Alkaline Metal Fluorooxalatouranilates: Structures and Selected Properties

IF 1.8 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry Pub Date : 2024-07-03 DOI:10.1134/s0036023623602866

V. N. Serezhkin, M. S. Grigoriev, M. V. Sukacheva, V. Yu. Losev, L. B. Serezhkina

{"title":"Alkaline Metal Fluorooxalatouranilates: Structures and Selected Properties","authors":"V. N. Serezhkin, M. S. Grigoriev, M. V. Sukacheva, V. Yu. Losev, L. B. Serezhkina","doi":"10.1134/s0036023623602866","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3>The structures of crystals Na3[UO2(C2O4)F3]⋅4H2O (I), K3[UO2(C2O4)F3] (II), K3[UO2(C2O4)2F]⋅3H2O (III), and Cs[UO2(C2O4)F]⋅H2O (IV) were studied for the first time using X-ray diffraction. The uranium-containing structural units are complexes [UO2(C2O4)F3]3– (for I and II), [UO2(C2O4)2F]3– (III), and [UO2(C2O4)F]– (IV) with crystal chemical formulas А(В01)M\\(_{3}^{1}\\), А(В01)2M1, and А(Q02)M1 (A = \\({\\text{UO}}_{{\\text{2}}}^{{{\\text{2 + }}}}\\); B01 or Q02 = \\({{{\\text{C}}}_{{\\text{2}}}}{\\text{O}}_{{\\text{4}}}^{{2 - }}\\); M1 = F–), respectively. In all compounds, the U(VI) atoms implement a pentagonal-bipyramidal coordination; in I–II the uranyl complexes have a mononuclear structure, and in crystals IV they have a chain structure similar to that known for [UO2(C2O4)(H2O)]⋅2H2O. The results obtained suggest that the sharp increase in the solubility of uranyl oxalate trihydrate in aqueous solutions with the addition of fluorides is due to the effect of structural depolymerization of coordination polymers in the presence of fluoride ions. A semi-empirical calculation was performed and the calculated and experimental vibration frequencies in the IR spectra of II and IV were compared.","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":1.8000,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1134/s0036023623602866","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

The structures of crystals Na₃[UO₂(C₂O₄)F₃]⋅4H₂O (I), K₃[UO₂(C₂O₄)F₃] (II), K₃[UO₂(C₂O₄)₂F]⋅3H₂O (III), and Cs[UO₂(C₂O₄)F]⋅H₂O (IV) were studied for the first time using X-ray diffraction. The uranium-containing structural units are complexes [UO₂(C₂O₄)F₃]^3– (for I and II), [UO₂(C₂O₄)₂F]^3– (III), and [UO₂(C₂O₄)F]^– (IV) with crystal chemical formulas А(В⁰¹)M\(_{3}^{1}\), А(В⁰¹)₂M¹, and А(Q⁰²)M¹ (A = \({\text{UO}}_{{\text{2}}}^{{{\text{2 + }}}}\); B⁰¹ or Q⁰² = \({{{\text{C}}}_{{\text{2}}}}{\text{O}}_{{\text{4}}}^{{2 - }}\); M¹ = F^–), respectively. In all compounds, the U(VI) atoms implement a pentagonal-bipyramidal coordination; in I–II the uranyl complexes have a mononuclear structure, and in crystals IV they have a chain structure similar to that known for [UO₂(C₂O₄)(H₂O)]⋅2H₂O. The results obtained suggest that the sharp increase in the solubility of uranyl oxalate trihydrate in aqueous solutions with the addition of fluorides is due to the effect of structural depolymerization of coordination polymers in the presence of fluoride ions. A semi-empirical calculation was performed and the calculated and experimental vibration frequencies in the IR spectra of II and IV were compared.

Abstract Image

查看原文本刊更多论文

碱金属氟氧基戊二酸酯：结构和选定特性

摘要利用 X 射线衍射法首次研究了 Na3[UO2(C2O4)F3]⋅4H2O（I）、K3[UO2(C2O4)F3]（II）、K3[UO2(C2O4)2F]⋅3H2O（III）和 Cs[UO2(C2O4)F]⋅H2O（IV）晶体的结构。含铀的结构单元是[UO2(C2O4)F3]3- 复合物（I 和 II）、[UO2(C2O4)2F]3- 复合物（III）和[UO2(C2O4)F]- 复合物（III）、和[UO2(C2O4)F]- (IV)，其晶体化学式为 А(В01)M\(_{3}^{1}\)、А(В01)2M1 和 А(Q02)M1（A = \({text{UO}}_{text{2}}^{{text{2 + }}}}\)；B01 或 Q02 = （{{text{C}}}_{{text{2}}}}\text{O}}_{{text{4}}}^{{2 - }}）；M1 = F-）。在所有化合物中，U(VI) 原子都实现了五角双锥配位；在 I-II 中，铀酰配合物具有单核结构，而在晶体 IV 中，它们具有类似于已知 [UO2(C2O4)(H2O)]⋅2H2O 的链状结构。所得结果表明，草酸铀酰三水合物在水溶液中的溶解度随着氟化物的加入而急剧增加，这是由于配位聚合物在氟离子存在下的结构解聚效应。对 II 和 IV 进行了半经验计算，并比较了红外光谱中的计算振动频率和实验振动频率。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Russian Journal of Inorganic Chemistry 化学-无机化学与核化学

CiteScore

3.10

自引率

38.10%

发文量

237

审稿时长

3 months

期刊介绍： Russian Journal of Inorganic Chemistry is a monthly periodical that covers the following topics of research: the synthesis and properties of inorganic compounds, coordination compounds, physicochemical analysis of inorganic systems, theoretical inorganic chemistry, physical methods of investigation, chemistry of solutions, inorganic materials, and nanomaterials.