The synthesis and characterization of crystalline coordination polymers has attracted substantial interest because of the potentially useful adsorbent, magnetic or optical properties of these materials. The choice of appropriate ligands plays crucial for constructing of multinuclear compounds. Thereby, we have selected the 2,2'-dithiodibenzoic acid (H2dtdb) for this study based on its multifunctionality: (1) the carboxylate groups can show different coordination modes, (2) the S–S bond makes the ligand flexible and (3) cleavage of the C–S and S–S bonds allow the fabrication of exciting coordination polymer topologies. Sometimes, after cleaving of C-S and S-S bonds, together with the newly obtained ligands, the extruded S atom is oxidized to the sulphate ion [1]. Being in line with these investigations we report herein the products of interaction of tetrafluoroborate Cu(II) with H2dtdb in the presence of 1,2-bis(4-pyridyl)ethane (bpe) ligand, under the same solvothermal conditions (Scheme). The structures of obtained crystals have been characterized by single-crystal X-ray diffraction (Table) and show that compound 1 represents a mononuclear compound, while 2 and 3 are 1D and 2D coordination polymers, respectively.FormulaThe Cu(II) atom in 1 has a distorted octahedral N2O4 geometry going from two bidentate-chelate Htdb^– anions and two neutral monodentate bpe ligands in the axial positions. Mononuclear compounds are combined into 1D supramolecular chains via intramolecular O–H···N hydrogen bonds involving the uncoordinated O atoms of Htdb^– carboxylate groups as donors and the pyridine N atoms as acceptors. Compound 2 is ionic and consists of anionic 1D coordination polymer, organic cations (H2bpe)2+, and water molecules. The metal ion has a tetragonal pyramidal N2O3 coordination polyhedron involving N atoms of two bpe ligands, two O atoms of two coordinated SO42- monodentate anions and one O atom of water molecule. Compound 3 is ionic to and its crystal structure consists of 2D coordination polymer cation, F^– anions and solvated water molecules. The copper atom is coordinated by four nitrogen atoms of four neutral bridging bpe ligands to form a tetrahedral surrounding, typical for diamondoid topology.