Plutonium(III) oxalate

While the structure of [[anhydrous]] plutonium(III) oxalate is unknown, two possible structures have been predicted with [[density functional theory]] calculations. One structure consists of plutonium-oxalate layers in a [[honeycomb]]-like arrangement, and the other consists of 2D sheets which are connected into a 3D network via [[Bridging ligand|bridging]] oxalate groups. Both of these structures have been calculated to be stable.{{cite journal | last1=Isbill | first1=Sara B. | last2=Miskowiec | first2=Andrew J. | title=Computational insights into the structure of anhydrous Pu(III) oxalate | journal=Journal of Nuclear Materials | date=2025 | volume=605 | article-number=155583 | doi=10.1016/j.jnucmat.2024.155583 | bibcode=2025JNuM..60555583I | osti=2491455 | url=https://doi.org/10.1016/j.jnucmat.2024.155583 }}

While the structure of [[anhydrous]] plutonium(III) oxalate is unknown, two possible structures have been predicted with [[density functional theory]] calculations. One structure consists of plutonium-oxalate layers in a [[honeycomb]]-like arrangement, and the other consists of 2D sheets which are connected into a 3D network via [[Bridging ligand|bridging]] oxalate groups. Both of these structures have been calculated to be stable.{{cite journal | last1=Isbill | first1=Sara B. | last2=Miskowiec | first2=Andrew J. | title=Computational insights into the structure of anhydrous Pu(III) oxalate | journal=Journal of Nuclear Materials | date=2025 | volume=605 | article-number=155583 | doi=10.1016/j.jnucmat.2024.155583 | bibcode=2025JNuM..60555583I | osti=2491455 | url=https://doi.org/10.1016/j.jnucmat.2024.155583 }}

On the other hand, the structure of plutonium(III) oxalate decahydrate ({{chem2|Pu2(C2O4)3*10H2O}}) is known. It has been determined to adopt the same structure as [[lanthanum(III) oxalate]] decahydrate, {{chem2|La2(C2O4)3*10H2O}}.{{cite journal | last1=Chackraburtty | first1=D. M. | title=X-ray evidence of plutonium(III) oxalate decahydrate | journal=Acta Crystallographica | date=1963 | volume=16 | issue=8 | page=834 | doi=10.1107/S0365110X63002127 | bibcode=1963AcCry..16..834C | url=https://doi.org/10.1107/S0365110X63002127 | url-access=subscription }} It is made up of repeating honeycomb-like layers of composition {{chem2|Pu2(C2O3)3(H2O)6}}. Within these layers, each plutonium atom is bonded to nine oxygen atoms, and has a [[coordination geometry]] of distorted [[Tricapped trigonal prismatic molecular geometry|tricapped trigonal prismatic]]. Three oxygen atoms come from three water molecules, and six oxygen atoms come from three oxalate groups, which are [[Chelation|chelating]] (forming a ring). Per [[formula unit]], there are approximately four water molecules separate from the layers, though this varies based on the level of hydration. Compositions that vary from {{chem2|Pu2(C2O4)3*10H2O}} correspond to disorder in the water molecules between layers.{{cite journal | last1=Uríková | first1=Daniela Veronika | last2=Kampitakis | first2=Giannis | last3=Císařová | first3=Ivana | last4=Alemayehu | first4=Adam | last5=Kloda | first5=Matouš | last6=Zákutná | first6=Dominika | last7=Lang | first7=Kamil | last8=Demel | first8=Jan | last9=Tyrpekl | first9=Václav | title=Lanthanide Oxalates: From Single Crystals to 2D Functional Honeycomb Nanosheets | journal=Inorganic Chemistry | date=2025 | volume=64 | issue=8 | pages=3686–3695 | doi=10.1021/acs.inorgchem.4c04293 | pmid=39964120 | pmc=11881034 | url=https://doi.org/10.1021/acs.inorgchem.4c04293 }}

On the other hand, the structure of plutonium(III) oxalate decahydrate ({{chem2|Pu2(C2O4)3*10H2O}}) is known. It has been determined to adopt the same structure as [[lanthanum(III) oxalate]] decahydrate, {{chem2|La2(C2O4)3*10H2O}}.{{cite journal | last1=Chackraburtty | first1=D. M. | title=X-ray evidence of plutonium(III) oxalate decahydrate | journal=Acta Crystallographica | date=1963 | volume=16 | issue=8 | page=834 | doi=10.1107/S0365110X63002127 | bibcode=1963AcCry..16..834C | url=https://doi.org/10.1107/S0365110X63002127 | url-access=subscription }} It is made up of repeating honeycomb-like layers of composition {{chem2|Pu2(C2O3)3(H2O)6}}. Within these layers, each plutonium(III) center is [[Chelation|chelated]] by three oxalate ions and coordinated by three water molecules, in a [[tricapped trigonal prismatic molecular geometry]]. Per [[formula unit]], there are approximately four water molecules separate from the layers, though this varies based on the level of hydration. Compositions that vary from {{chem2|Pu2(C2O4)3*10H2O}} correspond to disorder in the water molecules between layers.{{cite journal | last1=Uríková | first1=Daniela Veronika | last2=Kampitakis | first2=Giannis | last3=Císařová | first3=Ivana | last4=Alemayehu | first4=Adam | last5=Kloda | first5=Matouš | last6=Zákutná | first6=Dominika | last7=Lang | first7=Kamil | last8=Demel | first8=Jan | last9=Tyrpekl | first9=Václav | title=Lanthanide Oxalates: From Single Crystals to 2D Functional Honeycomb Nanosheets | journal=Inorganic Chemistry | date=2025 | volume=64 | issue=8 | pages=3686–3695 | doi=10.1021/acs.inorgchem.4c04293 | pmid=39964120 | pmc=11881034 | url=https://doi.org/10.1021/acs.inorgchem.4c04293 }}

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