Structural Diversity of Metallosupramolecular Assemblies from Cu(phen)2+ (phen = 1,10‐Phenanthroline) Building Blocks and 4,4′‐Bipyridine

Abstract

AbstractAttempts to crystal engineer metallosupramolecularcomplexes from Cu(phen)2+ building blocks and the prototypical,rod‐like, exo‐bidentate ligand 4,4′‐bipyridine (4,4′‐bipy) by layering techniques are described. Reactions of Cu(phen)2+ (phen = 1,10‐phenanthroline) with 4,4′‐bipy in the presence of NO3– counterions yielded two distinct, discrete, dinuclear, Ci symmetric, dumbbell‐typecomplexes, [{Cu(NO3)2(phen)}2(4,4′‐bipy)] (1) and [{Cu(NO3)(phen)(H2O)}2(4,4′‐bipy)](NO3)2 (2), depending upon the mixture of solvents used for crystallization. In compound 1, a mono‐ and a bidentate nitrato group coordinate to Cu2+, whereas in 2 the monodentate nitrato groups are replaced by aqua ligands, which introduce additional hydrogen‐bond donor functionality to the molecule. The crystal structure of 1 was determined by single‐crystal X‐ray analysis at 296 and 110 K. Upon cooling, a disorder‐order transition occurs, with retention of the space group symmetry. The crystal structure of 2 at room temperature was reported previously [Z.‐X. Du, J.‐X. Li, Acta Cryst. 2007, E63, m2282]. We have redetermined the crystal structure of 2 at 100 K. A phase transition is not observed for 2, but the low temperature single‐crystal structure determination is of significantly higher precision than the room temperature study. Both 1 and 2 are obtained phase‐pure, as proven by powder X‐ray diffraction of the bulk materials. Crystals of [Cu(phen)(CF3SO3)2(4,4′‐bipy)·0.5H2O]n (3), a one‐dimensional coordination polymer, were obtained from [Cu(CF3SO3)2(phen)(H2O)2] and 4,4′‐bipy. In 3, Cu(phen)2+ corner units are joined by 4,4′‐bipy via the two vacant cis sites to form polymeric zig‐zag chains, which are tightly packed in the crystal. Compounds 1–3 were further studied by infrared spectroscopy.