On the Colossal and Highly Anisotropic Thermal Expansion Exhibited by Imidazolium Salts PedroI. de García-SaizA. DupontJ. MigowskiP. VallcorbaO. JunqueraJ. RiusJ. Rodríguez FernándezJ. 2015 The imidazolium salts 1-ethyl-2,3-dimethylimidazolium chloride, Edimim­[Cl], and bromide, Edimim­[Br], exhibit negative and positive thermal expansions, as determined by variable-temperature synchrotron powder X-ray diffraction experiments. Both compounds crystallize in the same monoclinic centrosymmetric space group, showing an anisotropic H-bonding network and imidazolium–imidazolium π<sup>+</sup>–π<sup>+</sup> interactions, which have been corroborated by density functional theory studies. The chloride derivative displays a highly anisotropic thermal expansion with a colossal positive coefficient along one direction. Replacement of Cl<sup>–</sup> by Br<sup>–</sup> in the same crystal structure produces an increase of the colossal coefficient and induces a biaxial negative thermal expansion. By studying the molecular vibration factors and the H-bonding framework in their crystals as a function of temperature, it was possible to rationalize at the molecular level the mechanism for the observed anomalies in thermal expansion.