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 C6H5IF3+, which has a pseudotrigonal bipyramidal structure with the phenyl group occupying an equatorial position. Isoelectronic C6H5IOF2 has a similar structure, with the phenyl group and oxygen atom both occupying equatorial positions. (C) 2003 Elsevier B.V. All rights reserved.