Supramolecular fluoride and chloride anions

The Cambridge Structural Database has been searched for supramolecular anions of the form HnXn + 1− where X is fluorine (n = 1 to 6) and chlorine (n = 1 to 5); no credible evidence was found for comparable bromine or iodine species. Several structural isomers have been identified, and an experimental measure has been developed which seems to distinguish between two-centre and three-centre bonded species. There are also examples of suprafluoride and suprachloride anions as ligands in organometallic complexes. Most of these anions have not been previously described.