Description:
<jats:title>Abstract</jats:title><jats:p>The high temperature modification of lithium triflate (γ‐LiSO<jats:sub>3</jats:sub>CF<jats:sub>3</jats:sub>) crystallises in the orthorhombic space group <jats:italic>Cmca</jats:italic> with the lattice parameters a = 6.3022(4), b = 8.6989(5), and c = 20.1262(14) Å (synchrotron powder diffraction data, T = 456 K). The crystal structure of γ‐LiSO<jats:sub>3</jats:sub>CF<jats:sub>3</jats:sub> is disordered, in the cationic as well as the anionic partial structure, and exhibits double layers of triflate anions with the lipophilic CF<jats:sub>3</jats:sub>‐groups facing each other. The lithium ions could not be located by the diffraction experiment due to their high mobility. The staggered triflate anion is twofold disorderd leading to two different positions on top of each other which are tilted to one another.</jats:p>