Highlights  The crystal structures of the dichloromethane solvates of ( 5pentamethylcyclopentadienyl)rhodium(κC-1-(4-trifluoromethyl-2,3,5,6-the phenyl and trifluoromethyltetrafluorophenyl rings of molecules in a direction perpendicular to the columns and hydrogen bonding between the complex molecules. In contrast those of 1a and 1b display intermolecular lone pair- interactions in the same direction as the hydrogen bonding between the complex molecules. DFT calculations reveal that the - stacking and lone pair- interactions are of approximately the same energy. The difference in the structures arises from the steric requirements of the trifluoromethyl group.