The Tolman cone angle method assumes empirical bond data and defines the perimeter as the maximum possible circumscription of an idealized free-spinning substituent. The metal-ligand bond length in the Tolman model was determined empirically from crystal structures of tetrahedral nickel complexes. In contrast, the solid-angle concept derives both bond length and the perimeter from empirical solid state crystal structures. There are advantages to each system.
If the geometry of a ligand is known, either through crystallography or computations, an exact cone angle (θ) can be calculated. No assumptions about the geometry are made, unlike the Tolman method.