Study on the nature of interaction of pyrrole with various hydrides

► We investigated the intermolecular interaction of pyrrole with the various hydrides. ► There are NH⋯X and Hπ-type hydrogen-bonding complexes. ► With the exception of pyrrole-H2O and pyrrole-NH3 complexes, all of the other pyrrole-HnX complexes favors π-type H-bonding. ► The electrostatic and dispersion interactions dominate the Hπ-type complexes.