Abstract: | A novel infinite one‐dimensional silver cylinder, namely polyμ‐ethylenediamine‐μ5‐(2‐sulfanidylbenzoato)‐μ4‐(2‐sulfanidylbenzoato)‐tetrasilver(I)], Ag4(C7H4O2S)2(C2H8N2)]n, has been synthesized by one‐pot reaction of equivalent molar silver nitrate and 2‐mercaptobenzoic acid (H2mba) in the presence of ethylenediamine (eda). One Ag atom is located in an AgS2NO four‐coordinated tetrahedral geometry, two other Ag atoms are in an AgS2O three‐coordinated T‐shaped geometry and the fourth Ag atom is in an AgSNO coordination environment. The two mba ligands show two different binding modes. The μ2‐N:N′‐eda ligand, acting as a bridge, combines with mba ligands to extend the AgI ions into a one‐dimensional silver cylinder incorporating abundant Ag...Ag interactions ranging from 2.9298 (11) to 3.2165 (13) Å. Interchain N—H...O hydrogen bonds extend the one‐dimensional cylinder into an undulating two‐dimensional sheet, which is further packed into a three‐dimensional supramolecular framework by van der Waals interactions; no π–π interactions were observed in the crystal structure. |