Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses.
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| Title: | Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses. |
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| Authors: | Venkatesan, Perumal1, Thamotharan, Subbiah2, Kumar, Rajendran Ganesh1, Ilangovan, Andivelu1 |
| Source: | CrystEngComm. 2015, Vol. 17 Issue 4, p904-915. 12p. |
| Subjects: | Alkoxy compounds, Esters, Organic compounds, Crystals, Crystallography |
| Abstract: | A series of functionalized malonic acid half-ester derivatives (parent compound MHE-1), with variations in functional groups at different positions on the aromatic ring, have been synthesized and crystal structures are determined at room temperature (296 K). The methyl (4-CH3, MHE-2) and chloro (4-Cl, MHE-3) derivatives are isomorphous with each other. The overall crystal packing of MHE-1–3 is similar. However, there are few differences observed between stacking of layers in these structures. Compounds with nitro (3-NO2, MHE-4) and ethyl ester (2-COOC2H5, MHE-5) substituents crystallize in different space groups and thus crystal packing is different when compared to MHE-1–3. In all the structures, intramolecular N–H…O and O–H…O hydrogen bonds generate a two fused S(6) ring motif. A detailed study is carried out to visualize intermolecular interactions observed in all five crystal structures (MHE-1–5) using Hirshfeld surface (HS) analysis with two dimensional fingerprint plots. The relative contribution of intermolecular H…H contacts in MHE-3 is substantially lower than that in MHE-1–2, though similar crystal packing arrangements of MHE-1–3 and MHE-2 and MHE-3 are isomorphous. From HS analysis it is clear that the observed H…H contact contribution (MHE-3) is a consequence of the presence of the chlorine substituent and growing contribution of Cl…H contacts. The relative contributions of other intermolecular contacts involving various atoms are comparable in MHE-1–3 structures. The intermolecular interaction energies are quantified using PIXEL for various molecular pairs extracted from respective crystal structures. Interestingly, there are some invariant and variable intermolecular contacts observed between different groups in all five structures. [ABSTRACT FROM AUTHOR] |
| Copyright of CrystEngComm is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
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| Items | – Name: Title Label: Title Group: Ti Data: Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Venkatesan%2C+Perumal%22">Venkatesan, Perumal</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Thamotharan%2C+Subbiah%22">Thamotharan, Subbiah</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Kumar%2C+Rajendran+Ganesh%22">Kumar, Rajendran Ganesh</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Ilangovan%2C+Andivelu%22">Ilangovan, Andivelu</searchLink><relatesTo>1</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22CrystEngComm%22">CrystEngComm</searchLink>. 2015, Vol. 17 Issue 4, p904-915. 12p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Alkoxy+compounds%22">Alkoxy compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Esters%22">Esters</searchLink><br /><searchLink fieldCode="DE" term="%22Organic+compounds%22">Organic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Crystals%22">Crystals</searchLink><br /><searchLink fieldCode="DE" term="%22Crystallography%22">Crystallography</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: A series of functionalized malonic acid half-ester derivatives (parent compound MHE-1), with variations in functional groups at different positions on the aromatic ring, have been synthesized and crystal structures are determined at room temperature (296 K). The methyl (4-CH3, MHE-2) and chloro (4-Cl, MHE-3) derivatives are isomorphous with each other. The overall crystal packing of MHE-1–3 is similar. However, there are few differences observed between stacking of layers in these structures. Compounds with nitro (3-NO2, MHE-4) and ethyl ester (2-COOC2H5, MHE-5) substituents crystallize in different space groups and thus crystal packing is different when compared to MHE-1–3. In all the structures, intramolecular N–H…O and O–H…O hydrogen bonds generate a two fused S(6) ring motif. A detailed study is carried out to visualize intermolecular interactions observed in all five crystal structures (MHE-1–5) using Hirshfeld surface (HS) analysis with two dimensional fingerprint plots. The relative contribution of intermolecular H…H contacts in MHE-3 is substantially lower than that in MHE-1–2, though similar crystal packing arrangements of MHE-1–3 and MHE-2 and MHE-3 are isomorphous. From HS analysis it is clear that the observed H…H contact contribution (MHE-3) is a consequence of the presence of the chlorine substituent and growing contribution of Cl…H contacts. The relative contributions of other intermolecular contacts involving various atoms are comparable in MHE-1–3 structures. The intermolecular interaction energies are quantified using PIXEL for various molecular pairs extracted from respective crystal structures. Interestingly, there are some invariant and variable intermolecular contacts observed between different groups in all five structures. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of CrystEngComm is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/c4ce02125h Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 12 StartPage: 904 Subjects: – SubjectFull: Alkoxy compounds Type: general – SubjectFull: Esters Type: general – SubjectFull: Organic compounds Type: general – SubjectFull: Crystals Type: general – SubjectFull: Crystallography Type: general Titles: – TitleFull: Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Venkatesan, Perumal – PersonEntity: Name: NameFull: Thamotharan, Subbiah – PersonEntity: Name: NameFull: Kumar, Rajendran Ganesh – PersonEntity: Name: NameFull: Ilangovan, Andivelu IsPartOfRelationships: – BibEntity: Dates: – D: 23 M: 01 Text: 2015 Type: published Y: 2015 Identifiers: – Type: issn-print Value: 14668033 Numbering: – Type: volume Value: 17 – Type: issue Value: 4 Titles: – TitleFull: CrystEngComm Type: main |
| ResultId | 1 |
