Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals
Aniline–phenol recognition is studied in the crystal engineering context in several 1:1 cocrystals that contain a closed cyclic hydrogen-bonded [...O—H...N—H...]2 tetramer supramolecular synthon (II). Twelve cocrystals of 3,4,5- and 2,3,4-trichlorophenol with one of eight halogenated anilines have b...
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| Format: | Article |
| Language: | English |
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International Union of Crystallography
2014-07-01
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| Series: | IUCrJ |
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| Online Access: | http://scripts.iucr.org/cgi-bin/paper?S2052252514012081 |
| _version_ | 1818510699155947520 |
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| author | Arijit Mukherjee Karuna Dixit Siddhartha P. Sarma Gautam R. Desiraju |
| author_facet | Arijit Mukherjee Karuna Dixit Siddhartha P. Sarma Gautam R. Desiraju |
| author_sort | Arijit Mukherjee |
| collection | DOAJ |
| description | Aniline–phenol recognition is studied in the crystal engineering context in several 1:1 cocrystals that contain a closed cyclic hydrogen-bonded [...O—H...N—H...]2 tetramer supramolecular synthon (II). Twelve cocrystals of 3,4,5- and 2,3,4-trichlorophenol with one of eight halogenated anilines have been characterized. Ten of these cocrystals contain an extended octamer synthon that is assembled with hydrogen bonding and π...π stacking that defines a Long-Range Synthon Aufbau Module (LSAM). The design strategy is, therefore, based on the construction and transferability of the LSAM, which is a dimer of tetramers. Using the LSAM concept, two short cell axes in the crystal structures can be predicted. Whilst one of them is dictated by synthon II, the other one is dominated by π...π interactions. The third cell axis can also be predicted, in some cases, by systematic tuning of the halogen bonds. The design strategy is also verified in cocrystals of non-halogenated precursors. The observation of this large synthon in so many structures points to its stability and possible existence in solution. To this end, one-dimensional 1H and 15N NMR studies, performed on the 3,4,5-trichlorophenol–3,5-dichloroaniline cocrystal in CDCl3, show characteristic downfield shifts that point to a π...π stacked structure and to the robustness of the hydrogen-bonded aggregates. Nuclear Overhauser effects point to hydrogen bonding between aniline and phenol molecules in the aggregates. Diffusion-ordered spectroscopy and T1 inversion recovery experiments show that stacking is present in concentrated solution and lost at a certain dilution. A sequence of events is therefore established: molecules of the aniline and the phenol associate via hydrogen bonding to form tetramers, and tetramers subsequently stack to form octamers. |
| first_indexed | 2024-12-10T23:23:34Z |
| format | Article |
| id | doaj.art-e4b56084e9644cd595b13541766d81d8 |
| institution | Directory Open Access Journal |
| issn | 2052-2525 |
| language | English |
| last_indexed | 2024-12-10T23:23:34Z |
| publishDate | 2014-07-01 |
| publisher | International Union of Crystallography |
| record_format | Article |
| series | IUCrJ |
| spelling | doaj.art-e4b56084e9644cd595b13541766d81d82022-12-22T01:29:39ZengInternational Union of CrystallographyIUCrJ2052-25252014-07-011422823910.1107/S2052252514012081bi5032Aniline–phenol recognition: from solution through supramolecular synthons to cocrystalsArijit Mukherjee0Karuna Dixit1Siddhartha P. Sarma2Gautam R. Desiraju3Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, IndiaMolecular Biophysics Unit, Indian Institute of Science, Bangalore 560 012, IndiaMolecular Biophysics Unit, Indian Institute of Science, Bangalore 560 012, IndiaSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, IndiaAniline–phenol recognition is studied in the crystal engineering context in several 1:1 cocrystals that contain a closed cyclic hydrogen-bonded [...O—H...N—H...]2 tetramer supramolecular synthon (II). Twelve cocrystals of 3,4,5- and 2,3,4-trichlorophenol with one of eight halogenated anilines have been characterized. Ten of these cocrystals contain an extended octamer synthon that is assembled with hydrogen bonding and π...π stacking that defines a Long-Range Synthon Aufbau Module (LSAM). The design strategy is, therefore, based on the construction and transferability of the LSAM, which is a dimer of tetramers. Using the LSAM concept, two short cell axes in the crystal structures can be predicted. Whilst one of them is dictated by synthon II, the other one is dominated by π...π interactions. The third cell axis can also be predicted, in some cases, by systematic tuning of the halogen bonds. The design strategy is also verified in cocrystals of non-halogenated precursors. The observation of this large synthon in so many structures points to its stability and possible existence in solution. To this end, one-dimensional 1H and 15N NMR studies, performed on the 3,4,5-trichlorophenol–3,5-dichloroaniline cocrystal in CDCl3, show characteristic downfield shifts that point to a π...π stacked structure and to the robustness of the hydrogen-bonded aggregates. Nuclear Overhauser effects point to hydrogen bonding between aniline and phenol molecules in the aggregates. Diffusion-ordered spectroscopy and T1 inversion recovery experiments show that stacking is present in concentrated solution and lost at a certain dilution. A sequence of events is therefore established: molecules of the aniline and the phenol associate via hydrogen bonding to form tetramers, and tetramers subsequently stack to form octamers.http://scripts.iucr.org/cgi-bin/paper?S2052252514012081supramolecular synthoncrystal engineeringcocrystalcrystal structure prediction |
| spellingShingle | Arijit Mukherjee Karuna Dixit Siddhartha P. Sarma Gautam R. Desiraju Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals IUCrJ supramolecular synthon crystal engineering cocrystal crystal structure prediction |
| title | Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals |
| title_full | Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals |
| title_fullStr | Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals |
| title_full_unstemmed | Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals |
| title_short | Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals |
| title_sort | aniline phenol recognition from solution through supramolecular synthons to cocrystals |
| topic | supramolecular synthon crystal engineering cocrystal crystal structure prediction |
| url | http://scripts.iucr.org/cgi-bin/paper?S2052252514012081 |
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