Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids

Dmytro V Dudenko; P Andrew Williams; Colan E Hughes; Oleg N Antzutkin; Sitaram P Velaga; Steven P Brown; Kenneth D M Harris

doi:10.1021/jp4041106

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids

J Phys Chem C Nanomater Interfaces. 2013 Jun 13;117(23):12258-12265. doi: 10.1021/jp4041106. Epub 2013 May 3.

Authors

Dmytro V Dudenko¹, P Andrew Williams², Colan E Hughes², Oleg N Antzutkin³, Sitaram P Velaga⁴, Steven P Brown⁵, Kenneth D M Harris²

Affiliations

¹ School of Chemistry, Cardiff University , Park Place, Cardiff CF10 3AT, Wales, U.K. ; Department of Physics, University of Warwick , Coventry CV4 7AL, England, U.K.
² School of Chemistry, Cardiff University , Park Place, Cardiff CF10 3AT, Wales, U.K.
³ Department of Physics, University of Warwick , Coventry CV4 7AL, England, U.K. ; Chemistry of Interfaces, Luleå University of Technology , Luleå S-97187, Sweden.
⁴ Department of Health Science, Luleå University of Technology , Luleå S-97187, Sweden.
⁵ Department of Physics, University of Warwick , Coventry CV4 7AL, England, U.K.

Abstract

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The ¹H and ¹³C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of ¹H and ¹³C chemical shifts for directly bonded ¹³C-¹H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure.