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>
Why this work is in the frame
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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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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.012 | 0.007 |
| Meta-epidemiology (narrow) | 0.012 | 0.012 |
| Meta-epidemiology (broad) | 0.011 | 0.005 |
| Bibliometrics | 0.006 | 0.010 |
| Science and technology studies | 0.009 | 0.009 |
| Scholarly communication | 0.006 | 0.013 |
| Open science | 0.010 | 0.008 |
| Research integrity | 0.007 | 0.009 |
| Insufficient payload (model declined to judge) | 0.000 | 0.002 |
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 it