Reaction of sulfonium ylides (Me)(2)SCHC(O)C(6)H(4)R (R = H; m-NO(2); p-NO(2); p-OMe; p-Me and p-Br) with AgNO(3) in dichloromethane leads to various compounds. Single crystal X-ray diffraction analysis reveals that the adducts take 3 forms: (i) two-dimensional polymer, [AgNO(3)(Me(2)SCHC(O)C(6)H(5))](n) (1), with nitrate bridges in which each nitrate coordinates to three silver atoms through two oxygen atoms and two Me(2)SCHC(O)C(6)H(5) ligands coordinate to silver centers through carbon atoms; (ii) cationic binuclear, [Ag(Me(2)SCHC(O)C(6)H(4)-m-NO(2))(2)](2)(NO(3))(2)·2H(2)O (2), in which Me(2)SCHC(O)C(6)H(4)-m-NO(2) ligands simultaneously coordinate through both carbon and oxygen atoms with nitrate as a counter ion, and (iii) cationic mononuclear and anionic binuclear, [Ag(Me(2)SCHC(O)C(6)H(4)-p-NO(2))(2)](2)[{AgNO(3)(μ-NO(3)) (Me(2)SCHC(O)C(6)H(4)-p-NO(2))}(2)]·2CH(3)OH (3), in which nitrate groups act as bridging as well as terminal ligands, and Me(2)SCHC(O)C(6)H(4)-p-NO(2) ligands display C-coordination. Characterization of the obtained compounds was also performed by infrared, (1)H- and (13)C-NMR spectroscopy and analytical data indicated a 1 : 2 stoichiometry between the silver(I) nitrate and ylide p-OMe (4) and 1 : 1 for ylides p-Me (5) and p-Br (6). In addition, the antibacterial effects of DMSO-solutions of complexes 1-6 were evaluated by the agar disc diffusion method against three Gram positive and three Gram negative bacteria. All complexes displayed antibacterial activity against these bacteria, with high levels of inhibitory potency exhibited against the Gram negative species.