Six piperazinium salts, namely 4-(4-nitro-phenyl)-piperazin-1-ium 4-bromo-ben-zo-ate dihydrate, C10H14N3O2 +·C7H4BrO2 -·2H2O, (I), 4-(4-nitro-phenyl)-pi-per-a-zin-1-ium 4-iodo-benzoate dihydrate, C10H14N3O2 +·C7H4IO2 -·2H2O, (II), 4-(4-nitro-phenyl)-piperazin-1-ium 4-hy-droxy-benzoate monohydrate, C10H14N3O2 +·C7H5O3 -·H2O, (III), 4-(4-nitro-phenyl)-piperazin-1-ium 4-methyl-benzoate monohydrate, C10H14N3O2 +·C8H7O2 -·H2O, (IV), 4-(4-nitro-phenyl)-piperazin-1-ium 4-meth-oxy-benzoate hemihydrate, 2C10H14N3O2 +·2C8H7O3 -·H2O, (V), and 4-(4-nitro-phenyl)-piperazin-1-ium 4-eth-oxy-benzoate, 2C10H14N3O2 +·2C9H9O3 -, (VI), have been synthesized and their crystal structures solved by single-crystal X-ray diffraction, revealing that all of them crystallize in the triclinic space group P except for (V), which crystallizes in the monoclinic space group P21/c and has a disordered nitro group. Compounds (I) and (II) are isostructural. The crystal packing of (I)-(V) is constructed from organic chains formed by a combination of hydrogen bonds of type N-H⋯O and/or O-H⋯O and other weak inter-actions of type C-H⋯O and/or C-H⋯π, forming sheets, whereas (VI) shows a cationic and anionic-based layer structure.