Synthesis, X-ray characterization and theoretical study of 3: A,6:7,9 a-diepoxybenzo [de] isoquinoline derivatives: On the importance of F⋯O interactions

The synthesis, X-ray characterization and Hirshfeld surface analysis of a series of tetrahydro-diepoxybenzo[de]isoquinoline derivatives obtained by the tandem [4+2] cycloaddition between perfluorobut-2-yne dienophile (F3C-CC-CF3) and a row of N,N-bis(furan-2-ylmethyl)-4-R-benzenesulfonamides (bis-dienes, R = Me, F, Cl, Br, I) are reported in this manuscript. The implementation of kinetic/thermodynamic control allowed us to obtain both "pincer"- A nd "domino"-type adducts in good/moderate yields. In the solid state, most of the pincer adducts form self-assembled dimers (R = Me, Cl, Br, I) and, contrariwise, the domino adducts form 1D supramolecular chains, which are described in detail herein. Remarkably, in the self-assembled dimers, bifurcated halogen bonds involving one fluorine atom of the CF3 group and both O-atoms of sulfonamide are formed, which have been analyzed using DFT calculations, and the QTAIM and NCIplot computational tools. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.