Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2
Crystallography shows the universal adoption of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC([double bond, length as m-dash]S)N(H)(C6H4Y-4) for Y = H (1), Me (2), Cl (3) and NO2 (4). However, distinct topologies, i.e. linear (Y = H), helical...
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Royal Society of Chemistry
2021
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my.sunway.eprints.16032021-03-03T05:35:07Z http://eprints.sunway.edu.my/1603/ Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 Tan, Sang Loon * Tiekink, Edward R. T. * QD Chemistry Crystallography shows the universal adoption of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC([double bond, length as m-dash]S)N(H)(C6H4Y-4) for Y = H (1), Me (2), Cl (3) and NO2 (4). However, distinct topologies, i.e. linear (Y = H), helical (Y = Me and Cl) and zig-zag (Y = NO2) are noted with major differences in the pitch of the polymer. Geometry-optimisation, MEP and NPA analyses show a distinct electronic structure for the Y = NO2 derivative, in particular relating to the activation of the aryl ring. An exhaustive analysis of the molecular packing (point-to-point interactions, crystal structure similarity, Hirshfeld surface analysis, NCI and QTAIM, interaction energies and energy frameworks) points to the importance of C–H⋯π(aryl) interactions in stabilising the chains but these have a considerably reduced influence in the crystal with Y = NO2 (4), where π(aryl)⋯π(aryl) interactions are important. The more open arrangement for the linear chain in 1 facilitates the formation of C–H⋯π(aryl) interactions and the more compact arrangements enable the formation of stabilising, intra-chain methylene-C–H⋯S(thione) interactions 2–4. This study highlights the role of second-tier non-covalent interactions in the arrangement of conventional hydrogen bonding interactions. Royal Society of Chemistry 2021 Article PeerReviewed text en cc_by_nc_4 http://eprints.sunway.edu.my/1603/1/Tiekink%20acc%20cec%2023%201723.pdf Tan, Sang Loon * and Tiekink, Edward R. T. * (2021) Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2. CrystEngComm, 23 (8). pp. 1723-1743. ISSN 1466-8033 (In Press) http://doi.org/10.1039/D0CE01810D doi:10.1039/D0CE01810D |
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QD Chemistry Tan, Sang Loon * Tiekink, Edward R. T. * Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 |
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Crystallography shows the universal adoption of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC([double bond, length as m-dash]S)N(H)(C6H4Y-4) for Y = H (1), Me (2), Cl (3) and NO2 (4). However, distinct topologies, i.e. linear (Y = H), helical (Y = Me and Cl) and zig-zag (Y = NO2) are noted with major differences in the pitch of the polymer. Geometry-optimisation, MEP and NPA analyses show a distinct electronic structure for the Y = NO2 derivative, in particular relating to the activation of the aryl ring. An exhaustive analysis of the molecular packing (point-to-point interactions, crystal structure similarity, Hirshfeld surface analysis, NCI and QTAIM, interaction energies and energy frameworks) points to the importance of C–H⋯π(aryl) interactions in stabilising the chains but these have a considerably reduced influence in the crystal with Y = NO2 (4), where π(aryl)⋯π(aryl) interactions are important. The more open arrangement for the linear chain in 1 facilitates the formation of C–H⋯π(aryl) interactions and the more compact arrangements enable the formation of stabilising, intra-chain methylene-C–H⋯S(thione) interactions 2–4. This study highlights the role of second-tier non-covalent interactions in the arrangement of conventional hydrogen bonding interactions. |
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Article |
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Tan, Sang Loon * Tiekink, Edward R. T. * |
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Tan, Sang Loon * Tiekink, Edward R. T. * |
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Tan, Sang Loon * |
title |
Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 |
title_short |
Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 |
title_full |
Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 |
title_fullStr |
Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 |
title_full_unstemmed |
Non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-O–H⋯O(hydroxyl) hydrogen bonding in crystals of (HOCH2CH2)2NC(S)N(H)(C6H4Y-4) for Y = H, Me, Cl and NO2 |
title_sort |
non-covalent interactions involving remote substituents influence the topologies of supramolecular chains featuring hydroxyl-o–h⋯o(hydroxyl) hydrogen bonding in crystals of (hoch2ch2)2nc(s)n(h)(c6h4y-4) for y = h, me, cl and no2 |
publisher |
Royal Society of Chemistry |
publishDate |
2021 |
url |
http://eprints.sunway.edu.my/1603/1/Tiekink%20acc%20cec%2023%201723.pdf http://eprints.sunway.edu.my/1603/ http://doi.org/10.1039/D0CE01810D |
_version_ |
1693728571002978304 |
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13.209306 |