The experimental M-A and M-B distances in several series of [MA(n)B(m-n)]-type complexes have been studied by DFT. Many of the structural features of the series, such as trans influences and sterically induced bond elongations, are not reproduced correctly in gas-phase DFT calculations. However, the correct trends are recovered by explicitly including environmental effects via the COSMO solvation model. These observations imply that the condensed-phase environment plays a critical role in determining the geometric structure of coordination complexes. Thus, any apparently satisfactory reproduction of the condensed-phase structure by an in vacuo calculation may mask an incorrect treatment of the interplay between different ligands attached to the same metal center.