A new ionic saccharinate (sac) compound with the piperazinium dication (H(2)ppz)(sac)(2) (1), has been synthesized and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2(1)/c and consists of the (sac)(-) monoanion and (H(2p)pZ)(2+) dication. In addition to the ionic interactions, the ions are linked by strong N-H...O hydrogen bonds involving the NH hydrogen atoms of (H(2)ppZ)(2+) and the sulfonyl O atoms of (sac)(-). The intermolecular interactions are further reinforced by weak aromatic pi(sac)...pi(sac) stacking interactions, giving rise to a three-dimensional network. Molecular structure and vibrational frequencies of 1 have also been investigated by density functional theory (DFT) calculations using GAUSSIAN 03. Calculated frequencies are in good agreement with the corresponding experimental data.