Systematic study of intermolecular C-X center dot center dot center dot O=S (X = Cl, Br, I) halogen bonds in (E)-10-(1,2-dihalovinyl)-10H-phenothiazine 5,5-dioxides

作者：Umezono Satoru; Okuno Tsunehisa^*

来源：Journal of Molecular Structure, 2017, 1147: 636-642.

DOI：10.1016/j.molstruc.2017.06.135

• Halogen bond
• Phenothiazine
• Sulfone
• CT interaction
• DFT calculation

We have succeeded in preparation and crystallographical characterization of (E)-10-dihalovinyl-10H-phenothiazine 5,5-dioxides 1-3 (1: X = Cl, 2: X = Br, 3: X = I) and carried out a systematic study of C-X center dot center dot center dot O=S halogen bonds. The three compounds were found to have a similar molecular structure and halogen bonding pattern as planned, and we could detect even weak C-Cl center dot center dot center dot O=S halogen bonds in 1 owing to coexistence of C-X and S=O groups within one molecule. Judging by shrinkage from sum of the van der Waals radii of the corresponding atoms, the interaction of C-X center dot center dot center dot O=S halogen bonds increased in order X = Cl < Br < I. Since relatively smaller sigma-holes were made in the bonds, charge transfer interaction between n(o) and sigma*(C-X) orbitals was suggested to play an important role for the halogen bonds. Especially in 3 (X = I), localized and widely extended sigma*(C-1) orbital was considered to make an effective interaction.

• 出版日期2017-11-5