Abstract: | The synthesis is reported of the tricarboxylic acid 3‐(3,5‐dicarboxybenzyloxy)benzoic acid (H3L) and the product of its reaction under solvothermal conditions with ZnII cations, namely poly[[μ6‐3‐(3,5‐dicarboxylatobenzyloxy)benzoato](dimethylformamide)‐μ3‐hydroxido‐dizinc(II)], [Zn2(C16H9O7)(OH)(C3H7NO)]n, the formation of which is associated with complete deprotonation of H3L. Its crystal structure consists of a single‐framework coordination polymer of the organic L3− ligand with ZnII cations in a 1:2 ratio, with additional hydroxide and dimethylformamide (DMF) ligands coordinated to the ZnII centres. The ZnII cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxylate‐ and hydroxy‐bridged ZnII cations are arranged in coordination‐tessellated columns, which propagate along the a axis of the crystal structure, and each L3− ligand links to seven different ZnII centres via Zn—O bonds of two different columns. The coordination framework, composed of [Zn2(L)(OH)(DMF)]n units, forms an open architecture, the channel voids within it being filled by the zinc‐coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H3L via multiple metal–ligand bonds through its carboxylate groups. |