In this work, a new sigma-hole interaction formed between ZOF(2) (Z = Kr and Xe) as the Lewis acid and a series of metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CN, CH3) is reported. The nature of this interaction, called "aerogen-hydride" interaction, is unveiled by molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. Our results indicate that the aerogen-hydride interactions are quite strong and can be comparable in strength to other sigma-hole bonds. An important charge-transfer interaction is also associated with the formation of OF(2)Z center dot center dot center dot HMX complexes. (C) 2016 Elsevier B.V. All rights reserved.