Anhydrides of Real and Hypothetical [Hydroxy(R−O)iodo]benzenes

The anhydrides of [hydroxy(methanesulfonato−O)]iodobenzene (HMIB) and [hydroxy(toluenesulfonato−O)]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 I atoms vis-à-vis secondary I···O bonds were explored. The presence of delocalized bonding in groupings of O and I atoms was suggested. A linear relationship between the C−I−O angles and the I−O bond orders was observed.