Anion⋅⋅⋅Anion Interactions Involving σ‐Holes of Perrhenate, Pertechnetate and Permanganate Anions

In this communication experimental and theoretical results are reported affording strong evidence that interactions between electron rich atoms and the metal of tetroxide anions of group 7 elements are a new case of attractive and σ‐hole interactions. Single crystal X‐ray analyses, molecular electrostatic potentials, quantum theory of atoms‐in‐molecules, and noncovalent interaction plot analyses show that in crystalline permanganate and perrhenate salts the metal in Mn/ReO(4) (−) anion can act as electron acceptors, the oxygen of another Mn/ReO(4) (−) anion can act as the donor and supramolecular anionic dimers or polymers are formed. The name matere bond (MaB) is proposed to categorize these noncovalent interactions and to differentiate them from the classical metal‐ligand coordination bond.