Issue 34, 2022

Crystal engineering of molecules with through-space α-effect hydrogen bonds: 3a,6 : 7,9a-diepoxybenzo[de]isoquinolines possessing a free amino group

Abstract

This manuscript reports the synthesis, X-ray characterization and DFT study of a series of all-cis 3a,6 : 4,5 : 7,9a-triepoxy and 3a,6 : 7,9a-diepoxybenzo[de]isoquinolines obtained by the tandem intramolecular [4 + 2]/[4 + 2] cycloaddition in bis-furans (the IMDAF reaction) between difurfurylamine derivatives and dimethyl acetylenedicarboxylate (DMAD) as a dienophile. In one compound instead of DMAD, 1-phenyl-1H-pyrrole-2,5-dione (N-phenylmaleimide) was used as a dienophile. The existence of a “through-space” alpha-effect is analyzed in these compounds, since in three of them N–H⋯O2 H-bonds are observed in the solid state promoting the formation of self-assembled dimers. That is, the close O⋯O distance between the O-bridge atoms due to the rigidity of these molecules causes a lone pair⋯lone pair (LP⋯LP) interaction that enhances the H-bond acceptor ability of the bridging atoms (through-space α-effect). This fact has been studied using DFT calculations, molecular electrostatic potential (MEP) surfaces, electron localization function (ELF), quantum theory of atoms-in-molecules (QTAIM) and noncovalent interaction plot (NCIplot) index computational tools. This is the third study of the literature where “α-effect” hydrogen bonds (AEHBs) are described. The novelty of the present work resides in the utilization of an amine linker between the furan rings that allows the incorporation of a good H-bond donor in the model system. As a result, NH⋯O2 instead of CH⋯O2 AEHBs described in previous works are established. The X-ray analyses of the synthesized di- and tri-epoxides reveal that the AEHBs are predominant in the X-ray architecture of these compounds.

Graphical abstract: Crystal engineering of molecules with through-space α-effect hydrogen bonds: 3a,6 : 7,9a-diepoxybenzo[de]isoquinolines possessing a free amino group

Supplementary files

Article information

Article type
Paper
Submitted
02 Jul 2022
Accepted
29 Jul 2022
First published
11 Aug 2022

CrystEngComm, 2022,24, 6093-6100

Crystal engineering of molecules with through-space α-effect hydrogen bonds: 3a,6 : 7,9a-diepoxybenzo[de]isoquinolines possessing a free amino group

A. S. Antonova, E. V. Nikitina, K. S. Valchuk, M. S. Grigoriev, R. M. Gomila, A. Frontera and F. I. Zubkov, CrystEngComm, 2022, 24, 6093 DOI: 10.1039/D2CE00903J

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