The thermodynamics of the formation of 3-comp from either of the binary cocrystals is well understood from the periodic DFT calculations, also supported by experimental calorimetric measurements. Neither of these methods, however, truly explain the reason for the higher stability of the 3-comp compared to the two-component cocrystals. In order to rationalise the observed mechanochemical reactivity, we have looked into the structures of all the cocrystals and explored the role of different non-covalent interactions in stabilising the corresponding packing arrangements. Compared to the binary cocrystals, 3-comp has two potential halogen bond acceptors (N of pyr and S of tpss), capable of interacting with tftib. The energies of individual supramolecular interactions must be the key to explaining the higher stability of 3-comp with respect to the binary counterparts.