Hydrogen-Bonding Motifs in MS<sub>2</sub>N<sub>2</sub>H Metallacycles: A Crystallographic and Computational Study of [CpCoS<sub>2</sub>N<sub>2</sub>H][BF<sub>4</sub>]
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Bibliographic record
Abstract
The first preparation and full characterization of highly insoluble [{η5–Cp}CoS2N2H][BF4] is reported. Proof of structure and composition is established from a single-crystal X-ray diffraction experiment at 173 K, which determined a crystal structure containing two independent cations and two independent anions in the asymmetric unit. The site of protonation is the terminal N of the S–N–S–N2– ligand which is coordinated to cobalt in the metallacycle. The crystal lattice contains numerous interatomic interactions, of which the most important are formed from multiple hydrogen bonds that link four [{η5–Cp}CoS2N2H]+ ions and two [BF4]− ions into a tetrameric cluster. The second kind of [BF4]− is not involved in intermolecular bonding. Short S···S′ interactions link such tetramers into planes; the resulting double-layer planes are described by the (101) Miller planes. DFT calculations using the B3PW91/6-311+G(3df)(2p) and B3LYP/6-311+G(3df)(2p) methods are in excellent agreement with the structure of the title cation from crystallography. Comparison to newly calculated and literature-reported DFT calculations on the neutral starting material [{η5–Cp}CoS2N2] and to a recent low-temperature crystal structure of the latter shows that there are only minor changes (≤3%) in the bond lengths within the CoS2N2 ring upon protonation, whereas the bond angles change by up to 9%. The B3PW91 functional is shown to be superior to B3LYP for computing the molecular structures of these formally CoIII metallacycles.
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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 | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.003 | 0.001 |
| Bibliometrics | 0.002 | 0.004 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.000 | 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 it