Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction
In addition to a variety of conventional non-covalent intermolecular interactions such as C–H…π(arene), C–H…Cl and π(arene)…π(chelate-ring) contacts, the molecular packing in the crystal of an organotin dithiocarbamate compound, [SnCl(4-ClC6H4)2{S2CN(i-Pr)2}], exhibits evidence for a C–Cl…π(chelate-...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Royal Society of Chemistry
2021
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| Online Access: | http://eprints.sunway.edu.my/1551/ http://eprints.sunway.edu.my/1551/1/Tiekink%20accepted%20manuscript_crystengcomm%202021%2023%20119.pdf |
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| author | Tan, Sang Loon * Lee, See Mun * Lo, Kong Mun * Otero-de-la-Roza, Alberto Tiekink, Edward R. T. * |
| author_facet | Tan, Sang Loon * Lee, See Mun * Lo, Kong Mun * Otero-de-la-Roza, Alberto Tiekink, Edward R. T. * |
| author_sort | Tan, Sang Loon * |
| building | SU Institutional Repository |
| collection | Online Access |
| description | In addition to a variety of conventional non-covalent intermolecular interactions such as C–H…π(arene), C–H…Cl and π(arene)…π(chelate-ring) contacts, the molecular packing in the crystal of an organotin dithiocarbamate compound, [SnCl(4-ClC6H4)2{S2CN(i-Pr)2}], exhibits evidence for a C–Cl…π(chelate-ring) interaction. These interactions occur via a side-on approach of the chloride atom to the chelate-ring and therefore, are characterised as C–Cl(lone
pair)…π(chelate-ring) interactions, are shown to be attractive by NCI plots and QTAIM analysis, and are apparent in the calculated Hirshfeld surfaces. Theory suggests the energy of association provided the C–Cl…π(chelate-ring) interactions to be about 3-4 kcal/mol, a value greater than for analogous C–Cl…π(arene) and C–H…π(arene) interactions. A survey of the literature of related structures suggests these interactions are not common. The newly described C–Cl(lone-pair)…π(chelate-ring) interactions add to the variety of intermolecular
interactions able to be formed by chelate-rings in the supramolecular chemistry of metal complexes. |
| first_indexed | 2025-11-14T21:17:44Z |
| format | Article |
| id | sunway-1551 |
| institution | Sunway University |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:17:44Z |
| publishDate | 2021 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | sunway-15512021-01-12T08:45:21Z http://eprints.sunway.edu.my/1551/ Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction Tan, Sang Loon * Lee, See Mun * Lo, Kong Mun * Otero-de-la-Roza, Alberto Tiekink, Edward R. T. * QD Chemistry In addition to a variety of conventional non-covalent intermolecular interactions such as C–H…π(arene), C–H…Cl and π(arene)…π(chelate-ring) contacts, the molecular packing in the crystal of an organotin dithiocarbamate compound, [SnCl(4-ClC6H4)2{S2CN(i-Pr)2}], exhibits evidence for a C–Cl…π(chelate-ring) interaction. These interactions occur via a side-on approach of the chloride atom to the chelate-ring and therefore, are characterised as C–Cl(lone pair)…π(chelate-ring) interactions, are shown to be attractive by NCI plots and QTAIM analysis, and are apparent in the calculated Hirshfeld surfaces. Theory suggests the energy of association provided the C–Cl…π(chelate-ring) interactions to be about 3-4 kcal/mol, a value greater than for analogous C–Cl…π(arene) and C–H…π(arene) interactions. A survey of the literature of related structures suggests these interactions are not common. The newly described C–Cl(lone-pair)…π(chelate-ring) interactions add to the variety of intermolecular interactions able to be formed by chelate-rings in the supramolecular chemistry of metal complexes. Royal Society of Chemistry 2021 Article PeerReviewed text en cc_by_nc_4 http://eprints.sunway.edu.my/1551/1/Tiekink%20accepted%20manuscript_crystengcomm%202021%2023%20119.pdf Tan, Sang Loon * and Lee, See Mun * and Lo, Kong Mun * and Otero-de-la-Roza, Alberto and Tiekink, Edward R. T. * (2021) Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction. CrystEngComm, 23 (1). pp. 119-130. ISSN 1466-8033 (In Press) http://doi.org/10.1039/D0CE01478H doi:10.1039/D0CE01478H |
| spellingShingle | QD Chemistry Tan, Sang Loon * Lee, See Mun * Lo, Kong Mun * Otero-de-la-Roza, Alberto Tiekink, Edward R. T. * Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction |
| title | Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction |
| title_full | Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction |
| title_fullStr | Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction |
| title_full_unstemmed | Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction |
| title_short | Experimental and computational evidence for a stabilising C–Cl(lone-pair)⋯π(chelate-ring) interaction |
| title_sort | experimental and computational evidence for a stabilising c–cl(lone-pair)⋯π(chelate-ring) interaction |
| topic | QD Chemistry |
| url | http://eprints.sunway.edu.my/1551/ http://eprints.sunway.edu.my/1551/ http://eprints.sunway.edu.my/1551/ http://eprints.sunway.edu.my/1551/1/Tiekink%20accepted%20manuscript_crystengcomm%202021%2023%20119.pdf |