Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon
Single crystals of two polymorphic forms of 4′-methyl-2,4-dinitrodiphenylamine were obtained by crystallization and characterized by X-ray diffraction analysis. One of the forms is non-centrosymmetric (space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2), while the se...
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| Format: | Article |
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MDPI AG
2023-02-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/13/2/296 |
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| author | Ivan V. Fedyanin Aida I. Samigullina |
| author_facet | Ivan V. Fedyanin Aida I. Samigullina |
| author_sort | Ivan V. Fedyanin |
| collection | DOAJ |
| description | Single crystals of two polymorphic forms of 4′-methyl-2,4-dinitrodiphenylamine were obtained by crystallization and characterized by X-ray diffraction analysis. One of the forms is non-centrosymmetric (space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2), while the second is centrosymmetric (space group <i>P</i>¯1) and contains two crystallographically independent molecules in the asymmetric unit. In both forms, the same supramolecular synthon, a dimer linked by bonding N-H···O, O···O, and C-H···O interactions were found. Despite nearly the same connectivity of the bonding interactions, the conformation of the supramolecular synthon is different, including its unavoidably different symmetry in two polymorphs. The comparison of the crystal packing of the orthorhombic polymorph with that of the related 2,4-dinitrodiphenylamine (space group <i>P</i>2<sub>1</sub>/<i>n</i>) shows the quasi-isostructurality of the fragments, infinite π-stacks joined by weak non-directional intermolecular interactions. However, the fragments are linked by the supramolecular synthons via either a two-fold axis or an inversion center, which lead to only the partial isostructurality of the crystals. |
| first_indexed | 2024-03-11T08:57:54Z |
| format | Article |
| id | doaj.art-6ab29fe2650a407e8535f527371ce5c8 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-11T08:57:54Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-6ab29fe2650a407e8535f527371ce5c82023-11-16T19:56:15ZengMDPI AGCrystals2073-43522023-02-0113229610.3390/cryst13020296Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular SynthonIvan V. Fedyanin0Aida I. Samigullina1A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St. 28, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, 119991 Moscow, RussiaSingle crystals of two polymorphic forms of 4′-methyl-2,4-dinitrodiphenylamine were obtained by crystallization and characterized by X-ray diffraction analysis. One of the forms is non-centrosymmetric (space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2), while the second is centrosymmetric (space group <i>P</i>¯1) and contains two crystallographically independent molecules in the asymmetric unit. In both forms, the same supramolecular synthon, a dimer linked by bonding N-H···O, O···O, and C-H···O interactions were found. Despite nearly the same connectivity of the bonding interactions, the conformation of the supramolecular synthon is different, including its unavoidably different symmetry in two polymorphs. The comparison of the crystal packing of the orthorhombic polymorph with that of the related 2,4-dinitrodiphenylamine (space group <i>P</i>2<sub>1</sub>/<i>n</i>) shows the quasi-isostructurality of the fragments, infinite π-stacks joined by weak non-directional intermolecular interactions. However, the fragments are linked by the supramolecular synthons via either a two-fold axis or an inversion center, which lead to only the partial isostructurality of the crystals.https://www.mdpi.com/2073-4352/13/2/296polymorphismsupramolecular synthonsisostructuralitylattice energyelectron density |
| spellingShingle | Ivan V. Fedyanin Aida I. Samigullina Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon Crystals polymorphism supramolecular synthons isostructurality lattice energy electron density |
| title | Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon |
| title_full | Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon |
| title_fullStr | Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon |
| title_full_unstemmed | Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon |
| title_short | Two Crystal Forms of 4′-Methyl-2,4-dinitrodiphenylamine: Polymorphism Governed by Conformational Flexibility of a Supramolecular Synthon |
| title_sort | two crystal forms of 4 methyl 2 4 dinitrodiphenylamine polymorphism governed by conformational flexibility of a supramolecular synthon |
| topic | polymorphism supramolecular synthons isostructurality lattice energy electron density |
| url | https://www.mdpi.com/2073-4352/13/2/296 |
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