The activation of benzene by more than one transition metal fragment is associated with small but significant structural distortions. The crystal structure determination of the heterobimetallic complex (eta1 : eta6-C4H5{TiCp2Cl})Cr(CO)3 reveals that the ipso carbon of the eta6-coordinated benzene ligand is displaced out of the plane of the arene ring and away from the chromium tricarbonyl tripod. Linear correlations exist between the magnitude of the endocyclic bond angles and Pauling’s electronegativities of heteroatoms of ortho substituents in heterobimetallic complexes with sigma, pi-bonded benzene derivatives.