Can a neutral ligand bond to a metal center of a square pyramidal oxohalido anion at the available sixth octahedral position? Crystal structures of some compounds indeed suggest that ligands, such as THF, pyridine, H2O, NH3, and CH3CN, can interact with the central metal atom, because they are oriented with their heteroatom toward the metal center with distances being within the bonding range. However, this assumption that is based on chemical intuition is wrong. In-depth analysis of interactions between ligands and oxohalido anions (e.g., VOX4-, NbOCl4-) reveals that the bonding of a neutral ligand is almost entirely due to electrostatic interactions between the H atoms of a ligand and halido atoms of an anion. Furthermore, ab initio calculations indicate that the ligand-VOF4- interactions represent only about one-quarter of the total binding of the ligand within the crystal structure, whereas the remaining binding is due to crystal packing effects. The current study therefore shows that relying solely on the structural aspects of solved crystal structures, such as ligand orientation and bond distances, can lead to the wrong interpretation of the chemical bonding.