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

Malaspina, Lorraine A.; Hoser, Anna A.; Edwards, Alison J.; Woińska, Magdalena; Turner, Michael J.; Price, Jason R.; Sugimoto, Kunihisa; Nishibori, Eiji; Bürgi, Hans-Beat; Jayatilaka, Dylan; Grabowsky, Simon (2020). Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density. CrystEngComm, 22(28), pp. 4778-4789. Royal Society of Chemistry 10.1039/d0ce00378f

[img] Text
070_Malaspina2020_CrystEngComm.pdf - Published Version
Restricted to registered users only
Available under License Publisher holds Copyright.

Download (3MB)

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.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Malaspina, Lorraine, Grabowsky, Simon

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

1466-8033

Publisher:

Royal Society of Chemistry

Language:

English

Submitter:

Simon Grabowsky

Date Deposited:

02 Feb 2021 16:30

Last Modified:

05 Dec 2022 15:43

Publisher DOI:

10.1039/d0ce00378f

BORIS DOI:

10.48350/150591

URI:

https://boris.unibe.ch/id/eprint/150591

Actions (login required)

Edit item Edit item
Provide Feedback