Non-covalent interactions between aromatic ligands influence the conformations of metal complexes, and the system [M(OAr)₂L₂] has been used to investigate the difference between phenyl–phenyl, phenyl–pentafluorophenyl and pentafluorophenyl–pentafluorophenyl interactions. X-Ray crystal structures show that pentafluorophenyl groups adopt partially stacked orientations with the two aromatic rings close to parallel and with significant π overlap. In contrast, phenyl groups are skewed away from each other with only edge-to-face contacts. Phenyl–pentafluorophenyl interactions adopt a coplanar fully stacked geometry. These results have been rationalised on the basis of energy calculations (carried out blind) using a variety of empirical models for treating weak non-covalent interactions. The major cause of the different behaviour of the three systems lies in the electrostatic interactions between the π systems.