A new monoclinic form of the title compound, C14H17N3O3S, has been found upon slow crystallization from water. Another monoclinic form of the compound was obtained previously from a mixture of dichloromethane and diethyl ether [Clerici et al. (2002 ▶). Tetrahedron, 58, 5173–5178]. Both phases crystallize in space group P21/n with one molecule in the asymmetric unit. The formally single exocyclic C—N bond that connects the –NEt2 unit with the thiazete ring is considerably shorter than the adjacent, formally double, endocyclic C=N bond. This is likely to be due to the extended conjugated system between the electron-donor diethylammine fragment and the electron-withdrawing sulfonyl group. In the newly discovered polymorph, the methoxy group is rotated by almost 180° around the phenyl–OCH3 bond, resulting in a different molecular conformation.