The almost planar molecular complex, formed by 3,4,7,8-tetramethyl-phenantroline (Me 4 phen) and picric acid (2,4,6-trinitrophenol, PA), has been investigated by using X-ray diffraction, vibrational spectroscopy, tunnel splitting and theoretical analysis. In the crystal of Me 4 phen·PA two short bifurcated hydrogen bonds N + –H···O − [2.6238(14)Å] and N + –H···N [2.6898(15)Å] are created. Infra-red spectra show the hydrogen bonds are short. The neutron backscattering spectrum of Me 4 phen⋅PA at 3K shows two tunneling peaks at ca. 1 and 3μeV. The number of the peaks is consistent with X-ray diffraction studies, which disclosed the inequivalence of methyl groups in the crystal structure. The comparison of the tunnel splitting for neat Me 4 phen and for its complex with picric acid indicates that in the latter case the methyl groups are more strongly engaged in the intermolecular interactions, particularly with nitro group oxygen atoms of picric acid, leading to an increase of the CH 3 rotational barrier height.