Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide)
The structure of a new type of polyoxo cluster complex that contains thirteen uranium atoms, {U13}, is reported. The complex crystallized from methanol containing tetravalent uranium (UIV) with a basic organic ligand, and was characterized as dichloridooctacosa-μ2-methanolato-octakis(methanolato)oct...
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doaj-2b7bf715efab4419a2e5cb922b23ff992021-08-05T14:43:11ZengInternational Union of CrystallographyActa Crystallographica Section E: Crystallographic Communications2056-98902021-08-0177884785210.1107/S2056989021007623yz2009Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide)Sebastian Fichter0Thomas Radoske1Atsushi Ikeda-Ohno2Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Bautzner Landstrasse 400, 01328 Dresden, GermanyHelmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Bautzner Landstrasse 400, 01328 Dresden, GermanyCollaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), 2-4 Shirakata, Tokai-mura, Naka-gun, 319-1195 Ibaraki-ken, JapanThe structure of a new type of polyoxo cluster complex that contains thirteen uranium atoms, {U13}, is reported. The complex crystallized from methanol containing tetravalent uranium (UIV) with a basic organic ligand, and was characterized as dichloridooctacosa-μ2-methanolato-octakis(methanolato)octa-μ4-oxido-tridecauranium, [U13(CH3O)35.7Cl2.3O8] or [U13(μ4-Ooxo)8Clx(MeO)38–x] (x = 2.3, MeO = methoxide) (I), by single-crystal X-ray diffraction. The characterized {U13} polyoxo cluster complex (I) possesses a single cubic uranium polyhedron at the centre of the cluster core. To the best of our knowledge, this is the very first example of a polyoxo actinide complex that bears a single cubic polyhedron in its structure. The cubic polyhedron in I is well comparable in shape with those in bulk UO2. The U—O bonds in the cubic polyhedron of I are, however, significantly shorter than those not only in bulk UO2 but also in another analogue in the {U38} cluster. This shortening of U—O bonds, together with BVS calculations and the overall negative charge (2−) of I, suggests that the central uranium atom in I, which forms the single cubic coordination polyhedron, is presumably oxidized to the pentavalent state (UV) from the original tetravalent state (UIV). Complex I is, hence, the first example of a polyoxo cluster possessing a single cubic coordination polyhedron of UV.http://scripts.iucr.org/cgi-bin/paper?S2056989021007623polyoxo clusterf-block elementsactinidesuraniumtetravalentcrystal structure |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Sebastian Fichter Thomas Radoske Atsushi Ikeda-Ohno |
spellingShingle |
Sebastian Fichter Thomas Radoske Atsushi Ikeda-Ohno Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide) Acta Crystallographica Section E: Crystallographic Communications polyoxo cluster f-block elements actinides uranium tetravalent crystal structure |
author_facet |
Sebastian Fichter Thomas Radoske Atsushi Ikeda-Ohno |
author_sort |
Sebastian Fichter |
title |
Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide) |
title_short |
Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide) |
title_full |
Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide) |
title_fullStr |
Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide) |
title_full_unstemmed |
Structure of the {U13} polyoxo cluster U13O8Clx(MeO)38–x (x = 2.3, MeO = methoxide) |
title_sort |
structure of the {u13} polyoxo cluster u13o8clx(meo)38–x (x = 2.3, meo = methoxide) |
publisher |
International Union of Crystallography |
series |
Acta Crystallographica Section E: Crystallographic Communications |
issn |
2056-9890 |
publishDate |
2021-08-01 |
description |
The structure of a new type of polyoxo cluster complex that contains thirteen uranium atoms, {U13}, is reported. The complex crystallized from methanol containing tetravalent uranium (UIV) with a basic organic ligand, and was characterized as dichloridooctacosa-μ2-methanolato-octakis(methanolato)octa-μ4-oxido-tridecauranium, [U13(CH3O)35.7Cl2.3O8] or [U13(μ4-Ooxo)8Clx(MeO)38–x] (x = 2.3, MeO = methoxide) (I), by single-crystal X-ray diffraction. The characterized {U13} polyoxo cluster complex (I) possesses a single cubic uranium polyhedron at the centre of the cluster core. To the best of our knowledge, this is the very first example of a polyoxo actinide complex that bears a single cubic polyhedron in its structure. The cubic polyhedron in I is well comparable in shape with those in bulk UO2. The U—O bonds in the cubic polyhedron of I are, however, significantly shorter than those not only in bulk UO2 but also in another analogue in the {U38} cluster. This shortening of U—O bonds, together with BVS calculations and the overall negative charge (2−) of I, suggests that the central uranium atom in I, which forms the single cubic coordination polyhedron, is presumably oxidized to the pentavalent state (UV) from the original tetravalent state (UIV). Complex I is, hence, the first example of a polyoxo cluster possessing a single cubic coordination polyhedron of UV. |
topic |
polyoxo cluster f-block elements actinides uranium tetravalent crystal structure |
url |
http://scripts.iucr.org/cgi-bin/paper?S2056989021007623 |
work_keys_str_mv |
AT sebastianfichter structureoftheu13polyoxoclusteru13o8clxmeo38xx23meomethoxide AT thomasradoske structureoftheu13polyoxoclusteru13o8clxmeo38xx23meomethoxide AT atsushiikedaohno structureoftheu13polyoxoclusteru13o8clxmeo38xx23meomethoxide |
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