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

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

doi:10.1038/s41557-023-01366-z

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

Journal Article · Thu Nov 09 00:00:00 EST 2023 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-023-01366-z· OSTI ID:2311306

^[1]; ^[1]; ^[1]; Cary, Samantha K. ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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. In conclusion, barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra²⁺ chemistry cannot always be predicted using Ba²⁺.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2311306

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 2 Vol. 16; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

An Eighteen-Membered Macrocyclic Ligand for Actinium-225 Targeted Alpha Therapy Thiele, Nikki A.; Brown, Victoria; Kelly, James M. Angewandte Chemie, Vol. 129, Issue 46 https://doi.org/10.1002/ange.201709532	journal	October 2017
Alpha-Emitters and Targeted Alpha Therapy in Oncology: from Basic Science to Clinical Investigations Makvandi, Mehran; Dupis, Edouard; Engle, Jonathan W. Targeted Oncology, Vol. 13, Issue 2 https://doi.org/10.1007/s11523-018-0550-9	journal	February 2018
Evaluation of potential chelating agents for radium Henriksen, Gjermund; Hoff, Per; Larsen, Roy H. Applied Radiation and Isotopes, Vol. 56, Issue 5 https://doi.org/10.1016/S0969-8043(01)00282-2	journal	May 2002
Comparative radium-223 labeling with NOTA and DOTA-somatostatin derivatives for a potential use in targeted cancer therapy Riondato, M.; Pastorino, S.; Duce, V. Nuclear Medicine and Biology, Vol. 72-73 https://doi.org/10.1016/S0969-8051(19)30328-2	journal	July 2019
Effect of radium-223 dichloride on symptomatic skeletal events in patients with castration-resistant prostate cancer and bone metastases: results from a phase 3, double-blind, randomised trial Sartor, Oliver; Coleman, Robert; Nilsson, Sten The Lancet Oncology, Vol. 15, Issue 7 https://doi.org/10.1016/S1470-2045(14)70183-4	journal	June 2014
Targeted alpha therapy using Radium-223: From physics to biological effects Marques, I. A.; Neves, A. R.; Abrantes, A. M. Cancer Treatment Reviews, Vol. 68 https://doi.org/10.1016/j.ctrv.2018.05.011	journal	July 2018
Extended X-ray absorption fine structure spectroscopy measurements and ab initio molecular dynamics simulations reveal the hydration structure of the radium(II) ion Yamaguchi, Akiko; Nagata, Kojiro; Kobayashi, Keita iScience, Vol. 25, Issue 8 https://doi.org/10.1016/j.isci.2022.104763	journal	August 2022
Crystal structure of radium sulfate: An X-ray powder diffraction and density functional theory study Matyskin, Artem V.; Ylmen, Rikard; Lagerkvist, Petra Journal of Solid State Chemistry, Vol. 253 https://doi.org/10.1016/j.jssc.2017.05.024	journal	September 2017
Advances in containment methods and plutonium recovery strategies that led to the structural characterization of plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl4(OSPh2)3 Cary, Samantha K.; Boland, Kevin S.; Cross, Justin N. Polyhedron, Vol. 126 https://doi.org/10.1016/j.poly.2017.01.013	journal	April 2017
Advancing Chelation Strategies for Large Metal Ions for Nuclear Medicine Applications Hu, Aohan; Wilson, Justin J. Accounts of Chemical Research, Vol. 55, Issue 6 https://doi.org/10.1021/acs.accounts.2c00003	journal	March 2022
Radium Revisited: Revitalization of the Coordination Chemistry of Nature’s Largest +2 Cation Bai, Zhuanling; Brannon, Jacob; Celis-Barros, Cristian Inorganic Chemistry, Vol. 62, Issue 22 https://doi.org/10.1021/acs.inorgchem.3c01170	journal	May 2023
