Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods

Michael G Siskos; M Iqbal Choudhary; Ioannis P Gerothanassis

doi:10.3390/molecules22030415

Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods

Molecules. 2017 Mar 7;22(3):415. doi: 10.3390/molecules22030415.

Authors

Michael G Siskos¹, M Iqbal Choudhary², Ioannis P Gerothanassis^{3

4}

Affiliations

¹ Section of Organic Chemistry & Biochemistry, Department of Chemistry, University of Ioannina, Ioannina GR-45110, Greece. msiskos@cc.uoi.gr.
² H.E.J. Research Institute of Chemistry, International Center for Biological and Chemical Sciences, University of Karachi, Karachi 75270, Pakistan. iqbalhej@yahoo.com.
³ Section of Organic Chemistry & Biochemistry, Department of Chemistry, University of Ioannina, Ioannina GR-45110, Greece. igeroth@uoi.gr.
⁴ H.E.J. Research Institute of Chemistry, International Center for Biological and Chemical Sciences, University of Karachi, Karachi 75270, Pakistan. igeroth@uoi.gr.

Abstract

The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

Keywords: DFT; NMR; X-ray diffraction; chemical shifts; hydrogen bonding.

Publication types

Review

MeSH terms

Hydrogen Bonding*
Hydrogen*
Models, Chemical
Models, Molecular
Molecular Structure
Proton Magnetic Resonance Spectroscopy
Quantum Theory
Solutions
X-Ray Diffraction

Substances

Solutions
Hydrogen