Quantitative analysis of intermolecular interactions in cocrystals and a pair of polymorphous cocrystal hydrates from 1, 4-dihydroquinoxaline-2, 3-dione and 1H-benzo[d]imidazol-2(3H)-one with 2, 5-dihydroxy-1, 4-benzoquinones: a combined X-ray structural and theoretical analysis. Issue 40 (22nd September 2020) - Sosa-Rivadeneyra, Martha V.
Abstract : Study and quantification of intermolecular interactions in five cocrystals and cocrystals hydrates by PIXEL, DFT, Hirshfeld surface and QTAIM calculations. Abstract : Cocrystallization experiments of the cyclic amides (lactams) 1, 4-dihydroquinoxaline-2, 3-dione (DHQ) and 1 H -benzo[ d ]imidazol-2(3 H )-one (BIM) with the anilic acids 2, 5-dichloro-3, 6-dihydroxy-1, 4-benzoquinone (CA) and 2, 5-dihydroxy-1, 4-benzoquinone (AA) yielded a total of five cocrystals and cocrystal hydrates, i.e., (DHQ)2 CA (I ), (DHQ)2 CA·2H2 O in the form of two polymorphs (I A ·2H 2 O and I B ·2H 2 O ), (BIM)2 CA (II ) and (BIM)2 AA (III ). The products were characterized by single-crystal X-ray diffraction (SCXRD) and Hirshfeld surface analysis, which were accomplished by DFT, PIXEL, QTAIM, and MESP calculations to assess the intermolecular interaction energies and related parameters. In accordance with the p K a rule, hydrogen atom transfer between the proton donor and acceptor molecules used in this study was not observed. In the molecular packing, the cyclic amides are always involved in at least one double-bridged homodimeric hydrogen bonding motif based on N–H⋯OC interactions. In addition, all five crystal structures exhibit heterosynthons with O–HCA/AA ⋯OCDHQ/BIM and/or N–HDHQ/BIM ⋯OCCA/AA hydrogen bonds and π-stacking interactions, through which the molecular components are linked in the three-dimensional space. The crystal structures are further stabilized by C–H⋯Cl, C–H⋯O and C–H⋯π interactions. Quantification of the intermolecular interaction energies by PIXEL, DFT and QTAIM calculations afforded results consistent with the experimental crystal structures.