Nefedovite, Na5Ca4(PO4)4F: thermal evolution, phase transition and crystal structure refinement

Nefedovite, Na₅Ca₄(PO₄)₄F, has been investigated by in situ high-temperature powder (30–690 °C) and single crystal (27–827 °C) X-ray diffraction and Raman spectroscopy. Nefedovite is tetragonal, space group I-4, a = 11.6560(2), c = 5.4062(2) Å, V = 734.50(2) ų (R₁ = 0.0149). Nefedovite is a 1D antiperovskite, since its crystal structure contains chains of corner-sharing anion-centered [FCa₄Na₂]⁹⁺ octahedra. The chains are parallel to the c direction. Nefedovite is stable up to 727 °C and undergoes a displacive phase transition in the temperature range 277–327 °C. With increasing temperature, the PO₄ tetrahedra in the crystal structure of nefedovite gradually rotate around the imaginary fourfold inversion axes aligning the O2^…O3 edge parallel to [110], which ultimately leads to the appearance of the mirror plane perpendicular to the c direction and the change of space group from I-4 (82) to I4/m (87). The crystal structure of nefedovite expands strongly anisotropically with the direction of the maximum thermal expansion oriented perpendicular to the chains of anion-centered octahedra. The information-based structural complexity analysis demonstrates that both low- and high-temperature modifications of nefedovite are structurally simple with the I_G,total value less than 100 bits per unit cell. The structural complexity decreases along the phase transition, which is typical for displacive phase transitions.