Reining in Radium for Nuclear Medicine: Extra-Large Chelator Development for an Extra-Large Ion Simms, Megan E.; Sibley, Megan M.; Driscoll, Darren M. Inorganic Chemistry, Vol. 62, Issue 50 https://doi.org/10.1021/acs.inorgchem.3c02985	journal	October 2023
Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex White, Frankie D.; Celis-Barros, Cristian; Rankin, Jillian Inorganic Chemistry, Vol. 58, Issue 5 https://doi.org/10.1021/acs.inorgchem.8b03566	journal	February 2019
Ionizable Calixarene-Crown Ethers with High Selectivity for Radium over Light Alkaline Earth Metal Ions Chen, Xiaoyuan; Ji, Min; Fisher, Darrell R. Inorganic Chemistry, Vol. 38, Issue 23 https://doi.org/10.1021/ic990135+	journal	October 1999
Hydration Energies and Structures of Alkaline Earth Metal Ions, M ²⁺ (H ₂ O) _n , n = 5−7, M = Mg, Ca, Sr, and Ba Rodriguez-Cruz, Sandra E.; Jockusch, Rebecca A.; Williams, Evan R. Journal of the American Chemical Society, Vol. 121, Issue 38 https://doi.org/10.1021/ja9911871	journal	September 1999
Crystal Structure of the Diaqua(1,10-Diaza-18-Crown-6) (Tetrafluorosuccinato-O)barium Complex Chekhlov, A. N. Russian Journal of Coordination Chemistry, Vol. 28, Issue 2, p. 137-142 https://doi.org/10.1023/A:1014292320015	journal	February 2002
Crystal Structure of an Unusual Hydrated Complex of 1,4,7,10,13-Pentaoxacyclohexadecane-14,16-Dione with Calcium Thiocyanate Chekhlov, A. N. Russian Journal of Coordination Chemistry, Vol. 28, Issue 3, p. 163-169 https://doi.org/10.1023/A:1014767817232	journal	March 2002
Twinned and Disordered Crystal Structure of Solvated Bis[Aqua(2.2.2-Cryptand)Calcium] Hexa(Isothiocyanato)Calcium Chekhlov, A. N. Russian Journal of Coordination Chemistry, Vol. 28, Issue 7, p. 454-460 https://doi.org/10.1023/A:1016288909060	journal	July 2002
Crystal Structure of Diaqua(2.2.2-cryptand)strontium Bis(thiocyanate) Chekhlov, A. N. Journal of Structural Chemistry, Vol. 43, Issue 3, p. 501-506 https://doi.org/10.1023/A:1020353503220	journal	March 2002
Basics of X-ray Diffraction Stanjek, H.; Häusler, W. Hyperfine Interactions, Vol. 154, Issue 1-4 https://doi.org/10.1023/B:HYPE.0000032028.60546.38	journal	January 2004
Matching chelators to radiometals for radiopharmaceuticals Price, Eric W.; Orvig, Chris Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60304K	journal	January 2014
Selective oxo ligand functionalisation and substitution reactivity in an oxo/catecholate-bridged U^IV/U^IV Pacman complex Cowie, Bradley E.; Douair, Iskander; Maron, Laurent Chemical Science, Vol. 11, Issue 27 https://doi.org/10.1039/D0SC02297G	journal	January 2020
Towards the stable chelation of radium for biomedical applications with an 18-membered macrocyclic ligand Abou, Diane S.; Thiele, Nikki A.; Gutsche, Nicholas T. Chemical Science, Vol. 12, Issue 10 https://doi.org/10.1039/D0SC06867E	journal	January 2021
Elucidating the coordination chemistry of the radium ion for targeted alpha therapy Ivanov, Alexander S.; Simms, Megan E.; Bryantsev, Vyacheslav S. Chemical Communications, Vol. 58, Issue 71 https://doi.org/10.1039/D2CC03156F	journal	January 2022
Crystal structures of complexes between alkali-metal salts and cyclic polyethers. Part IV. The crystal structures of dibenzo-30-crown-10 (2,3:17,18-dibenzo-1,4,7,10,13,16,19,22,25,28-decaoxacyclotriaconta-2,17-diene) and of its complex with potassium iodide Bush, M. A.; Truter, Mary R. Journal of the Chemical Society, Perkin Transactions 2, Issue 3 https://doi.org/10.1039/p29720000345	journal	January 1972
Alpha Emitter Radium-223 and Survival in Metastatic Prostate Cancer Parker, C.; Nilsson, S.; Heinrich, D. New England Journal of Medicine, Vol. 369, Issue 3 https://doi.org/10.1056/NEJMoa1213755	journal	July 2013
