Abstract: | The title compound, Ag(C15H11N4O2S)]n, was synthesized by the reaction of 4‐{(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoic acid (Hptmba) with silver nitrate and triethylamine at room temperature. The asymmetric unit contains one crystallographically independent AgI cation and one ptmba− ligand. Each AgI cation is tricoordinated by two carboxylate O atoms and one tetrazole N atom from three different ptmba− ligands, displaying a distorted T‐shaped geometry. Three AgI cations are linked by tris‐monodentate bridging ptmba− ligands to form a one‐dimensional double chain along the c axis, which is further consolidated by an intrachain π–π contact with an offset face‐to‐face distance of 4.176 (3) Å between the centroids of two adjacent aromatic rings in neighbouring benzoate groups. The one‐dimensional chains are linked into a three‐dimensional supramolecular framework by additional π–π interchain interactions, viz. of 3.753 (3) Å between two phenyl substituents of the tetrazole rings and of 4.326 (2) Å between a benzoate ring and a tetrazole ring. Thermogravimetric analysis and the fluorescence spectrum of the title compound reveal its good thermal stability and a strong green luminescence at room temperature. |