Anomalous dielectric behaviour in centrosymmetric organic–inorganic hybrid chlorobismuthate(III) containing functional N,N-dimethylethylammonium ligand. Crystal structure and properties

Graphical abstract: Display Omitted Highlights: ► Novel organic–inorganic hybrid chlorobismuthate(III). ► Unprecedented dielectric response in non-polar material. ► Dielectric relaxation characterized by an exceptionally large dielectric increment. ► The NMR measurements confirmed dynamic disorder of cations. -- Abstract: The structure of [C{sub 2}H{sub 5}NH(CH{sub 3}){sub 2}{sup +}]{sub 3}[BiCl{sub 6}{sup −}] (abbreviated as DCB) was determined by a single-crystal X-ray diffraction at 115 K. The compound adopts tetragonal symmetry with the space group I4{sub 1}/acd; a = 23.35 Å, c = 17.60 Å, V = 9598 Å{sup 3} and Z = 16. The crystal structure of DCB is built up of isolated [BiCl{sub 6}]{sup 3−} units and N,N-dimethylethylammonium counterions that are accommodated in the large voids. At ambient temperature two-thirds of the counterions appear to be dynamically disordered. Dynamics of this type of cations contributes to the enhanced dielectric permittivity of DCB. A low frequency dielectric relaxation process that takes place between 200 and 300 K is characterized by an exceptionally large dielectric increment, Δe > 100, which is unprecedented in nonferroelectric materials. The molecular motions of the N,N-dimethylethylammonium cations were studied by means of {sup 1}H NMR spin-lattice relaxation time measurements.