Abstract: | The title compound, [Ag2(NO3)2(C5H5NS)]n, was obtained from the reaction of silver nitrate with bis(4‐pyridyl) disufide (4‐PDS) in a mixture of ethanol and water, which suggests that the disulfide bond of 4‐PDS can be cleaved under mild conditions. The structure of the title compound is a two‐dimensional infinite array in which the asymmetric unit contains two Ag atoms, a pyridinium‐4‐thiolate molecule and two nitrate groups. Each pyridinium‐4‐thiolate molecule acts as a μ4 bridge, linking four Ag atoms, with Ag—S bond distances of 2.4870 (19), 2.5791 (19), 2.5992 (19) and 2.848 (2) Å. The Ag⋯Ag distances lie in the range 2.889 (2)–3.049 (1) Å. |