Two series of sulphones, containing respectively the cyanomethylsulphonyl and the benzylsulphonyl groups, have been prepared, in which a polar methylene group is allowed on steric grounds to interact intramolecularly with a nearby donor atom. The i.r. and ¹H n.m.r. spectra of these sulphones are compared with spectra of reference compounds in which no such interaction is possible. No conclusive evidence for intramolecular hydrogen bonds is found: possible causes for the observed spectral shifts are discussed.