Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates
In this study, we investigated how the presence of multiple intermolecular interaction sites influences the heteromeric supramolecular assembly of <i>N</i>-[(3-pyridinylamino) thioxomethyl] carbamates with fluoroiodobenzenes. Three targets—R-<i>N</i>-[(3-pyridinylamino) thiox...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/12/3685 |
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| author | Kelly N. Shunje Boris B. Averkiev Christer B. Aakeröy |
| author_facet | Kelly N. Shunje Boris B. Averkiev Christer B. Aakeröy |
| author_sort | Kelly N. Shunje |
| collection | DOAJ |
| description | In this study, we investigated how the presence of multiple intermolecular interaction sites influences the heteromeric supramolecular assembly of <i>N</i>-[(3-pyridinylamino) thioxomethyl] carbamates with fluoroiodobenzenes. Three targets—R-<i>N</i>-[(3-pyridinylamino) thioxomethyl] carbamate (R = methyl, ethyl, and isobutyl)—were selected and crystallized, resulting in three parent structures, five co-crystals, and one co-crystal solvate. Three hydrogen-bonded parent crystal structures were stabilized by N-H···N hydrogen bonding and assembled into layers that stacked on top of one another. Molecular electrostatic potential surfaces were employed to rank binding sites (Npyr > C=S > C=O) in order to predict the dominant interactions. The N-H⋯H hydrogen bond was replaced by I⋯Npyr in 3/6 cases, I⋯C=S in 4/6 cases, and I⋯O=C in 1 case. Interestingly, the I⋯C=S halogen bond coexisted twice with I⋯Npyr and I⋯O=C. Overall, the MEPs were fairly reliable for predicting co-crystallization outcomes; however, it is crucial to also consider factors such as molecular flexibility. Finally, halogen-bond donors are capable of competing for acceptor sites, even in the presence of strong hydrogen-bond donors. |
| first_indexed | 2024-03-09T22:57:09Z |
| format | Article |
| id | doaj.art-6f1543cc17cd4b27a5b231adad00056f |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T22:57:09Z |
| publishDate | 2022-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-6f1543cc17cd4b27a5b231adad00056f2023-11-23T18:09:32ZengMDPI AGMolecules1420-30492022-06-012712368510.3390/molecules27123685Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] CarbamatesKelly N. Shunje0Boris B. Averkiev1Christer B. Aakeröy2Department of Chemistry, Kansas State University, Manhattan, KS 66506, USADepartment of Chemistry, Kansas State University, Manhattan, KS 66506, USADepartment of Chemistry, Kansas State University, Manhattan, KS 66506, USAIn this study, we investigated how the presence of multiple intermolecular interaction sites influences the heteromeric supramolecular assembly of <i>N</i>-[(3-pyridinylamino) thioxomethyl] carbamates with fluoroiodobenzenes. Three targets—R-<i>N</i>-[(3-pyridinylamino) thioxomethyl] carbamate (R = methyl, ethyl, and isobutyl)—were selected and crystallized, resulting in three parent structures, five co-crystals, and one co-crystal solvate. Three hydrogen-bonded parent crystal structures were stabilized by N-H···N hydrogen bonding and assembled into layers that stacked on top of one another. Molecular electrostatic potential surfaces were employed to rank binding sites (Npyr > C=S > C=O) in order to predict the dominant interactions. The N-H⋯H hydrogen bond was replaced by I⋯Npyr in 3/6 cases, I⋯C=S in 4/6 cases, and I⋯O=C in 1 case. Interestingly, the I⋯C=S halogen bond coexisted twice with I⋯Npyr and I⋯O=C. Overall, the MEPs were fairly reliable for predicting co-crystallization outcomes; however, it is crucial to also consider factors such as molecular flexibility. Finally, halogen-bond donors are capable of competing for acceptor sites, even in the presence of strong hydrogen-bond donors.https://www.mdpi.com/1420-3049/27/12/3685hydrogen bondshalogen bondsbinding preferenceintermolecular interactions |
| spellingShingle | Kelly N. Shunje Boris B. Averkiev Christer B. Aakeröy Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates Molecules hydrogen bonds halogen bonds binding preference intermolecular interactions |
| title | Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates |
| title_full | Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates |
| title_fullStr | Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates |
| title_full_unstemmed | Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates |
| title_short | Influence of Multiple Binding Sites on the Supramolecular Assembly of <i>N</i>-[(3-pyridinylamino) Thioxomethyl] Carbamates |
| title_sort | influence of multiple binding sites on the supramolecular assembly of i n i 3 pyridinylamino thioxomethyl carbamates |
| topic | hydrogen bonds halogen bonds binding preference intermolecular interactions |
| url | https://www.mdpi.com/1420-3049/27/12/3685 |
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