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

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.