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
| dc.contributor.author | Kondage, Savini S. | |
| dc.contributor.author | Roemmele, Tracey L. | |
| dc.contributor.author | Boeré, René T. | |
| dc.date.accessioned | 2024-07-26T18:25:54Z | |
| dc.date.available | 2024-07-26T18:25:54Z | |
| dc.date.issued | 2023 | |
| dc.description | Accepted author manuscript | |
| dc.description.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···Nδ−}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···Nδ−}2 motif, suggesting that CX3 interactions contribute 21% (CF3) to 37% (CCl3) of the total. | |
| dc.description.peer-review | Yes | |
| dc.identifier.citation | Kondage, S. S., Roemmele, T. L., & Boeré, R. T. (2023). 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 chloride. SynnLett, 34(10), 1113-1121. https://10.1055/a-2071-4235 | |
| dc.identifier.uri | https://hdl.handle.net/10133/6830 | |
| dc.language.iso | en | |
| dc.publisher | Thieme | |
| dc.publisher.department | Department of Chemistry and Biochemistry | |
| dc.publisher.faculty | Arts and Science | |
| dc.publisher.institution | University of Lethbridge | |
| dc.subject | Chlorothiatrazine | |
| dc.subject | Thiazyl | |
| dc.subject | Supramolecular interaction | |
| dc.subject | Disperson correction | |
| dc.subject | Counterpoise correction | |
| dc.subject | Density functional theory | |
| dc.subject | X-ray crystallography | |
| dc.subject | Molecular squares | |
| dc.title | 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 | |
| dc.type | Article |