DFT-calculated structures based on 1H NMR chemical shifts in solution vs. structures solved by single-crystal X-ray and crystalline-sponge methods: Assessing specific sources of discrepancies |
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| Authors: | Michael G. Siskos M. Iqbal Choudhary Ioannis P. Gerothanassis |
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| Affiliation: | 1. Section of Organic Chemistry & Biochemistry, Department of Chemistry, University of Ioannina, Ioannina, GR-45110, Greece;2. H.E.J. Research Institute of Chemistry, International Center for Biological and Chemical Sciences, University of Karachi, Karachi, 75270, Pakistan |
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| Abstract: | DFT calculations of 1H NMR chemical shifts, using various functionals and basis sets, the conductor-like polarizable continuum model and discrete solute-solvent hydrogen bond interactions have been used to derive the solution structures of methyl salicylate and methyl 2,5-dihydroxybenzoate. We demonstrate that very good agreement between experimental and computed 1H NMR chemical shifts can be obtained for various basis sets. The DFT structures in solution were compared with the recently reported X-ray structure, solved by the crystalline-sponge method, of the methyl salicylate and the single-crystal X-ray structure of methyl 2,5-dihydroxybenzoate. It is demonstrated that the information provided by 1H NMR chemical shifts about the solution structure is significantly more precise than that obtained by the single-crystal X-ray and the crystalline-sponge methods. |
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| Keywords: | DFT calculations Hydrogen bonding Single-crystal X-ray diffraction Crystalline-sponge method (CSM) |
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