Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study
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...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Published: |
De Gruyter
2015
|
| Subjects: |
| _version_ | 1796960646073417728 |
|---|---|
| author | Zukerman-Schpector, J. Madureira, L.S. Poplaukhin, P. Arman, H.D. Miller, T. Tiekink, Edward R.T. |
| author_facet | Zukerman-Schpector, J. Madureira, L.S. Poplaukhin, P. Arman, H.D. Miller, T. Tiekink, Edward R.T. |
| author_sort | Zukerman-Schpector, J. |
| collection | UM |
| description | 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. |
| first_indexed | 2024-03-06T05:47:46Z |
| format | Article |
| id | um.eprints-19262 |
| institution | Universiti Malaya |
| last_indexed | 2024-03-06T05:47:46Z |
| publishDate | 2015 |
| publisher | De Gruyter |
| record_format | dspace |
| spelling | um.eprints-192622020-05-20T00:27:57Z http://eprints.um.edu.my/19262/ Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study Zukerman-Schpector, J. Madureira, L.S. Poplaukhin, P. Arman, H.D. Miller, T. Tiekink, Edward R.T. Q Science (General) QD Chemistry 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. De Gruyter 2015 Article PeerReviewed 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 <https://doi.org/10.1515/zkri-2015-1840>. http://dx.doi.org/10.1515/zkri-2015-1840 doi:10.1515/zkri-2015-1840 |
| spellingShingle | Q Science (General) QD Chemistry Zukerman-Schpector, J. Madureira, L.S. Poplaukhin, P. Arman, H.D. Miller, T. Tiekink, Edward R.T. Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study |
| title | Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study |
| title_full | Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study |
| title_fullStr | Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study |
| title_full_unstemmed | Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study |
| title_short | Conformational preferences for isomeric N,N′-bis(pyridin-n-ylmethyl)ethanedithiodiamides, n = 2, 3 and 4: a combined crystallographic and DFT study |
| title_sort | conformational preferences for isomeric n n bis pyridin n ylmethyl ethanedithiodiamides n 2 3 and 4 a combined crystallographic and dft study |
| topic | Q Science (General) QD Chemistry |
| work_keys_str_mv | AT zukermanschpectorj conformationalpreferencesforisomericnnbispyridinnylmethylethanedithiodiamidesn23and4acombinedcrystallographicanddftstudy AT madureirals conformationalpreferencesforisomericnnbispyridinnylmethylethanedithiodiamidesn23and4acombinedcrystallographicanddftstudy AT poplaukhinp conformationalpreferencesforisomericnnbispyridinnylmethylethanedithiodiamidesn23and4acombinedcrystallographicanddftstudy AT armanhd conformationalpreferencesforisomericnnbispyridinnylmethylethanedithiodiamidesn23and4acombinedcrystallographicanddftstudy AT millert conformationalpreferencesforisomericnnbispyridinnylmethylethanedithiodiamidesn23and4acombinedcrystallographicanddftstudy AT tiekinkedwardrt conformationalpreferencesforisomericnnbispyridinnylmethylethanedithiodiamidesn23and4acombinedcrystallographicanddftstudy |