Hirshfeld atom refinement for modelling strong hydrogen bonds

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dc.contributor.authorWoinska, Men_AU
dc.contributor.authorJayatilaka, Den_AU
dc.contributor.authorSpackman, MAen_AU
dc.contributor.authorEdwards, AJen_AU
dc.contributor.authorDominiak, DJen_AU
dc.contributor.authorWozniak, PMen_AU
dc.contributor.authorNishibori, Een_AU
dc.contributor.authorSugimoto, Ken_AU
dc.contributor.authorGrabowsky, Sen_AU
dc.date.accessioned2016-12-12T00:28:12Zen_AU
dc.date.available2016-12-12T00:28:12Zen_AU
dc.date.issued2014-01-01en_AU
dc.date.statistics2016-12-12en_AU
dc.description.abstractHigh-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position. © 2014, International Union of Crystallography.en_AU
dc.identifier.citationWoinska, M., Jayatilaka, D., Spackman, M. A., Edwards, A. J., Dominiak, P. M., Wozniak, K., Nishibori, E., Sugimoto, K., & Grabowsky, S. (2014). Hirshfeld atom refinement for modelling strong hydrogen bonds. Acta Crystallographica Section A: Foundations and Advances, A70(Part 5), 483-498. doi:10.1107/S2053273314012443en_AU
dc.identifier.govdoc7687en_AU
dc.identifier.issn2053-2733en_AU
dc.identifier.issuePart 5en_AU
dc.identifier.journaltitleActa Crystallographica Section A: Foundations and Advancesen_AU
dc.identifier.pagination483-498en_AU
dc.identifier.urihttp://dx.doi.org/10.1107/S2053273314012443en_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/8144en_AU
dc.identifier.volumeA70en_AU
dc.language.isoenen_AU
dc.publisherInternational Union of Crystallographyen_AU
dc.subjectSynchrotronsen_AU
dc.subjectX-ray diffractionen_AU
dc.subjectHydrogenen_AU
dc.subjectAnionsen_AU
dc.subjectDataen_AU
dc.titleHirshfeld atom refinement for modelling strong hydrogen bondsen_AU
dc.typeJournal Articleen_AU
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