Abstract
The reaction of tetraethylammonium polychlorides or polybromides in propionitrile with substoichiometric amounts of diluted fluorine at low temperatures leads to the non-classical interhalogen compounds [NEt(4)]-[F-(X(2))(3)] (X = Cl and Br). These compounds are the first examples of anions containing a central μ(6) fluoride anion, which is octahedrally surrounded by Br(2) or Cl(2) units, respectively. Single-crystal X-ray diffraction revealed that these compounds crystallize in the cubic system with every fluoride anion bridged by halogen units, resulting in a 3D network. Furthermore, single-crystal Raman and IR spectra were measured, and investigations using solid-state calculations were carried out.