American Journal of Organic Chemistry
p-ISSN: 2163-1271 e-ISSN: 2163-1301
2024; 12(1): 1-19
doi:10.5923/j.ajoc.20241201.01
Received: Dec. 22, 2023; Accepted: Dec. 29, 2023; Published: Jan. 15, 2024
Zakaria Koulabiga 1, Kouadio Honoré Yao 2, Akoun Abou 2, Abdoulaye Djandé 1, Michel Giorgi 3, Stéphane Coussan 4
1Laboratory of Molecular Chemistry and Materials (LC2M), Research Team: Organic Chemistry and Phytochemistry, University Joseph KI-ZERBO, 03 BP 7021 Ouagadougou 03, Burkina Faso
2Department of Training and Research in Electrical and Electronic Engineering, Research Team: Instrumentation, Image and Spectroscopy, Felix Houphouet-Boigny National Polytechnic Institute, BP 1093 Yamoussoukro, Cote d’Ivoire
3Spectropole, Federation of Chemical Sciences, Marseille FR1739 Campus St. Jérôme, 52 av. Escadrille Normandie-Niemen, Marseille, France
4Laboratory: Physics of Ionic and Molecular Interactions (PIIM), Research Team H2M, UMR 7345, CNRS/Aix-Marseille University, Marseille, France
Correspondence to: Akoun Abou , Department of Training and Research in Electrical and Electronic Engineering, Research Team: Instrumentation, Image and Spectroscopy, Felix Houphouet-Boigny National Polytechnic Institute, BP 1093 Yamoussoukro, Cote d’Ivoire.
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Copyright © 2024 The Author(s). Published by Scientific & Academic Publishing.
This work is licensed under the Creative Commons Attribution International License (CC BY).
http://creativecommons.org/licenses/by/4.0/
This article deals with a combined experimental and computational study of a 6-substituted coumarin derivative, namely, 2-oxo-2H-chromen-6-yl 4-methoxybenzoate (I). The compound was synthetized by O-acetylation of 6-hydroxycoumarin with 4-methoxybenzoyl chloride in the presence of tetrahydrofuran as a solvent and triethylamine as a base. The crystal structure has a P21 space group and crystallizes in the monoclinic system with dimensions of 𝑎 = 3.8956 (4) Å, 𝑏 = 10.1366 (6) Å, and 𝑐 = 17.3178 (13) Å. The angles between the crystal axes are 𝛼 = 𝛾 = 90° and 𝛽 = 90.580 (7)°, with a 𝑍 value of 2. The compound was structurally characterized by both spectroscopy and single-crystal X-ray diffraction (XRD). In the latter, the structure of (I) was solved by direct methods and refined as a 2-component twin to a final R value of 0.0495 for 2966 independent reflections. The structure is stabilized by H-π and π-π stacking interactions between neighboring aromatic rings, as well as intra- and intermolecular C—H…O hydrogen bonds that extend along the [001] direction. The analysis of intermolecular interactions was conducted using dnorm and shape-index mappings. The results of this analysis highlighted the same interactions as those found by XRD analysis, namely C-H...O hydrogen bonds, H-π and π-π stacking interactions. As well, the two-dimensional fingerprint plots (FP) show specific close contacts between atom pairs and the contributions from different contacts. The largest contributions to the Hirshfeld surface, 34.9% and 33.3%, come from O···H/H…O and H···H contacts, respectively. In additionally, the molecular geometry of (I) was optimized using both ab initio method namely restricted Hartree-Fock (RHF) method and density functional theory (DFT/RB3LYP) with the 6-311++G(d, p) basis set in ground state. The outcomes of these quantum chemical calculations are consistent with the observed structure. The only reported difference concerns the Hartree-Fock calculations where the computed torsion angle between the coumarin ring system and the benzoate ring, C10—O3—C8—C9, of -85.6° is slightly larger than the observed value (−51.3 (8)°). Also, frequency calculations were carried out with the optimizing structures to perform vibrational analysis, check compound stability and obtain some thermodynamic parameters. Molecular orbital calculations providing electron-density plots of the HOMO and LUMO molecular orbitals were also performed with the frequency calculation methods using the same basis sets. The theoretical values of the HOMO-LUMO energy gap yielding from these calculations are 4.40 eV for (DFT/B3LYP/6–311++G(d,p)) and 9.77 eV for (RHF/6–311++G(d)) methods.
