Experimental charge-density study of paracetamol - multipole refinement in the presence of a disordered methyl group

Bak, J.M., Dominiak, P.M., Wilson, C.C. and Wozniak, K. (2009) Experimental charge-density study of paracetamol - multipole refinement in the presence of a disordered methyl group. Acta Crystallographica. Section A: Foundations of Crystallography, 65(6), pp. 490-500. (doi:10.1107/S0108767309031729)

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Abstract

A high-resolution single-crystal X-ray study of paracetamol has been performed at 85 K. Different approaches to modeling the experimental electron density (ED) were tested for the dynamically disordered portions of the molecule in order to check to what extent it is possible to obtain a proper ED distribution in the ordered part. Models were examined in which the methyl-group ED was built from pseudoatoms taken from the University at Buffalo Pseudoatom Databank or the Invariom database, with multipole parameters for the remaining atoms being obtained from free refinement. The κ' restricted multipolar model (KRMM) and free κ' refinements were compared; restriction of the κ' parameters was essential in order to obtain values of the electrostatic interaction energy consistent with the results of theoretical single-point periodic calculations. After simultaneous use of KRMM refinement and the databases to model the methyl group, the bond critical point properties and interaction electrostatic energy values were found to be closer to those obtained from theory. Additionally, some discrepancies in the ED distribution and dipole moment among transferred aspherical atom model refinements utilizing both theoretical databases and parameters from theoretical periodic calculations are shown. Including the influence of the crystal field in the periodic calculations increases the ED in the hydroxyl and amide groups, thus leading to higher values of the electrostatic interaction energy, changes in the electrostatic potential values mapped on the isodensity surface and changes in the shape of the anisotropic displacement parameters with respect to results found for both database models.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wilson, Professor Charles
Authors: Bak, J.M., Dominiak, P.M., Wilson, C.C., and Wozniak, K.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Acta Crystallographica. Section A: Foundations of Crystallography
ISSN:0108-7673
ISSN (Online):1600-5724
Published Online:17 October 2009

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