Structure of three 6-aryl-5-pentafluorophenyl-2,2'-bipyridines was studied by single crystal X-ray diffraction analysis. The effect of some functional fragments on the structural organization of compounds, in particular, donor and acceptor substituents in the aryl moiety, as well as annelated benzene and cyclopentane rings on the molecular structure and crystal packing of pentafluorophenyl-modified 2,2'-bipyridine ligand systems, was analyzed.