Supramolecular networks are an important subset in the field of coordination polymer (CP) frameworks and are widely encountered in crystal engineering research. The search for novel topologies continues to be a significant goal in CP chemistry. The dimeric compound bis(μ-5-carboxybenzene-1,3-dicarboxylato-κ2O1:O3)bis[(triethanolamine-κ4N,O,O′,O′′)cobalt(II)], [Co2(C9H4O6)2(C6H15NO3)2], formed from the coligands 5-carboxybenzene-1,3-dicarboxylate (tmaH2−) and triethanolamine (teaH3), namely [Co(μ2-tmaH)(teaH3)]2, was synthesized and characterized by single-crystal and powder X-ray diffraction analyses, IR spectroscopy, thermogravimetric analysis (TGA) and magnetic measurements. The crystal structure features a zero-dimensional molecular structure consisting of centrosymmetric macrocyclic dinuclear complexes. Four classical hydrogen bonds between carboxylate groups and hydroxyethyl arms stabilize and extend the molecules into a two-dimensional supramolecular network. The topological analysis indicates that an unreported (3,5)-binodal supramolecular topology with a short Schläfli symbol of (4.5.6)(4.55.63.7) can be achieved by means of intermolecular hydrogen bonds. The crystal structure accounts for the potential to obtain unique topological types from two excellent hydrogen-bonding candidates,i.e.tmaH3and teaH3. A variable-temperature magnetic study shows the existence of antiferromagnetic behaviour in the complex.