The known compound phenyltetrafluoroiodine (V) is shown by X-ray diffraction to have a tetragonal pyramidal structure with an apical phenyl group. This structure is compared to that of IF (OTeF5) 4, where the apical position is occupied by the fluorine atom. C6H5IF4 adds F−, forming C6H5IF5−, which has a pentagonal pyramidal structure with an apical phenyl group. Fluoride abstraction from C6H5IF4 by SbF5 results in the formation of the cation ...