Theoretical investigation on the interactions between borazine and first-row hydrides

► We investigated the intermolecular interaction of borazine with the first-row hydrides. ► In the B3N3H6-BH3, the B3N3H6 and BH3 are in the same units. ► The strength of the π-H interaction is enhanced as one progresses from CH4 to HF of the borazine complexes. ► Both electrostatic and dispersive energies are important in the description of these π-H interactions.