Two bismuth(III) compounds of ciprofloxacin (cf) were synthesized. The crystal structure of one--(cfH2) (cfH) [BiCl6].2H2O (cfH2 = doubly protonated molecule of cf, cfH = protonated molecule of cf)--is presented and discussed. The compound crystallizes in the monoclinic space group P 21/c with a = 17.758(4), b = 7.600(10), c = 31.908(6) A, beta = 101.03(2)0, Z = 4. The charge of the isolated hexachlorobismuthate(III) anions is compensated with protonated of molecules (ionic interactions). One of the cf molecules is protonated at carbonyl oxygen O(1) and nitrogen N(24) of the piperazine residue, and the other at N(24) only. Two water molecules participate in the hydrogen bond network. Antimicrobial activity of this compound was tested against different microorganisms. The results of TG and FT-IR measurements are also included.