Abstract: This contribution addresses standing questions about the nature and consequences of the ion self-assembly and magnetic structures, as well as the molecular motion of the crystalline structure as a function of the temperature, in halometalate materials based on imidazolium cation. We present the magnetic structure and magnetostructural correlations of 1-ethyl-2,3-dimethylimidazolium tetrachloridoferrate, (Edimim)[FeCl4], resolved by neutron diffraction studies. Single-crystal, synchrotron powder X-ray diffraction and powder neutron diffraction techniques have been combined to follow the temperature evolution on its crystallographic structure from 2 K close to its melting point (340 K). In this sense, slightly above room temperature (307 K) (Edimim)[FeCl4] presents a single-crystal to single-crystal transition (SCSC), from phase I (space group P21/n) to phase II (P21/m), accompanied by a notable increase in the disorder of the imidazolium cation, as well as in the metal complex anion. The temperature evolution and solid-phase transitions of the presented compound were followed in detail by synchrotron X-ray powder diffraction (SXPD), which confirms the occurrence of another phase transition at 330 K, phase III (P21/m), the crystal structure of which was elucidated from the SXPD pattern. Moreover, this material presents an anisotropic thermal expansion with a switch from axial positive to negative thermal expansion coefficients as the temperature is raised above the first phase transition, which has been correlated with the molecular motion of the imidazolium-based molecules, producing not only a shortening of the counterion···counterion distances but also the occurrence of different quasi-isoenergetic crystal structures as a function of the temperature.

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