{"title":"利用构建模块 [MIII(C6O4Cl2)3]3-（MIII = 铁和铬）获得的不同核性的同金属和异金属氯烷基配合物","authors":"Lidija Molčanov, Marijana Jurić, Sanja Burazer, Krešimir Molčanov","doi":"10.1016/j.poly.2025.117498","DOIUrl":null,"url":null,"abstract":"<div><div>The crystal structures of seven homo- or heterometallic chloranilate-based compounds containing units of different nuclearity have been reported and described: mononuclear [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N][Cr(H<sub>2</sub>O)<sub>2</sub>(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>]·CH<sub>3</sub>CN·3H<sub>2</sub>O (<strong>1</strong>), [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>3</sub>[Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (<strong>2</strong>) and [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>2</sub>[Cu(H<sub>2</sub>O)(terpy)Cl][Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>] (<strong>3</strong>; terpy = 2,2′:6′,2′′-terpyridine), dinuclear chloranilato-bridged [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N][Cu(H<sub>2</sub>O)<sub>2</sub>(phen)(<em>µ-</em>chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>]·2CH<sub>3</sub>CN·7H<sub>2</sub>O (<strong>4</strong>; phen = 1,10-phenanthroline) and chloride-bridged {[Cu(H<sub>2</sub>O)(terpy)(<em>µ</em>-Cl)Cu(terpy)Cl][Cu(H<sub>2</sub>O)(terpy)Cl][Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>]}<sub>2</sub>·X (X = <em>n</em>CH<sub>3</sub>CN, <em>n</em>CH<sub>3</sub>OH, <em>n</em>H<sub>2</sub>O) (<strong>5</strong>), trinuclear chloranilato-bridged [Cu(H<sub>2</sub>O)(terpy)Cl][Cu(H<sub>2</sub>O)(terpy)(<em>µ-</em>chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cu(terpy) (<em>µ-</em>chloranilato-1κ<em>O<sup>1</sup>:</em>2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>]·3CH<sub>3</sub>CN (<strong>6</strong>) and [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>4</sub>[Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>(<em>µ-</em>chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cu(im)<sub>2</sub>(<em>µ</em>-chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>] (<strong>7</strong>; im = imidazole). The compounds were studied by single-crystal and powder X-ray diffraction and IR spectroscopy. Crystallographic analysis revealed that compounds <strong>1</strong>–<strong>4</strong> and <strong>7</strong> comprise one or more [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>4</sub><sup>+</sup> cations, while compounds <strong>3</strong> and <strong>6</strong> contain mononuclear copper(II) cation, [Cu(H<sub>2</sub>O)(terpy)Cl]<sup>+</sup>. The structure of the solvate of the starting building block, [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>3</sub>[Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (<strong>2</strong>), whose crystal structure has not been known, was determined. Compound <strong>4</strong> is the first dinuclear compound in which two different metal centers are bridged by a bis(bidentate) chloranilate group. In <strong>6</strong>, there is a rare case of a bridging bidentate-monodentate coordination mode whose geometry resembles hydrogen chloranilate monoanion.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"274 ","pages":"Article 117498"},"PeriodicalIF":2.4000,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Homo- and heterometallic chloranilate-based complexes of different nuclearity obtained using building blocks [MIII(C6O4Cl2)3]3− (MIII = Fe and Cr)\",\"authors\":\"Lidija Molčanov, Marijana Jurić, Sanja Burazer, Krešimir Molčanov\",\"doi\":\"10.1016/j.poly.2025.117498\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The crystal structures of seven homo- or heterometallic chloranilate-based compounds containing units of different nuclearity have been reported and described: mononuclear [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N][Cr(H<sub>2</sub>O)<sub>2</sub>(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>]·CH<sub>3</sub>CN·3H<sub>2</sub>O (<strong>1</strong>), [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>3</sub>[Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (<strong>2</strong>) and [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>2</sub>[Cu(H<sub>2</sub>O)(terpy)Cl][Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>] (<strong>3</strong>; terpy = 2,2′:6′,2′′-terpyridine), dinuclear chloranilato-bridged [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N][Cu(H<sub>2</sub>O)<sub>2</sub>(phen)(<em>µ-</em>chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>]·2CH<sub>3</sub>CN·7H<sub>2</sub>O (<strong>4</strong>; phen = 1,10-phenanthroline) and chloride-bridged {[Cu(H<sub>2</sub>O)(terpy)(<em>µ</em>-Cl)Cu(terpy)Cl][Cu(H<sub>2</sub>O)(terpy)Cl][Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>]}<sub>2</sub>·X (X = <em>n</em>CH<sub>3</sub>CN, <em>n</em>CH<sub>3</sub>OH, <em>n</em>H<sub>2</sub>O) (<strong>5</strong>), trinuclear chloranilato-bridged [Cu(H<sub>2</sub>O)(terpy)Cl][Cu(H<sub>2</sub>O)(terpy)(<em>µ-</em>chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cu(terpy) (<em>µ-</em>chloranilato-1κ<em>O<sup>1</sup>:</em>2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>]·3CH<sub>3</sub>CN (<strong>6</strong>) and [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>4</sub>[Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>(<em>µ-</em>chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cu(im)<sub>2</sub>(<em>µ</em>-chloranilato-1κ<sup>2</sup><em>O<sup>1</sup>,O<sup>2</sup></em>:2κ<sup>2</sup><em>O<sup>3</sup>,O<sup>4</sup></em>)Cr(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>] (<strong>7</strong>; im = imidazole). The compounds were studied by single-crystal and powder X-ray diffraction and IR spectroscopy. Crystallographic analysis revealed that compounds <strong>1</strong>–<strong>4</strong> and <strong>7</strong> comprise one or more [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>4</sub><sup>+</sup> cations, while compounds <strong>3</strong> and <strong>6</strong> contain mononuclear copper(II) cation, [Cu(H<sub>2</sub>O)(terpy)Cl]<sup>+</sup>. The structure of the solvate of the starting building block, [(C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>3</sub>[Fe(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (<strong>2</strong>), whose crystal structure has not been known, was determined. Compound <strong>4</strong> is the first dinuclear compound in which two different metal centers are bridged by a bis(bidentate) chloranilate group. In <strong>6</strong>, there is a rare case of a bridging bidentate-monodentate coordination mode whose geometry resembles hydrogen chloranilate monoanion.</div></div>\",\"PeriodicalId\":20278,\"journal\":{\"name\":\"Polyhedron\",\"volume\":\"274 \",\"pages\":\"Article 117498\"},\"PeriodicalIF\":2.4000,\"publicationDate\":\"2025-03-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polyhedron\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0277538725001123\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polyhedron","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0277538725001123","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Homo- and heterometallic chloranilate-based complexes of different nuclearity obtained using building blocks [MIII(C6O4Cl2)3]3− (MIII = Fe and Cr)
The crystal structures of seven homo- or heterometallic chloranilate-based compounds containing units of different nuclearity have been reported and described: mononuclear [(C4H9)4N][Cr(H2O)2(C6O4Cl2)2]·CH3CN·3H2O (1), [(C4H9)4N]3[Fe(C6O4Cl2)3]·CH3CN·H2O (2) and [(C4H9)4N]2[Cu(H2O)(terpy)Cl][Cr(C6O4Cl2)3] (3; terpy = 2,2′:6′,2′′-terpyridine), dinuclear chloranilato-bridged [(C4H9)4N][Cu(H2O)2(phen)(µ-chloranilato-1κ2O1,O2:2κ2O3,O4)Cr(C6O4Cl2)2]·2CH3CN·7H2O (4; phen = 1,10-phenanthroline) and chloride-bridged {[Cu(H2O)(terpy)(µ-Cl)Cu(terpy)Cl][Cu(H2O)(terpy)Cl][Fe(C6O4Cl2)3]}2·X (X = nCH3CN, nCH3OH, nH2O) (5), trinuclear chloranilato-bridged [Cu(H2O)(terpy)Cl][Cu(H2O)(terpy)(µ-chloranilato-1κ2O1,O2:2κ2O3,O4)Cu(terpy) (µ-chloranilato-1κO1:2κ2O3,O4)Fe(C6O4Cl2)2]·3CH3CN (6) and [(C4H9)4N]4[Cr(C6O4Cl2)2(µ-chloranilato-1κ2O1,O2:2κ2O3,O4)Cu(im)2(µ-chloranilato-1κ2O1,O2:2κ2O3,O4)Cr(C6O4Cl2)2] (7; im = imidazole). The compounds were studied by single-crystal and powder X-ray diffraction and IR spectroscopy. Crystallographic analysis revealed that compounds 1–4 and 7 comprise one or more [(C4H9)4N]4+ cations, while compounds 3 and 6 contain mononuclear copper(II) cation, [Cu(H2O)(terpy)Cl]+. The structure of the solvate of the starting building block, [(C4H9)4N]3[Fe(C6O4Cl2)3]·CH3CN·H2O (2), whose crystal structure has not been known, was determined. Compound 4 is the first dinuclear compound in which two different metal centers are bridged by a bis(bidentate) chloranilate group. In 6, there is a rare case of a bridging bidentate-monodentate coordination mode whose geometry resembles hydrogen chloranilate monoanion.
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