Transition metal complexes with 2,4-substituted tetradentate, 2,3,4- and 2,4,7-substituted pentadentate, and 2,3,4,7-substituted hexadentate bispidine ligands (bispidine) 7-diazabicyclo[3.3.1]nonane) with two tertiary amine and two, three, or four pyridine donors are relatively stable (10 < log KCUL < 18). Interestingly, the two isomeric pentadentate ligands have very different stabilities with a variety of metal ions and, depending on the metal ion, one of the isomers leads to more stable complexes than the hexadentate and the other to less stable complexes than the tetradentate ligand. Another interesting observation is that the complex stabilities of all bispidine ligands reported here do not follow the Iriving-Williams series since the stability constants of the cobalt(II) complexes are up to 4 log units larger than those of the corresponding nickel(II) complexes. All these observations are analyzed on the basis of subtle distortions of the coordination geometries, and these have been related previously to Jahn-Tellerderived distortions for the copper(II) complexes. However, similar but less pronounced structural properties are observed with other metal centers, as shown, e.g., with the experimental structures of the two zinc(II) complexes with the isomeric pentadentate ligands reported here. The structural properties and the related stabilities are also discussed on the basis of force field calculations.