Abstract: | The dirhodium complex bis(benzonitrile)tetrakisμ‐4‐(diethylamino)benzoato‐κ2O:O′]dirhodium(II)(Rh—Rh) benzonitrile disolvate, Rh2(C11H14NO2)4(C7H5N)2]·2C7H5N, lies about an inversion centre. The dirhodium complex (methanol)tetrakis(μ‐4‐nitrobenzoato‐κ2O:O′)(pyridine)dirhodium(II)(Rh—Rh) dichloromethane solvate, Rh2(C7H4NO4)4(C5H5N)(CH4O)]·CH2Cl2, lies in a general position in the unit cell, but the complexes dimerize around an inversion centre via O—H⋯O hydrogen bonding of the axial MeOH to a carboxylate O atom. In the latter crystal structure, π–π stacking interactions between the bridging 4‐nitrobenzoate ligands and the axial pyridine ligand are observed between adjacent molecules. |