Keywords: 6-substituted coumarin derivative, Spectroscopic analysis, Crystal structure, Conformational analysis, Hirshfeld surface analysis, Quantum chemical calculations
Cite this paper: Zakaria Koulabiga , Kouadio Honoré Yao , Akoun Abou , Abdoulaye Djandé , Michel Giorgi , Stéphane Coussan , Synthesis, Characterization, Hirshfeld Surface Analysis and Quantum Chemical Calculations of 2-oxo-2H- Chromen-6-yl 4-Methoxybenzoate, American Journal of Organic Chemistry, Vol. 12 No. 1, 2024, pp. 1-19. doi: 10.5923/j.ajoc.20241201.01.
Scheme 1. Numbering of carbon atoms used in spectra analysis. |
Figure 1. Electrospray ionization mass spectrum of the molecule |
Figure 2. 13C-NMR Spectrum of compound (I) |
Figure 3. Experimental 1H-NMR spectrum |
Figure 4. Experimental 13C (APT)-NMR spectrum |
Figures 5. Experimental HSQC spectra |
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Figure 6. An ORTEP [9] view of the title compound with the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. Dashed lines indicate hydrogen bonds |
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Figure 7. Part of the crystal packing of the title compound showing the infinite 1D chain along [100]. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity. |
Figure 8. A view of the crystal packing showing π–π stacking interactions (dashed lines). The green dots are ring centroids of rings |
Figure 9a. Hirshfeld surfaces mapped over dnorm (-0.117 to 1.324 a.u.) |
Figure 9b. Shape-index map (-1.000 to 1.000 a.u) |
Figure 9c. 2D plot showing the exact location of π–π stacking interactions |
Figure 10. Decomposed two-dimensional fingerprint plots for the title compound. Various close contacts and their relative contributions are indicated |
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Figure 11. DFT/B3LYP correlation graphic between the experimental and theoretical bond lengths in (Å) |
Figure 12. RHF correlation graphic between the experimental and theoretical bond lengths in (Å) |
Figure 13. DFT/B3LYP correlation graphic between the experimental and theoretical bond angles in (°) |
Figure 14. RHF correlation graphic between the experimental and theoretical bond angles in (°) |
Figure 15. Atom-by-atom superimposition of the X-ray structure (blue) on the calculated structure of (I), red, by (DFT/ B3LYP/6-311++G(d,p) |
Figure 16. Atom-by-atom superimposition of the X-ray structure (blue) on the calculated structure of (I), green, by RHF/6-311++G(d,p) |
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Figure 17. Correlation graphic between the experimental and theoretical DFT vibration frequencies (cm–1) |
Figure 18. Correlation graphic between the experimental and theoretical HF vibration frequencies (cm–1) |
Figure 19. DFT Calculated vibrational spectra of compound (I) |
Figure 20. DFT Calculated vibrational spectra of compound (I) |
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(1) |
Figure 21. MEP map (in atomic units) calculated using DFT/RB3LYP/6-311++G(d,p) and RHF/6-311++G(d,p) |
(2) |
(3) |
(4) |
(5) |
(6) |
(7) |
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Figure 22. The distributions and energy levels of the HOMO and LUMO orbitals computed for compound (I) |
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(8) |
(9) |
(10) |
(11) |
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Table 14. All β (a.u.) components and β ×10−30 (esu) values calculated using HF and DFT levels of theory |
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