Key indicatorsSingle-crystal X-ray study T = 297 K Mean (C-C) = 0.003 Å R factor = 0.043 wR factor = 0.110 Data-to-parameter ratio = 21.7For details of how these key indicators were automatically derived from the article, see

The title compound, C15H16NO2+·C6H4ClO3S−, is isomorphous with the 4‐bromo­benzene­sulfonate derivative. The cation is almost planar and the benzene ring of the anion makes dihedral angles of 82.79 (1) and 76.39 (1)° with the mean planes through the benzene ring of the cation and the pyridinium ring, respectively. The cations and anions are packed as alternate layers parallel to the ac plane. These layers are inter­connected through O—H⋯O, C—H⋯O and C—H⋯π inter­actions to form a three‐dimensional network.

Key indicatorsSingle-crystal X-ray study T = 293 K Mean (C-C) = 0.004 Å R factor = 0.035 wR factor = 0.092 Data-to-parameter ratio = 15.6For details of how these key indicators were automatically derived from the article, see

In the title compound, C14H14NO+·C7H7O3S−, the cation is almost planar and adopts an E configuration. In the crystal structure, the cations and anions are packed as alternate layers parallel to the ac plane. These layers are inter­connected through O—H⋯O, C—H⋯O and C—H⋯π inter­actions, forming a three‐dimensional supramol­ecular network.

Organic molecules that exhibit second-order nonlinear optical (NLO) properties usually consist of a frame with a delocalized π system, and end-capped with either a donor or an acceptor substituent or both. The most important requirement for these materials to exhibit second-order NLO properties is for the molecules to be oriented in a non-centrosymmetric environment. 1 Benzenesulfonate is frequently used to co-crystallize with cations to form compounds which are expected to have NLO properties. 2 Our continuing research on non-linear optical materials 3,4 has led us to synthesize the title compound x27