The C–HCl2Cu(II) synthon in the structural direction and assembly of supramolecular complexes with the 3,3′-bis(2-benzimidazolyl)-2,2′-dipyridine ligand and its N-substituted derivatives

Three new Cu(II) supramolecular complexes [Cu(L₁)Cl₂]·2DMF (1), [Cu(L₂)Cl₂] (2) and [Cu(L₃)Cl₂]·DMF (3) (L₁ = 3,3′-bis(2-benzimidazolyl)-2,2′-dipyridine, L₂ = 3,3′- bis(N-ethyl-2-benzimidazolyl)-2,2′-dipyridine and L₃ = 3,3′-bis(N-benzyl-2-benzimidazolyl)-2,2′-dipyridine) have been prepared and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. X-ray structural analysis of L₁, L₂·3.5H₂O and L₃·H₂O indicates that all three ligands adopt the trans conformation with the two benzimidazole fragments located on opposite sides of the dipyridyl backbone. While in complexes 1–3, all the ligands display the cis conformation and behave as bidentate chelating reagents to coordinate with Cu(II). The inorganic chloride ions always act as a reliable hydrogen bonded acceptor in these structures, and the resulting C–HCl₂Cu supramolecular synthons play a significant role in the formation and stabilization of the structures. Moreover, additional non-covalent interactions, such as C–Hπ, are also identified to extend the discrete (0-D) or low-dimensional (1-D) motifs into high-dimensional architectures.