Key indicators: single-crystal X-ray study; T = 100 K; mean (C-C) = 0.002 Å; R factor = 0.033; wR factor = 0.093; data-to-parameter ratio = 20.3.The title compound, C 7 H 8 NO 2 + ÁH 2 PO 3 À , is formed from alternating layers of organic cations and inorganic anions stacked along the a-axis direction. They are associated via O-HÁ Á ÁO, N-HÁ Á ÁO and C-HÁ Á ÁO hydrogen bonding, giving rise to two different R 2 2 (8) graph-set motifs and generating a three-dimensional network. Related literature ExperimentalCrystal data

The cohesion in the title structure (p‐CPABS), C7H8NO2+·HSO4−, is assured by an intricate three‐dimensional hydrogen‐bonded network of types N—H...O and O—H...O involving anions, carboxyl and amino groups in addition to the ionic interactions.

The structure of the title compound, C7H8NO2+·H2PO4−, shows that a single proton transfer occurs. The anions and cations are held together via strong and short O—H...O hydrogen bonds, in addition to N—H...O interactions. The three‐dimensional complex network of hydrogen bonds ensures the cohesion of the ionic structure.

The crystal structure analysis of the title compound, C7H8NO2+·H2PO4−, has revealed a three‐dimensional hydrogen‐bonded network structure, involving the dihydrogenphosphate anions, the carboxyl groups and the ammonium groups. The anions are held together via strong O—H...O hydrogen bonds. In addition to the N—H...O and O—H...O interactions, involving all the H atoms covalently bonded to the anion, the nitrogen and the carboxyl group, the crystal structure is also stabilized by C—H...O and C—H...π short contacts.

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