UMP2 calculations with aug-cc-pVDZ basis set were used to analyse intermolecular interactions in R3C···XCN···LiCN and R3C···LiCN···XCN triads (R = H, CH3; X = Cl, Br) which are connected via lithium bond and halogen bond. To understand the properties of the systems better, the corresponding dyads are also studied. Molecular geometries and binding energies of dyads, and triads are investigated at the UMP2/aug-cc-pVDZ computational level. Particular attention is paid to parameters such as cooperative energies, and many-body interaction energies. All studied complexes, with the simultaneous presence of a lithium bond and a halogen bond, show cooperativity with energy values ranging between −1.20 and −7.71 kJ mol−1. A linear correlation was found between the interaction energies and magnitude of the product of most positive and negative electrostatic potentials (VS,maxVS,min). The electronic properties of the complexes are analysed using parameters derived from the atoms in molecules (AIM) methodology. According to energy decomposition analysis, it is revealed that the electrostatic interactions are the major source of the attraction in the title complexes.
