To ensure we avoid introducing bias in our hemilabile ligand dataset by including ligands that strongly prefer either high-or low-denticity conformations, we evaluated how many times they appear in each denticity in the unique complexes of these ligands (Supporting Information Figures ). While different denticity changes are possible for hemilabile tridentate (e.g., to bidentate or monodentate) and tetradentate ligands (e.g., to bidentate), here we define only two classes, i.e., hemilabile and non-hemilabile, to ensure sufficient data for each class (Supporting Information Figures ). There is a wide distribution of the hemilabile ligands occurring in the low-denticity configuration relative to the total occurrences that is nevertheless centered around 0.5 (i.e., both low and high denticity are equally weighted). For the majority of ligands (i.e., 75.8% bidentate, 75.4% tridentate, 76.8% tetradentate), the ratio of low denticity to total count is between 0.2 and 0.8, indicating that these hemilabile ligands appear in higher-and lower-denticity conformations with similar frequency. Only a very minor fraction of ligands (i.e., 1.2% bidentate, 0.6% tridentate, 0.8% tetradentate) strongly prefer either high-or low-denticity conformations (i.e., the ratio of low denticity to total count is < 0.01 or > 0.99). Thus, most ligands in our hemilabile set can be expected to sample both denticities based on their occurrence in crystal structures.