We report the temperature-dependent synchrotron based x-ray diffraction analysis of NASICON type ${\mathrm{Na}}_3\mathrm{FeCr}{\left({\mathrm{PO}}_4\right)}_3$ sample, which undergoes a symmetry-lowering structural transition from a monoclinic ($C2/c$) phase with long-range Na-vacancy order to a rhombohedral ($R\overline{3}c$) phase with statistical disordered Na ions. The [FeCr(${\mathrm{PO}}_4{)}_3$] polyanionic framework remains essentially unchanged, confirming that the transition is governed by redistribution of the Na sublattice rather than by reconstruction of the host framework. The structural evolution is accompanied by a discontinuous increase in the $c$ axis and the unit-cell volume, reflecting the progressive depopulation of the Na(1) sites and transfer of Na ions toward the Na(2) sublattice. The temperature dependence of superstructure intensity is found to deviate from mean-field critical behavior, instead, the experimental evolution is accurately captured by a sigmoidal phase-fraction model. The calorimetric measurements show that the enthalpy change for the first transition around 350 K is significantly larger than that of the anomaly around 445 K, indicating the dominant configurational rearrangement of Na ions occurs within the lower-temperature interval. Overall, the diffraction and calorimetric results demonstrate that Na ordering proceeds through an order-disorder transition involving intermediate Na configurations and a finite coexisting regime. The quantitative correlation between Na-vacancy ordering, lattice strain, and symmetry lowering reveals the central role of configurational interactions within the Na conduction channels in governing the phase stability of NASICON-type materials.

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• Phase transitions
• Structural properties
• Batteries
• Ionic solids
• Differential scanning calorimetry
• X-ray diffraction