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The title compound, C13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-dinitrophenol and p-toluenesulfonyl chloride. This crystal structure is a polymorph of CSD entry WUVYUH [Vembu et al. (2003). Acta Cryst, E59, o378–380]. The aromatic substituents on the sulfonate group are oriented gauche to one another with a C—O—S—C torsion angle of −62.0 (3)°. The supramolecular features that contribute to the crystal stability are offset π–π [centroid–centroid distance = 3.729 (2) Å] and multiple C—H...O interactions.