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
Bibliographic record
Abstract
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.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".