The ligand 1,3-bis(1 -methylbenzimidazol-2-yl)benzene (mbzimbe, L³) reacts with copper(I) to give [Cu₂(L³)₂](Cl0₄)₂. The crystal structure of this compound (Cu₂C₄₄H₃₆N₈Cl₂0₈, a = 13.661 (1) Å, b = 19.829 (3) Å, c = 15.413 (2) Å, orthorhombic, Pbca, Z = 4) shows a dinuclear centrosymmetrical nonhelical structure in which each copper is linearly coordinated by a benzimidazole group of each ligand. The complex displays a weak intramolecular stacking interaction between the benzene groups. This complex can be considered as a stereoconformer of the double-helical complex [Cu₂(L¹)₂](Cl0₄)₂ (L¹; 2,6-bis(l-methylbenzimidazol-2-yl)pyridine). Conductivity measurements and UV-visible spectra show that the dimeric structures are maintained in solution in polar aprotic solvents. ¹H NMR measurements show that [Cu₂(L¹)₂]²⁺ retains its helical structure in solution. Comparison of helical and nonhelical structures with those formed by Cu(I) with related ligands allows discussion of the factors favoring the formation of self-assembled dinuclear complexes.