A series of C-shaped, 1,1'-alkyl-bridged 4,4'-diaryl-2,2'-bibenzimidazoles has been synthesized. The crystal structures of these compounds have been determined and packing diagrams demonstrate that these molecules either form linear intercalated molecular chains or include solvent molecules in the solid state. Crystal structures are compared to computational structures determined using density functional theory, with the BMK/DZV(2d,p) method. The C-shaped or tweezer-like geometry enables them to act as building blocks for supramolecular architectures.