Theoretical studies of intermolecular interactions of arachno-pentaborane (11) with HF and LiH

► Coexistence of H-bond and dihydrogen bond interactions in the complexes of B5H11 with HF. ► Coexistence of Li-bond and dihydrogen bond interactions in the complexes of B5H11 with LiH. ► The arachno-B5H11 could trapped small polar molecules in host-guest like interactions. ► LiH give more stable complexes than HF with arachno-B5H11.