HTBZ-SAC crystallized in the triclinic P-1 space group, featuring one HTBZ cation and one SAC anion in the asymmetric unit. The cation exhibited structural disorder, with a statistical distribution between a major and minor position, with occupancies of 0.91 and 0.09, respectively. The saccharinate anion's N-C-O fragment accepts two hydrogen atoms from symmetrically equivalent HTBZ cations with an H⋅⋅⋅O bond distance of 1.948(1) Å and an H⋅⋅⋅N bond distance of 2.776(2) Å. The opening angle of the N-C-O fragment allows for the close packing of HTBZ cations in a head-to-tail arrangement, stabilized by π-π interactions (Figure ). This interplay of π-π interactions and hydrogen bonding leads to the formation of HTBZ columns that characterize the crystal packing of HTBZ-SAC (Figure ). Similar structural changes resulting from saccharin's protonation have already been extensively studied .