Zukerman-Schpector, J. and Madureira, L.S. and Poplaukhin, P. and Arman, H.D. and Miller, T. and Tiekink, Edward R.T. (2015) Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study. Zeitschrift fur Kristallographie Crystalline Materials, 230 (8). pp. 531-541. ISSN 2194-4946, DOI https://doi.org/10.1515/zkri-2015-1840.
Full text not available from this repository.Abstract
Crystal structure analysis of the isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithioamides, n = 2 (1), 3 (2) and 4 (3), show a planar conformation for 1 and conformations whereby the pyridyl rings lie orthogonal and to either side of the central residue for each of 2 and 3. The universal adoption of the all ZZ conformation about the central C-N bonds, which have double bond character, is ascribed to the presence of intramolecular N-H...S hydrogen bonds that close S(5) rings. The gasphase geometry optimised structure for 1 is the same as the experimental structure which features intramolecular amine-N-H...N(pyridyl) hydrogen bonds. The open structures found for 2 and 3 differ from the somewhat flattened optimised structures. Systematic variations in the geometric parameters characterising the central C2N2S2 residue, in particular the double-bond character of the C-N bond and the elongation of the central C-C bond are shown by theory to be due to conjugative nN → π∗C=S interactions and nS → σ∗C-C hyperconjugation, respectively.
| Item Type: | Article |
|---|---|
| Funders: | UNSPECIFIED |
| Uncontrolled Keywords: | Conformation; Crystal structure analysis; DFT; Thioamide; X-ray diffraction |
| Subjects: | Q Science > Q Science (General) Q Science > QD Chemistry |
| Divisions: | Faculty of Science > Department of Chemistry |
| Depositing User: | Ms. Juhaida Abd Rahim |
| Date Deposited: | 18 Sep 2018 09:11 |
| Last Modified: | 20 May 2020 00:27 |
| URI: | http://eprints.um.edu.my/id/eprint/19262 |
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