Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide
The crystal and molecular structures of the one-dimensional coordination polymer [Zn(S2COEt)2(4LH2)]n (1) and binuclear [Zn(S2COCy)2]2(4LH2) (2) are described, where 4LH2 is N,N'-bis(pyridin4-ylmethyl)ethanediamide. In 1, the Zn(S2COEt)2 entities are linked by bidentate bridging 4 LH2 ligands...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Oldenbourg Wissenschaftsverlag
2019
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| Online Access: | http://eprints.sunway.edu.my/1001/ http://eprints.sunway.edu.my/1001/1/Tieink%20Steric%20%20control%20Z%20Kristallogr%202019%20234%20165%20175_ACCEPTED.pdf |
| _version_ | 1848801938138726400 |
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| author | Tan, Yee Seng * Chu, Hao Zhe * Jotani, Mukesh M. Tiekink, Edward R. T. * |
| author_facet | Tan, Yee Seng * Chu, Hao Zhe * Jotani, Mukesh M. Tiekink, Edward R. T. * |
| author_sort | Tan, Yee Seng * |
| building | SU Institutional Repository |
| collection | Online Access |
| description | The crystal and molecular structures of the one-dimensional
coordination polymer [Zn(S2COEt)2(4LH2)]n (1) and binuclear
[Zn(S2COCy)2]2(4LH2) (2) are described, where 4LH2 is N,N'-bis(pyridin4-ylmethyl)ethanediamide. In 1, the Zn(S2COEt)2 entities are linked by bidentate bridging 4 LH2 ligands through the pyridyl-N atoms to generate a twisted supramolecular chain. As a result of monodentate xanthate ligands, the N2S4 donor set defines a distorted tetrahedral coordination geometry and, crucially, allows the participation of the non-coordinating sulphur atoms in supramolecular association. Thus, in the crystal amide-N‒
H…O(amide) and amide-N‒H…S(thione) hydrogen bonds link chains into a three-dimensional architecture. The substitution of the ethyl group in the xanthate ligand with a cyclohexyl group results in very different structural
outcomes. In 2, a binuclear molecule is observed with the coordination geometry for zinc being defined by chelating xanthate ligands and a pyridyl-N atom with the NS4 donor set defining a highly distorted geometry. In the molecular packing, amide-N‒H…S(thione) hydrogen bonds stabilise a supramolecular chain along the a-axis and these are connected into a three-dimensional arrangement by methylene-C‒H…O and methylene-C‒H…π(pyridyl) interactions. The relative importance of the specified intermolecular interactions and weaker, contributing contacts has been revealed by an analysis of the Hirshfeld surfaces of 1 and 2. |
| first_indexed | 2025-11-14T21:15:24Z |
| format | Article |
| id | sunway-1001 |
| institution | Sunway University |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:15:24Z |
| publishDate | 2019 |
| publisher | Oldenbourg Wissenschaftsverlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | sunway-10012020-10-07T08:51:44Z http://eprints.sunway.edu.my/1001/ Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide Tan, Yee Seng * Chu, Hao Zhe * Jotani, Mukesh M. Tiekink, Edward R. T. * QD Chemistry The crystal and molecular structures of the one-dimensional coordination polymer [Zn(S2COEt)2(4LH2)]n (1) and binuclear [Zn(S2COCy)2]2(4LH2) (2) are described, where 4LH2 is N,N'-bis(pyridin4-ylmethyl)ethanediamide. In 1, the Zn(S2COEt)2 entities are linked by bidentate bridging 4 LH2 ligands through the pyridyl-N atoms to generate a twisted supramolecular chain. As a result of monodentate xanthate ligands, the N2S4 donor set defines a distorted tetrahedral coordination geometry and, crucially, allows the participation of the non-coordinating sulphur atoms in supramolecular association. Thus, in the crystal amide-N‒ H…O(amide) and amide-N‒H…S(thione) hydrogen bonds link chains into a three-dimensional architecture. The substitution of the ethyl group in the xanthate ligand with a cyclohexyl group results in very different structural outcomes. In 2, a binuclear molecule is observed with the coordination geometry for zinc being defined by chelating xanthate ligands and a pyridyl-N atom with the NS4 donor set defining a highly distorted geometry. In the molecular packing, amide-N‒H…S(thione) hydrogen bonds stabilise a supramolecular chain along the a-axis and these are connected into a three-dimensional arrangement by methylene-C‒H…O and methylene-C‒H…π(pyridyl) interactions. The relative importance of the specified intermolecular interactions and weaker, contributing contacts has been revealed by an analysis of the Hirshfeld surfaces of 1 and 2. Oldenbourg Wissenschaftsverlag 2019-02 Article PeerReviewed text en http://eprints.sunway.edu.my/1001/1/Tieink%20Steric%20%20control%20Z%20Kristallogr%202019%20234%20165%20175_ACCEPTED.pdf Tan, Yee Seng * and Chu, Hao Zhe * and Jotani, Mukesh M. and Tiekink, Edward R. T. * (2019) Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide. Zeitschrift für Kristallographie - Crystalline Materials, 234 (3). pp. 165-175. ISSN 2194-4946 (In Press) http://doi.org/10.1515/zkri-2018-2120 doi:10.1515/zkri-2018-2120 |
| spellingShingle | QD Chemistry Tan, Yee Seng * Chu, Hao Zhe * Jotani, Mukesh M. Tiekink, Edward R. T. * Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide |
| title | Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide |
| title_full | Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide |
| title_fullStr | Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide |
| title_full_unstemmed | Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide |
| title_short | Steric control of supramolecular association in structures of Zn(S2COR)2 with N,N′-bis(pyridin-4-ylmethyl)oxalamide |
| title_sort | steric control of supramolecular association in structures of zn(s2cor)2 with n,n′-bis(pyridin-4-ylmethyl)oxalamide |
| topic | QD Chemistry |
| url | http://eprints.sunway.edu.my/1001/ http://eprints.sunway.edu.my/1001/ http://eprints.sunway.edu.my/1001/ http://eprints.sunway.edu.my/1001/1/Tieink%20Steric%20%20control%20Z%20Kristallogr%202019%20234%20165%20175_ACCEPTED.pdf |