Norfloxacin and ciprofloxacin crystallize with phosphoric acid in aqueous solution to give the salts 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-1,4-dihydro-7-quinolyl)piperazinium dihydrogenphosphate monohydrate, C16H19FN3O3(+) x H2PO4(-) x H2O, and 4-(3-carboxy-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydro-7-quinolyl)piperazinium dihydrogenphosphate monohydrate, C17H19FN3O3(+) x H2PO4(-) x H2O, respectively. In the crystal structures, the phosphate anions and the piperazine rings of norfloxacin or ciprofloxacin form a 12-membered supramolecular synthon, viz. R4(4)(12). The synthons R4(4)(12) and R2(2)(8) formed between adjacent phosphate anions result in the three-dimensional structures.