Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density

Lorraine A. Malaspina; Anna A. Hoser; Alison J. Edwards; Magdalena Woińska; Michael J. Turner; Jason R. Price; Kunihisa Sugimoto; Eiji Nishibori; Hans-Beat Bürgi; Dylan Jayatilaka; Simon Grabowsky

doi:10.1039/D0CE00378F

Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density†

Lorraine A. Malaspina,

^a Anna A. Hoser,

^b Alison J. Edwards,

^c Magdalena Woińska,

^b Michael J. Turner,^d Jason R. Price,

^e Kunihisa Sugimoto,

^fg Eiji Nishibori,

^h Hans-Beat Bürgi,

^ij Dylan Jayatilaka

^d and Simon Grabowsky

*^ai

Author affiliations

* Corresponding authors

^a Institute for Inorganic Chemistry and Crystallography, University of Bremen, Leobener Str. 3, 28359 Bremen, Germany

^b Biological and Chemical Research Centre, Chemistry Department, University of Warsaw, Zwirki i Wigury 101, 02-089 Warsaw, Poland

^c Australian Centre for Neutron Scattering, ANSTO, New Illawarra Road, Lucas Heights NSW 2234, Australia

^d School of Molecular Sciences, Chemistry M313, The University of Western Australia, 35 Stirling Highway, Perth WA 6009, Australia

^e Australian Synchrotron, ANSTO, 800 Blackburn Rd, Clayton VIC 3168, Australia

^f Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

^g Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida-Ushinomiya-cho, Sakyo-ku, Kyoto 606-8501, Japan

^h Division of Physics, Faculty of Pure and Applied Sciences, Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, Japan

ⁱ Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland
E-mail: simon.grabowsky@dcb.unibe.ch

^j Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland

Abstract

Resonance-assisted hydrogen bonds (RAHBs) are exploited in chemical synthesis or serve as models for biologically relevant proton-transfer reactions [K. T. Mahmudov and A. J. L. Pombeiro, Chem. – Eur. J., 2016, 22, 16356–16398]. Their properties depend on the position of the hydrogen atom between donor and acceptor atoms. In the intramolecular RAHB of hydrogen maleate salts, this position is strongly influenced by the counter cation and varies from highly asymmetric to perfectly symmetric. This compound class is therefore ideally suited to investigate the factors determining geometry and electron density of intramolecular RAHBs. Here, it is shown that Hirshfeld atom refinements (HARs) of X-ray diffraction data of different hydrogen maleate salts can accurately and precisely match the hydrogen atom positions obtained from neutron diffraction and are independent of the model used for the hydrogen atom displacement parameters. Thus, the simplest, i.e. isotropic, HAR model can be used to locate hydrogen atoms also in bridging positions. In contrast, the determination of electron-density parameters with X-ray constrained wavefunction (XCW) fitting requires anisotropic, highly accurate hydrogen atom displacement parameters.

CrystEngComm

Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density†

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Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density

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