Structure and phase transitions in chloroantimonate(V) crystals: [(C2H5)3NH]SbCl6 and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl Original Research Article

New triethylammonium salts: [(C2H5)3NH]SbCl6 (TCA) and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P21/n and P21/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C2H5)3NH]SbCl6 consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N–H⋯Cl hydrogen bonds. The crystal structure of [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.