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Reaction between dibenzo-30-crown-10 and potassium thiocyanate; structures of the 1:1 complexes, anhydrous and monohydrated, [K(C28H40O10)]+.SCN− and [K(C28H40O10)]+.SCN−.H2O Owen, J. D.; Truter, M. R.; Wingfield, J. N. Acta Crystallographica Section C Crystal Structure Communications, Vol. 40, Issue 9 https://doi.org/10.1107/S0108270184008568	journal	September 1984
Barium (cryptand 222B)Cl2.6H2O Pettit, W. A.; Baenziger, N. C. Acta Crystallographica Section C Crystal Structure Communications, Vol. 50, Issue 2 https://doi.org/10.1107/S0108270193009205	journal	February 1994
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
Tumor Therapy with Targeted Atomic Nanogenerators McDevitt, M. R. Science, Vol. 294, Issue 5546 https://doi.org/10.1126/science.1064126	journal	November 2001
Radium Ra 223 Dichloride Injection: U.S. Food and Drug Administration Drug Approval Summary Kluetz, P. G.; Pierce, W.; Maher, V. E. Clinical Cancer Research, Vol. 20, Issue 1 https://doi.org/10.1158/1078-0432.CCR-13-2665	journal	November 2013
Radium-223 dichloride bone-targeted alpha particle therapy for hormone-refractory breast cancer metastatic to bone Takalkar, Amol; Adams, Scott; Subbiah, Vivek Experimental Hematology & Oncology, Vol. 3, Issue 1 https://doi.org/10.1186/2162-3619-3-23	journal	January 2014
The Radiochemical and Radiopharmaceutical Applications of Radium Gott, Matthew; Steinbach, Jörg; Mamat, Constantin Open Chemistry, Vol. 14, Issue 1 https://doi.org/10.1515/chem-2016-0011	journal	January 2016
Chelators and metal complex stability for radiopharmaceutical applications Okoye, Nkemakonam C.; Baumeister, Jakob E.; Najafi Khosroshahi, Firouzeh Radiochimica Acta, Vol. 107, Issue 9-11 https://doi.org/10.1515/ract-2018-3090	journal	July 2019
Zur Kristallchemie des Radiums Weigel, F.; Trinkl, A. ract, Vol. 10, Issue 1-2 https://doi.org/10.1524/ract.1968.10.12.78	journal	November 1968
Zur Kristallchemie des Radiums Weigel, F.; Trinkl, A. ract, Vol. 9, Issue 1 https://doi.org/10.1524/ract.1968.9.1.36	journal	May 1968
Zur Kristallchemie des Radiums Weigel, F.; Trinkx, A. ract, Vol. 9, Issue 2-3 https://doi.org/10.1524/ract.1968.9.23.140	journal	August 1968
Zur Kristallchemie des Radiums Weigel, F.; Trinkl, A. ract, Vol. 12, Issue 1 https://doi.org/10.1524/ract.1969.12.1.29	journal	July 1969
Zur Kristallchemie des Radiums Weigel, F.; Trinkl, A. ract, Vol. 19, Issue 4 https://doi.org/10.1524/ract.1973.19.4.199	journal	April 1973
225Ac-PSMA-617 for PSMA-Targeted -Radiation Therapy of Metastatic Castration-Resistant Prostate Cancer Kratochwil, C.; Bruchertseifer, F.; Giesel, F. L. Journal of Nuclear Medicine, Vol. 57, Issue 12 https://doi.org/10.2967/jnumed.116.178673	journal	July 2016
Harnessing α-Emitting Radionuclides for Therapy: Radiolabeling Method Review Yang, Hua; Wilson, Justin J.; Orvig, Chris Journal of Nuclear Medicine, Vol. 63, Issue 1 https://doi.org/10.2967/jnumed.121.262687	journal	September 2021
Overview of the Most Promising Radionuclides for Targeted Alpha Therapy: The “Hopeful Eight” Eychenne, Romain; Chérel, Michel; Haddad, Férid Pharmaceutics, Vol. 13, Issue 6 https://doi.org/10.3390/pharmaceutics13060906	journal	June 2021
Examination of the complexation ability of different calixarene derivatives towards [223Ra]RaCl2 in a hospital radiopharmaceutical laboratory Freesmeyer, Martin; Weigand, Wolfgang; Weisheit, Thomas Nuklearmedizin, Vol. 57, Issue 06 https://doi.org/10.3413/Nukmed-0933-18-08	journal	December 2018

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

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