The anhydrides of [hydroxy(methanesulfonato-O)]iodobenzene (HMIB) and [hydroxy(toluenesulfonato 0)]iodobenzene (HTIB) were prepared by drying acetonitrile solutions of the compounds. The anhydrides of the hypothetical compounds [hydroxy(chloroacetato) O]iodobenzene and [hydroxy(iodoacetato) O]iodobenzene were obtained from aqueous solutions. Crystallographic structures were obtained for the anhydrides, except that of HTIB. The electron-domain geometries of the 1 atoms vis-a-vis secondary I center dot center dot center dot O bonds were explored. The presence of delocalized bonding in groupings of 0 and I atoms was suggested. A linear relationship between the C-I-O angles and the I-O bond orders was observed.