Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate
The title compound, 2C14H14N4OH2O, comprises a neutral molecule containing a central pyrazol-3-one ring flanked by an N-bound phenyl group and a C-bound 5-methyl-1H-pyrazol-3-yl group (at positions adjacent to the carbonyl substituent), its zwitterionic tautomer, whereby the N-bound proton of the c...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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International Union of Crystallography
2019
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| Online Access: | http://eprints.sunway.edu.my/1015/ http://eprints.sunway.edu.my/1015/1/Tiekink%20Co%20Crystallization%20of%20a%20neutral%20molecule%20Acta%20Cryst%202019%20E75%20565.pdf |
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| author | Asiri, Abdullah M. Alzahrani, Khalid A. H. Faidallah, Hassan M. Alamry, Khalid A. Jotani, Mukesh M. Tiekink, Edward R. T. * |
| author_facet | Asiri, Abdullah M. Alzahrani, Khalid A. H. Faidallah, Hassan M. Alamry, Khalid A. Jotani, Mukesh M. Tiekink, Edward R. T. * |
| author_sort | Asiri, Abdullah M. |
| building | SU Institutional Repository |
| collection | Online Access |
| description | The title compound, 2C14H14N4OH2O, comprises a neutral molecule containing a central pyrazol-3-one ring flanked by an N-bound phenyl group and a C-bound 5-methyl-1H-pyrazol-3-yl group (at positions adjacent to the carbonyl
substituent), its zwitterionic tautomer, whereby the N-bound proton of the central ring is now resident on the pendant ring, and a water molecule of crystallization. Besides systematic variations in geometric parameters, the two independent organic molecules have broadly similar conformations, as seen in the dihedral angle between the five-membered rings [9.72 (9) for the neutral
molecule and 3.32 (9) for the zwitterionic tautomer] and in the dihedral angles between the central and pendant five-membered rings [28.19 (8) and 20.96 (8)
(neutral molecule); 11.33 (9) and 11.81 (9)]. In the crystal, pyrazolyl-N—HO(carbonyl) and pyrazolium-N—HN(pyrazolyl) hydrogen bonds between the independent organic molecules give rise to non-symmetric ninemembered {HNNHNC3O} and {HNNHNC3O} synthons, which differ
in the positions of the N-bound H atoms. These aggregates are connected into a supramolecular layer in the bc plane by water-O—HN(pyrazolide), waterO—HO(carbonyl) and pyrazolyl-N—HO(water) hydrogen bonding. The
layers are linked into a three-dimensional architecture by methyl-C—H(phenyl) interactions. The different interactions, in particular the weaker contacts, formed by the organic molecules are clearly evident in the calculated Hirshfeld surfaces, and the calculated electrostatic potentials differentiate the
tautomers. |
| first_indexed | 2025-11-14T21:15:27Z |
| format | Article |
| id | sunway-1015 |
| institution | Sunway University |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:15:27Z |
| publishDate | 2019 |
| publisher | International Union of Crystallography |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | sunway-10152020-10-07T08:44:20Z http://eprints.sunway.edu.my/1015/ Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate Asiri, Abdullah M. Alzahrani, Khalid A. H. Faidallah, Hassan M. Alamry, Khalid A. Jotani, Mukesh M. Tiekink, Edward R. T. * QD Chemistry The title compound, 2C14H14N4OH2O, comprises a neutral molecule containing a central pyrazol-3-one ring flanked by an N-bound phenyl group and a C-bound 5-methyl-1H-pyrazol-3-yl group (at positions adjacent to the carbonyl substituent), its zwitterionic tautomer, whereby the N-bound proton of the central ring is now resident on the pendant ring, and a water molecule of crystallization. Besides systematic variations in geometric parameters, the two independent organic molecules have broadly similar conformations, as seen in the dihedral angle between the five-membered rings [9.72 (9) for the neutral molecule and 3.32 (9) for the zwitterionic tautomer] and in the dihedral angles between the central and pendant five-membered rings [28.19 (8) and 20.96 (8) (neutral molecule); 11.33 (9) and 11.81 (9)]. In the crystal, pyrazolyl-N—HO(carbonyl) and pyrazolium-N—HN(pyrazolyl) hydrogen bonds between the independent organic molecules give rise to non-symmetric ninemembered {HNNHNC3O} and {HNNHNC3O} synthons, which differ in the positions of the N-bound H atoms. These aggregates are connected into a supramolecular layer in the bc plane by water-O—HN(pyrazolide), waterO—HO(carbonyl) and pyrazolyl-N—HO(water) hydrogen bonding. The layers are linked into a three-dimensional architecture by methyl-C—H(phenyl) interactions. The different interactions, in particular the weaker contacts, formed by the organic molecules are clearly evident in the calculated Hirshfeld surfaces, and the calculated electrostatic potentials differentiate the tautomers. International Union of Crystallography 2019-03-31 Article NonPeerReviewed text en cc_by_nc_4 http://eprints.sunway.edu.my/1015/1/Tiekink%20Co%20Crystallization%20of%20a%20neutral%20molecule%20Acta%20Cryst%202019%20E75%20565.pdf Asiri, Abdullah M. and Alzahrani, Khalid A. H. and Faidallah, Hassan M. and Alamry, Khalid A. and Jotani, Mukesh M. and Tiekink, Edward R. T. * (2019) Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate. Acta Crystallographica Section E Crystallographic Communications, 75 (5). pp. 565-570. ISSN 2056-9890 http://doi.org/10.1107/S2056989019004389 doi:10.1107/S2056989019004389 |
| spellingShingle | QD Chemistry Asiri, Abdullah M. Alzahrani, Khalid A. H. Faidallah, Hassan M. Alamry, Khalid A. Jotani, Mukesh M. Tiekink, Edward R. T. * Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate |
| title | Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate |
| title_full | Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate |
| title_fullStr | Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate |
| title_full_unstemmed | Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate |
| title_short | Co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and Hirshfeld surface analysis of 5-methyl-4-(5-methyl-1H-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1H-pyrazol-3-one 5-methyl-4-(5-methyl-1H-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-1-ide monohydrate |
| title_sort | co-crystallization of a neutral molecule and its zwitterionic tautomer: structure and hirshfeld surface analysis of 5-methyl-4-(5-methyl-1h-pyrazol-3-yl)-2-phenyl-2,3-dihydro-1h-pyrazol-3-one 5-methyl-4-(5-methyl-1h-pyrazol-2-ium-3-yl)-3-oxo-2-phenyl-2,3-dihydro-1h-pyrazol-1-ide monohydrate |
| topic | QD Chemistry |
| url | http://eprints.sunway.edu.my/1015/ http://eprints.sunway.edu.my/1015/ http://eprints.sunway.edu.my/1015/ http://eprints.sunway.edu.my/1015/1/Tiekink%20Co%20Crystallization%20of%20a%20neutral%20molecule%20Acta%20Cryst%202019%20E75%20565.pdf |