Dispersion in Crystal Structures of 1-Chloro-3-aryl-5-trihalomethyl-1λ⁴,2,4,6-thiatriazines: Towards an Understanding of the Supramolecular Organization of Covalent Thiazyl Chlorides

Abstract

The syntheses of five new 1-chloro-3-aryl-5-trichloromethyl-1λ⁴,2,4,6-thiatriazines, aryl = 4-R-C₆H₄- (R = CH₃O, CH₃, H, Cl and CF₃), are reported with full characterization. Single-crystal X-ray diffraction structure determinations on all, as well as the 5-CF₃ analogue which also has R = CF₃, with models produced by Hirshfeld atom refinement, produced high-accuracy structures. All six exemplars form lateral dimers with short contacts that define a centrosymmetric {^δ+S···N^δ−}₂ motif, with interaction distances from 3.0473(9) to 3.422(3) Å, which do not vary in an expected manner with R. Normal population analysis charges computed by B3LYP-D3/6-311++G(d,p) DFT methods show small variations, and entirely as expected from the inductive effects of R. Gas-phase minimization of the dimers with M06-2X/aug-cc-pVDZ or B3LYP-D3/6-311++G(d,p) methods, with full counterpoise correction, replicate the experimental geometries for the 5-CF₃, the 5-CCl₃/CH₃OC₆H₄ and the 5-CCl₃/CH₃C₆H₄ experimental structures, but diverge for other CCl₃ exemplars. Interaction energies are more than double those computed for [(HC)₂N₂S]₂. Using a geometry-optimized model with H in place of CX₃, the interaction energy reduces to a very realistic –22 to –24 kJ/mol for just the {^δ+S···N^δ−}₂ motif, suggesting that CX₃ interactions contribute 21% (CF₃) to 37% (CCl₃) of the total.

Key words

chlorothiatriazine - thiazyl - supramolecular interaction - dispersion correction - counterpoise correction - density functional theory - X-ray crystallography - molecular squares

Publikationsverlauf

Eingereicht: 26. Februar 2023

Angenommen nach Revision: 12. April 2023

Accepted Manuscript online:
12. April 2023

Artikel online veröffentlicht:
23. Mai 2023

• References and Notes

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