Insight into the nature of the interactions of pyridine, funan and thiophene with LiNH2

► We investigated the intermolecular interaction of pyridine, funan, thiophene with LiNH2. ► There are σ-type and π-type lithium bond complexes. ► Li-N stretch vibration has a red shift in the C5H5N, and a blue shift in the C5H5O and C4H4S complexes. ► The electrostatic dominate the σ-type complexes, while the induction forces dominate the π-type complexes.