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Six copper(II) arenedisulfonate complexes with the general formula Cu(N4)(nds/bpds)·nH2O (nds = naphthalenedisulfonate, bpds = biphenyldisulfonate) have been synthesized in aqueous solution and structurally characterized by X-ray single crystal diffraction, IR and UV spectroscopies, TGA and DSC. In Cu(en)2(1,5nds)·2H2O 1, Cu(N-meen)2(2,6nds)·2H2O 2 (N-meen = N-methylethylenediamine), Cu(dpn)2(bpds) 3 (dpn = 2,3-diaminopropane), and Cu(cylam)(1,5nds) 4 the SO3 group coordinates monodentately to the axial position of Cu2+ which is equatorially coordinated by four amino nitrogens. In 1 and 4 intramolecular hydrogen bonds are formed between the SO3 oxygens and amino hydrogens which reinforce interaction between the SO3 group and Cu2+ complex cation. In Cu(dpn)2(1,5nds)·2H2O 5 and Cu(N,N′-meen)2(1,5nds)·3H2O 6 (N,N′-meen = N,N′-dimethylethylenediamine), due to the steric hindrance caused by the methyl substitution of the amino ligands and the rigidity of the naphthalene ring, water molecules, instead of the bulky SO3 group, coordinate to the axial position of Cu2+. Structures 1–4 represent the first synthesis and structural characterization of polymeric 1-dimensional structures constructed by arenedisulfonates and divalent transition metals. Also, 1 crystallizes in the enantiomorphic space group P41212 and displays interesting chiral grids constructed by ionic hydrogen bonds. The coordination geometries of Cu2+, as well as the coordination modes of arenedisulfonates, are discussed in detail.

Graphical abstract: Variation in the coordination mode of arenedisulfonates to copper(II): synthesis and structural characterization of six copper(II) arenedisulfonate complexes

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