Structural studies of dithiatetrazocines: X-ray crystal structures of the symmetric dithiatetrazocines <i>p</i>-XC<sub>6</sub>H<sub>4</sub>CN<sub>4</sub>S<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>X [X = NO<sub>2</sub>, Br] and the first unsymmetric dithiatetrazocine, <i>p</i>-BrC<sub>6</sub>H<sub>4</sub>CN<sub>4</sub>S<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub>
Bibliographic record
Abstract
Oxidation of equimolar amounts of [p-BrC6H4CNSSN]Cl and [p-O2NC6H4CNSSN]Cl with elemental O2 in the presence of Ph3Sb in MeCN yields a mixture of the symmetric dithiatetrazocines, O2NC6H4CN4S2CC6H4NO2 (1) and BrC6H4CN4S2CC6H4Br (2) as well as the unsymmetrically substituted derivative BrC6H4CN4S2CC6H4NO2 (3). The structures of compounds 13 are determined by X-ray diffraction: 1 crystallizes in the monoclinic space group P21/c (a = 8.6397(4), b = 5.8359(4), c = 14.9767(11) Å, β = 92.088(4)°) with half a molecule in the asymmetric unit; 2 crystallizes in the triclinic space group P[Formula: see text] (a = 6.5330(5), b = 8.2084(6), c = 14.7264(9) Å, α = 84.483(4)°, β = 77.112(4)°, γ = 87.879(3)°); 3 was found to crystallize in two forms: recrystallization from CH2Cl2 at room temperature yielded a solvent-free, triclinic phase, space group P[Formula: see text] (a = 6.5060(9), b = 7.0739(9), c = 9.1164(8) Å, α = 81.860(3)°, β = 83.406(5)°, γ = 66.589(5)°), whereas cooling a solution to 5°C yielded a solvated form, 3·CH2Cl2, which crystallizes in the monoclinic space group P21/m (a = 6.179(1), b = 10.960(2), c = 13.884(3) Å, β = 92.69(3)°). The NO2···Br intermolecular interactions observed in the unsolvated structure of 3 are disrupted in the solvate structure; the CH2Cl2 molecule in the latter is aligned such that its molecular dipole interacts with both nitro and bromo groups, retaining a molecular chain motif. The structures are discussed in relation to their semi-empirically calculated molecular electrostatic potentials and calculations of intermolecular interactions using van der Waals forces combined with an electrostatic point charge model.Key words: dithiatetrazocine, crystal structure, crystal engineering, molecular electrostatic potential.
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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 | 0.000 |
| 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".