A new class of halogen bonds that avoids the σ-hole

► A new class of halogen bonds with the type of X = Hal⋯Y. ► The strength of this new class of halogen bonds is in the range of 90-120 kcal/mol. ► The geometry of this new class of halogen bonds is not determined by the halogen's positive σ-hole. ► The n → π∗ interaction determines the geometry of this new class of halogen bonds.