Structure and bonding of a radium coordination compound in the solid state

Frankie D. White; Nikki A. Thiele; Megan E. Simms; Samantha K. Cary

doi:10.1038/s41557-023-01366-z

Structure and bonding of a radium coordination compound in the solid state

Frankie D. White, Nikki A. Thiele, Megan E. Simms, Samantha K. Cary

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra²⁺ complex using ²²⁶Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra²⁺ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba²⁺) yielded a 10-coordinate ‘Pac-Man’-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra²⁺ and by analogy with Ba²⁺, supporting greater water lability in Ra²⁺ complexes than in their Ba²⁺ counterparts. Barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra²⁺ chemistry cannot always be predicted using Ba²⁺.

Original language	English
Pages (from-to)	168-172
Number of pages	5
Journal	Nature Chemistry
Volume	16
Issue number	2
DOIs	https://doi.org/10.1038/s41557-023-01366-z
State	Published - Feb 2024

Funding

The staff of the Medical Isotopes Development Group and the Building 3047 Operations Group at Oak Ridge National Laboratory are thanked for their Ra production, purification and dispensing efforts. This research was supported by the Laboratory Directed Research and Development (N.A.T.) programme of Oak Ridge National Laboratory. The Ra used in this research was supplied by the United States Department of Energy Isotope Program, managed by the Office of Isotope R&D and Production. The manuscript was produced by UT–Battelle, LLC under contract no. DE-AC05-00OR22725 with the United States Department of Energy. The publisher acknowledges the United States Government licence to provide public access under the Department of Energy (DOE) Public Access Plan ( https://energy.gov/downloads/doe-public-access-plan ). The funders had no role in the study design, data collection and analysis, decision to publish or preparation of the manuscript. 226 226 The staff of the Medical Isotopes Development Group and the Building 3047 Operations Group at Oak Ridge National Laboratory are thanked for their 226Ra production, purification and dispensing efforts. This research was supported by the Laboratory Directed Research and Development (N.A.T.) programme of Oak Ridge National Laboratory. The 226Ra used in this research was supplied by the United States Department of Energy Isotope Program, managed by the Office of Isotope R&D and Production. The manuscript was produced by UT–Battelle, LLC under contract no. DE-AC05-00OR22725 with the United States Department of Energy. The publisher acknowledges the United States Government licence to provide public access under the Department of Energy (DOE) Public Access Plan (https://energy.gov/downloads/doe-public-access-plan). The funders had no role in the study design, data collection and analysis, decision to publish or preparation of the manuscript.

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title = "Structure and bonding of a radium coordination compound in the solid state",

abstract = "The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra2+ complex using 226Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra2+ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba2+) yielded a 10-coordinate {\textquoteleft}Pac-Man{\textquoteright}-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra2+ and by analogy with Ba2+, supporting greater water lability in Ra2+ complexes than in their Ba2+ counterparts. Barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra2+ chemistry cannot always be predicted using Ba2+.",

author = "White, {Frankie D.} and Thiele, {Nikki A.} and Simms, {Megan E.} and Cary, {Samantha K.}",

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PY - 2024/2

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N2 - The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra2+ complex using 226Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra2+ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba2+) yielded a 10-coordinate ‘Pac-Man’-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra2+ and by analogy with Ba2+, supporting greater water lability in Ra2+ complexes than in their Ba2+ counterparts. Barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra2+ chemistry cannot always be predicted using Ba2+.

AB - The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra2+ complex using 226Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra2+ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba2+) yielded a 10-coordinate ‘Pac-Man’-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra2+ and by analogy with Ba2+, supporting greater water lability in Ra2+ complexes than in their Ba2+ counterparts. Barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra2+ chemistry cannot always be predicted using Ba2+.

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Structure and bonding of a radium coordination compound in the solid state

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