Noncovalent interactions between benzochalcogenadiazoles and nitrogen bases

A theoretical study has been carried out on the intermolecular interactions between tetrafluoro-benzochalcogenadiazoles (chalcogen = S, Se, Te) and a series of nitrogen bases (FCN, ClCN, NP, trans-N₂H₂, pyridine, pyrazole, imidazole) at the B97-D3/def2-TZVP level, to obtain a better insight into the nature and strength of Ch···N chalcogen bond and secondary interaction in the binary and 1:2 ternary complexes. The dispersion force plays a prominent role on the stability of the sulfur complexes, and the electrostatic effect enhanced for the heavier chalcogen complexes. Most of intermolecular bonds display the characters of closed-shell and noncovalent interaction. For the complexes involving pyridine and imidazole, chalcogen bond is stronger than hydrogen bond, while the strength of chalcogen bond is equivalent to the secondary interaction for other complexes. With the addition of nitrogen base in the 1:2 complexes, chalcogen bond is weakened, while the secondary interaction remains unchanged. In the 1:2 complexes formed by pyridine and imidazole, stronger chalcogen bond results in larger negative cooperativity than that of other complexes.