Preparation and crystal structures of the isomeric series 4-tolyl-1,2,3,5-dithiadiazolyl, (o-MeC<sub>6</sub>H<sub>4</sub>CNSSN)<sub>2</sub>, (m-MeC<sub>6</sub>H<sub>4</sub>CNSSN)<sub>2</sub>and (p-MeC<sub>6</sub>H<sub>4</sub>CNSSN)<sub>2</sub>
Bibliographic record
Abstract
The radicals (p-MeC6H4CNSSN)2 (1) (m-MeC6H4CNSSN)2 (2) and (o-MeC6H4CNSSN)2 (3) were prepared from the corresponding tolunitriles using conventional synthetic methodologies and were crystallised by vacuum sublimation. All three structures comprise cis-cofacial π*–π* dimers with one dimer in the asymmetric unit for 1 and 2 and four dimers in the asymmetric unit for 3. In both 1 and 2 the crystal packing reveals close S⋯π(aryl) interactions which drive formation of a double herringbone motif, analogous to that observed in the parent radical [PhCNSSN]2. The double herringbone sheets in both 1 and 2 are linked via Sδ+⋯Nδ− contacts. The presence of the methyl group in the ortho-position has a pronounced effect on the solid state structure of 3; the steric demand of the ortho-methyl group generates a substantially larger twist angle between aryl and heterocyclic rings (19.43–28.07° in 3 compared with 5.20–10.91° in 1 and 2). This induces a larger mean intra-dimer separation (mean S⋯S = 3.117(2) Å, cf.1 and 2 at 3.0759(9) and 3.078(1) Å) and also inhibits formation of S⋯π interactions in 3. Instead the structure of 3 reveals a layered arrangement of dimers with intra-layer Sδ+⋯Nδ− contacts. The lengthening of the intramolecular S⋯S bond in 3 leads to a weakening of the π*–π* dimer and is manifested in the observation of a thermally accessible triplet state (S = 1) at room temperature by EPR spectroscopy. Warming above room temperature leads to a rapid increase in EPR intensity above 320 K associated with melting of 3.
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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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 0.001 |
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".