Formation of twelve-fold iodine coordination at high pressure

Abstract Halogen compounds have been studied widely due to their unique hypercoordinated and hypervalent features. Generally, in halogen compounds, the maximal coordination number of halogens is smaller than eight. Here, based on the particle swarm optimization method and first-principles calculations, we report an exotically icosahedral cage-like hypercoordinated IN 6 compound composed of N 6 rings and an unusual iodine−nitrogen covalent bond network. To the best of our knowledge, this is the first halogen compound showing twelve-fold coordination of halogen. High pressure and the presence of N 6 rings reduce the energy level of the 5d orbitals of iodine, making them part of the valence orbital. Highly symmetrical covalent bonding networks contribute to the formation of twelve-fold iodine hypercoordination. Moreover, our theoretical analysis suggests that a halogen element with a lower atomic number has a weaker propensity for valence expansion in halogen nitrides.