Comprehensive structural study of lanthanide(III) chloride hydrates: [RECl3·xH2O (RE = La–Nd, Sm–Lu; x = 6, 7)]

IF 0.5 Q4 CRYSTALLOGRAPHY

Acta Crystallographica Section E: Crystallographic Communications Pub Date : 2024-11-01 DOI:10.1107/S2056989024011319

Thimira Kandabadage , Beau Legnon , Sviatoslav Baranets

{"title":"Comprehensive structural study of lanthanide(III) chloride hydrates: [RECl3·xH2O (RE = La–Nd, Sm–Lu; x = 6, 7)]","authors":"Thimira Kandabadage , Beau Legnon , Sviatoslav Baranets","doi":"10.1107/S2056989024011319","DOIUrl":null,"url":null,"abstract":"<div><div>This study presents a comprehensive crystallographic analysis of the lanthanide(III) chloride hydrates [RECl3·xH2O (RE = La–Nd, Sm–Lu; x = 6, 7)], offering new structural data for the series. The research highlights the influence of hydration levels and lanthanide contraction on the crystal structures, while identifying missing data for specific hydrates in existing structural databases.</div></div><div><div>A comprehensive crystallographic study is presented of the complete series of rare-earth(III) chloride hydrates. Early lanthanides form dimeric [(H2O)7RE(μ-Cl)2RE(H2O)7]4+ binuclear complexes in which each RE atom (RE = La3+, Ce3+) is coordinated by seven H2O molecules and two bridging inner-sphere chloride ions. Di-μ-chlorido-bis[heptaaqualanthanide(III)] tetrachloride, [(H2O)7RE(μ-Cl)2RE(H2O)7]Cl4, crystallizes in the triclinic space group P1. Heavier lanthanides exhibit monomeric [RECl2(H2O)6]+ units where each RE atom (RE = Pr3+, Nd3+, Sm3+–Lu3+) is coordinated by six H2O molecules and two inner-sphere chloride ions. Hexaaquadichloridolanthanide(III) chlorides, [RECl2(H2O)6]Cl, adopt the monoclinic space group P2/c. In both structures, the cationic inner-sphere complex is counter-charged by the corresponding number of outer-sphere Cl− anions, in which the metal ion and outer-sphere chloride ion lie on crystallographic twofold axes. Crystal structures for all compounds were determined in high quality with refined H-atom positions and were collected at the same temperature (100 K), providing a uniform structural dataset and addressing discrepancies in previous reports. The crystal structure of [HoCl2(H2O)6]Cl is reported for the first time.</div></div>","PeriodicalId":7367,"journal":{"name":"Acta Crystallographica Section E: Crystallographic Communications","volume":"80 12","pages":"Pages 1342-1349"},"PeriodicalIF":0.5000,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section E: Crystallographic Communications","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2056989024002342","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CRYSTALLOGRAPHY","Score":null,"Total":0}

引用次数: 0

Abstract

This study presents a comprehensive crystallographic analysis of the lanthanide(III) chloride hydrates [RECl₃·xH₂O (RE = La–Nd, Sm–Lu; x = 6, 7)], offering new structural data for the series. The research highlights the influence of hydration levels and lanthanide contraction on the crystal structures, while identifying missing data for specific hydrates in existing structural databases.

A comprehensive crystallographic study is presented of the complete series of rare-earth(III) chloride hydrates. Early lanthanides form dimeric [(H₂O)₇RE(μ-Cl)₂RE(H₂O)₇]⁴⁺ binuclear complexes in which each RE atom (RE = La³⁺, Ce³⁺) is coordinated by seven H₂O molecules and two bridging inner-sphere chloride ions. Di-μ-chlorido-bis[heptaaqualanthanide(III)] tetrachloride, [(H₂O)₇RE(μ-Cl)₂RE(H₂O)₇]Cl₄, crystallizes in the triclinic space group P1. Heavier lanthanides exhibit monomeric [RECl₂(H₂O)₆]⁺ units where each RE atom (RE = Pr³⁺, Nd³⁺, Sm³⁺–Lu³⁺) is coordinated by six H₂O molecules and two inner-sphere chloride ions. Hexaaquadichloridolanthanide(III) chlorides, [RECl₂(H₂O)₆]Cl, adopt the monoclinic space group P2/c. In both structures, the cationic inner-sphere complex is counter-charged by the corresponding number of outer-sphere Cl⁻ anions, in which the metal ion and outer-sphere chloride ion lie on crystallographic twofold axes. Crystal structures for all compounds were determined in high quality with refined H-atom positions and were collected at the same temperature (100 K), providing a uniform structural dataset and addressing discrepancies in previous reports. The crystal structure of [HoCl₂(H₂O)₆]Cl is reported for the first time.

查看原文本刊更多论文

氯化镧（III）水合物的综合结构研究：[RECl3·xH2O (RE = La-Nd, Sm-Lu；X = 6,7)]

本文对镧系（III）氯化物水合物[RECl3·xH2O (RE = La-Nd, Sm-Lu；X = 6,7)]，为该系列提供了新的结构数据。该研究强调了水化水平和镧系元素收缩对晶体结构的影响，同时确定了现有结构数据库中特定水合物的缺失数据。对全系列稀土（III）氯化物水合物进行了全面的晶体学研究。早期镧系元素形成二聚体[(H2O)7RE(μ-Cl)2RE(H2O)7]4+双核配合物，其中每个RE原子（RE = La3+, Ce3+）由7个H2O分子和2个桥接的内球氯离子配位。[(H2O)7RE(μ-Cl)2RE(H2O)7]Cl4在三斜空间群P1中结晶。较重的镧系元素表现为单体[RECl2(H2O)6]+单元，其中每个稀土原子（RE = Pr3+, Nd3+, Sm3+ -Lu3 +）由6个H2O分子和2个内球氯离子配位。六水二氯镧系（III）氯化物[RECl2(H2O)6]Cl采用单斜空间基团P2/c。在这两种结构中，带阳离子的内球配合物被相应数量的外球Cl−阴离子反荷，其中金属离子和外球氯离子位于晶体双轴上。所有化合物的晶体结构都是在相同的温度（100 K）下以精确的h原子位置高质量地确定的，提供了统一的结构数据集，并解决了以前报告中的差异。本文首次报道了[HoCl2(H2O)6]Cl的晶体结构。

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

Acta Crystallographica Section E: Crystallographic Communications Chemistry-Chemistry (all)

CiteScore

1.90

自引率

0.00%

发文量

351

审稿时长

3 weeks

期刊介绍： Acta Crystallographica Section E: Crystallographic Communications is the IUCr''s open-access structural communications journal. It provides a fast, simple and easily accessible publication mechanism for crystal structure determinations of inorganic, metal-organic and organic compounds. The electronic submission, validation, refereeing and publication facilities of the journal ensure rapid and high-quality publication of fully validated structures. The primary article category is Research Communications; these are peer-reviewed articles describing one or more structure determinations with appropriate discussion of the science.