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In the title salt, C12H11N2O2+·C7H5O6S, the dihedral angle between the benzene and pyridine rings in the 4-(4-nitro­benz­yl)pyridinium cation is 82.7 (2)°. Within the anion there is an intramolecular hydroxy-O—H...O(carboxylic acid) bond. In the crystal, the cation forms a single N+—H...Osulfonate hydrogen bond with the anion. These cation–anion pairs inter­act through duplex anion carb­oxy­lic acid O—H...Osulfonate hydrogen bonds, giving a centrosymmetric cyclic association [graph set R22(16)]. The crystals studied were non-merohedrally twinned.

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In the asymmetric unit of the title co-crystal, C12H14N4O2S·C7H5NO4, the sulfamethazine and 2-nitro­benzoic acid mol­ecules form a heterodimer through inter­molecular amide–carb­oxy­lic acid N—H...O and carb­oxy­lic acid–pyrimidine O—H...N hydrogen-bond pairs, giving a cyclic motif [graph set R22(8)]. The dihedral angle between the two aromatic ring systems in the sulfamethazine mol­ecule is 88.96 (18)° and the nitro group of the acid is 50% rotationally disordered. Secondary aniline N—H...Osulfone hydrogen-bonding associations give a two-dimensional structure lying parallel to the ab plane.
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