Considerable interest in hydrogen bonding involving chalcogen has been growing since the IUPAC committee has redefined hydrogen bonding. Not only the focus is on unconventional acceptors, but also on donors not discus...Considerable interest in hydrogen bonding involving chalcogen has been growing since the IUPAC committee has redefined hydrogen bonding. Not only the focus is on unconventional acceptors, but also on donors not discussed before. It has been mentioned in previous studies that the proton of the H-C group could be involved in hydrogen bonding, but with conventional acceptors. In this study, we explored the ability of hydrogen bond formation of Se, S and Te acceptors with the H-C donor using Cambridge Structural Database in conjunction with Ab Initio calculations. In the CSD, there are respectively 256, 6249 and 11 R1,R2,-C=Se, R1,R2,-C=S and R1,R2,-C=Te structures that form hydrogen bonds, in which the N,N groups are majority. Except for C=S acceptor which can form a hydrogen bond with its C, C group, both C=Se and C=Te acceptors could form a hydrogen bond only with N,C and N,N groups. CSD analysis shows very similar d (norm) around -0.04 Å, while DFT-calculated interaction for N,C and N,N groups are also similar. Both interaction distances derived from CSD analysis and DFT-calculated interaction energies demonstrate that the acceptors form stable complexes with H-CF3. Besides hydrogen bonds, dispersion interactions are forces stabilizing the complexes since their contribution can reach 50%. Analysis of intra-molecular geometries and Ab Initio partial charges show that this bonding stems from resonance induced C<sup>δ+</sup>=X<sup>δ-</sup> dipoles. In many respects, both C=Se, C=S and C=Te are similar to C=S, with similar d (norm) and calculated interaction strengths.展开更多
Hirshfeld surface analysis has been widely used in recent years as a means to quantify and visualize various types of intermolecular interactions in molecular crystals. This review article introduces intermolecular in...Hirshfeld surface analysis has been widely used in recent years as a means to quantify and visualize various types of intermolecular interactions in molecular crystals. This review article introduces intermolecular interactions discussed with Hirshfeld surface analysis and 2D fingerprint plots. In addition, using CIF files obtained from our previous results, Hirshfeld surface analysis was newly performed, and the resulting 3DHirshfeld surfaces, 2D print plots, molecular structural features, and crystal structure relationships were described. Classification of their intermolecular interactions, statistical discussion focused on crystalline water and perspective on ligand-protein docking are also mentioned.展开更多
文摘Considerable interest in hydrogen bonding involving chalcogen has been growing since the IUPAC committee has redefined hydrogen bonding. Not only the focus is on unconventional acceptors, but also on donors not discussed before. It has been mentioned in previous studies that the proton of the H-C group could be involved in hydrogen bonding, but with conventional acceptors. In this study, we explored the ability of hydrogen bond formation of Se, S and Te acceptors with the H-C donor using Cambridge Structural Database in conjunction with Ab Initio calculations. In the CSD, there are respectively 256, 6249 and 11 R1,R2,-C=Se, R1,R2,-C=S and R1,R2,-C=Te structures that form hydrogen bonds, in which the N,N groups are majority. Except for C=S acceptor which can form a hydrogen bond with its C, C group, both C=Se and C=Te acceptors could form a hydrogen bond only with N,C and N,N groups. CSD analysis shows very similar d (norm) around -0.04 Å, while DFT-calculated interaction for N,C and N,N groups are also similar. Both interaction distances derived from CSD analysis and DFT-calculated interaction energies demonstrate that the acceptors form stable complexes with H-CF3. Besides hydrogen bonds, dispersion interactions are forces stabilizing the complexes since their contribution can reach 50%. Analysis of intra-molecular geometries and Ab Initio partial charges show that this bonding stems from resonance induced C<sup>δ+</sup>=X<sup>δ-</sup> dipoles. In many respects, both C=Se, C=S and C=Te are similar to C=S, with similar d (norm) and calculated interaction strengths.
文摘Hirshfeld surface analysis has been widely used in recent years as a means to quantify and visualize various types of intermolecular interactions in molecular crystals. This review article introduces intermolecular interactions discussed with Hirshfeld surface analysis and 2D fingerprint plots. In addition, using CIF files obtained from our previous results, Hirshfeld surface analysis was newly performed, and the resulting 3DHirshfeld surfaces, 2D print plots, molecular structural features, and crystal structure relationships were described. Classification of their intermolecular interactions, statistical discussion focused on crystalline water and perspective on ligand-protein docking are also mentioned.
