas the structures of β- and α-Sr2B2O5 were determined for the first time. The sequence of phase transitions is associated with an unusual change of symmetry, with triclinic intermediate β-Sr2B2O5 phase and monoclinic low-temperature γ-Sr2B2O5 as well as high-temperature α-Sr2B2O5 phase. Taking the α-Sr2B2O5 phase with space group P21/c as a parent structure, the γ-Sr2B2O5 phase was refined as a twofold superstructure with symmetry P21/c, whereas the β-Sr2B2O5 phase was a sixfold superstructure with symmetry P{\overline 1}. To construct a unified structure model for all Sr2B2O5 modifications, phases of γ- and β-Sr2B2O5 were also refined as commensurately modulated structures using the basic unit cell of the parent α-Sr2B2O5. The phase transitions are related to the orientational order–disorder arrangement of B2O5 pyroborate groups, where the degree of disorder grows towards the high-temperature phase. Thermal expansion is strongly anisotropic and dictated by preferable orientations of BO3 triangles in the structure. The intermediate phase α′-Sr2B2O5, stable over a narrow temperature range (637–651 K), features the largest anisotropy of expansion for the known borates: α11 = 205, α22 = 57, α33 = −81 × 10−6 K−1.
Orientational order-disorder γ ↔ β ↔ α′ ↔ α phase transitions in Sr2B2O5 pyroborate and crystal structures of β and α phases