Crystal structure elucidation of a geminal and vicinal bis(trifluoromethanesulfonate) ester

Geminal and vicinal bis(trifluoromethanesulfonate) esters are highly reactive alkylene synthons used as potent electrophiles in the macrocyclization of imidazoles and the transformation of bypyridines to diquat derivatives via nucleophilic substitution reactions. Herein we report the crystal structures of methylene (C3H2F6O6S2) and ethylene bis(trifluoromethanesulfonate) (C4H4F6O6S2), the first examples of a geminal and vicinal bis(trifluoromethanesulfonate) ester characterized by single-crystal X-ray diffraction (SC-XRD). With melting points slightly below ambient temperature, both reported bis(trifluoromethanesulfonate)s are air- and moisture-sensitive oils and were crystallized at 277 K to afford two-component non-merohedrally twinned crystals. The dominant interactions present in both compounds are non-classical C-H center dot center dot center dot O hydrogen bonds and intermolecular C-F center dot center dot center dot F-C interactions between trifluoromethyl groups. Molecular electrostatic potential (MEP) calculations by DFT-D3 helped to quantify the polarity between O center dot center dot center dot H and F center dot center dot center dot F contacts to rationalize the self-sorting of both bis(trifluoromethanesulfonate) esters in polar (non-fluorous) and non-polar (fluorous) domains within the crystal structure.