Two novel symmetric fluorene-based ligands, namely, 2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene [L1 or (I), C21H18N4] and 2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene (L2), have been used to construct the coordination polymers catena-poly[[dichloridodicopper(I)(Cu-Cu)]-μ-2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene], [Cu2Cl2(C21H18N4)]n, (II), and catena-poly[[tetra-μ2-chlorido-tetracopper(I)]-bis[μ-2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene]], [Cu4Cl4(C25H26N4)2]n, (III). There are three types of C-H···N hydrogen bonds in (I), resulting a two-dimensional network in the ab plane, including a chiral helical chain along the b axis. Compounds (II) and (III) are related one-dimensional polymers. In both, Cu(I) atoms connect the symmetric ligands (L1 or L2) into a one-dimensional chain. In (II), the {[Cu(I)Cl2](-)} unit, acting as a co-anion, adheres to the one-dimensional chain through a weak Cu···Cu interaction. However, in (III), the {[Cu(I)2Cl4](2-)} unit links two different chains into a one-dimensional rope-ladder-type chain. In addition, there are C-H···Cl hydrogen bonds and π-π interactions in the extended structures of (II) and (III), the difference is that the chains in (II) are linked into a two-dimensional network while the chains in (III) are stacked into a three-dimensional framework.
Keywords: coordination polymers; copper(I) complexes; crystal structure; fluorene-based ligands.