Substituent effects on the crystallization mechanisms of 7-chloro-4-substituted-quinolines
| Autor: | João Paulo Gomes de Oliveira, Tainára Orlando, Gabriela Fehn Fiss, Marcos A. P. Martins, João P. P. Copetti, Mário L. A. A. Vasconcellos, Paulo R. S. Salbego, Jéssica M. L. Rosa, Nilo Zanatta, Helio G. Bonacorso |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Substituent Supramolecular chemistry Nucleation General Chemistry Crystal structure 010402 general chemistry Condensed Matter Physics 01 natural sciences 0104 chemical sciences law.invention Crystal chemistry.chemical_compound Crystallography Monomer chemistry law General Materials Science Crystallization Alkyl |
| Zdroj: | CrystEngComm. 22:4094-4107 |
| ISSN: | 1466-8033 |
| DOI: | 10.1039/d0ce00214c |
| Popis: | The crystallization mechanisms of a series of fourteen 7-chloro-4-substituted-quinolines (substituents: (1) OCH3, (2) OCH2CH3, (3) OCH2CHCH2, (4) O(CH2)2OH, (5) O(CH2)3OH, (6) NH(CH2)2CH3, (7) NH(CH2)3CH3, (8) NH(CH2)2OH, (9) NHCH(CH2CH3)CH2OH, (10) NH(CH2)2Cl, (11) NHNCH(C6H5), (12) NHNCH(2-FC6H4), (13) NHNCH(3-FC6H4), and (14) NHNCH(4-FC6H4)) were proposed based on a retrocrystallization approach using the supramolecular cluster as demarcation. Crystallization mechanism stage parameters – NCG% and NG/NC – were determined. The 4-substituents present in quinolines caused six different mechanisms, starting from the monomers in solution to dimers, 1D nuclei, and 2D nuclei (6, 11, 12); 2D nucleus formation (5); 1D nuclei to 2D nuclei (7, 9); concomitant dimers and 1D nuclei to a 3D crystal (8); 1D nuclei directly to a 3D crystal lattice (1–4, 10, 14), and dimers to 2D nuclei and then to a 3D crystal (13). Analysis of GAI showed atom⋯atom intermolecular interactions in the proposed first nuclei for compounds 4 and 5. The nucleation process inferred in the solid state was partially confirmed during the formation of the proto-crystal in solution due to the changes of the hydrogen chemical shift in variable-concentration 1H-NMR experiments. Results revealed that the size of the alkyl chain and the presence of different functional groups in the 4-substituents influenced the crystallization process. |
| Databáze: | OpenAIRE |
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