María K. Salomón-Flores , Josue Valdes-García , Diego Martínez-Otero , Alejandro Dorazco-González , N. Alvarez Failache (Editor)
{"title":"5,10,15,20-四(1-苄基吡啶-1-鎓-4-基)-21H,23H-卟啉的三氟甲磺酸盐及其 CaII 复合物","authors":"María K. Salomón-Flores , Josue Valdes-García , Diego Martínez-Otero , Alejandro Dorazco-González , N. Alvarez Failache (Editor)","doi":"10.1107/S205698902400447X","DOIUrl":null,"url":null,"abstract":"<div><p>The synthesis and crystallization of a trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21<em>H</em>,23<em>H</em>-porphyrin, C<sub>68</sub>H<sub>54</sub>N<sub>8</sub> <sup>4+</sup>·4CF<sub>3</sub>O<sub>3</sub>S·4H<sub>2</sub>O, <strong>1</strong>·OTf, are reported. The asymmetric unit contains half a porphyrin molecule, two trifluoromethanesulfonate anions and two water molecules of crystallization. The macrocycle of tetrapyrrole moieties is planar and unexpectedly it has coordinated Ca<sup>II</sup> ions in occupational disorder. This Ca<sup>II</sup> ion has only 10% occupancy (C<sub>72</sub>H<sub>61.80</sub>Ca<sub>0.10</sub>F<sub>12</sub>N<sub>8</sub>O<sub>16</sub>S<sub>4</sub>).</p></div><div><p>The synthesis, crystallization and characterization of a trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21<em>H</em>,23<em>H</em>-porphyrin, C<sub>68</sub>H<sub>54</sub>N<sub>8</sub> <sup>4+</sup>·4CF<sub>3</sub>SO<sub>3</sub> <sup>−</sup>·4H<sub>2</sub>O, <strong>1</strong>·OTf, are reported in this work. The reaction between 5,10,15,20-tetrakis(pyridin-4-yl)-21<em>H</em>,23<em>H</em>-porphyrin and benzyl bromide in the presence of 0.1 equiv. of Ca(OH)<sub>2</sub> in CH<sub>3</sub>CN under reflux with an N<sub>2</sub> atmosphere and subsequent treatment with silver trifluoromethanesulfonate (AgOTf) salt produced a red–brown solution. This reaction mixture was filtered and the solvent was allowed to evaporate at room temperature for 3 d to give <strong>1</strong>·OTf. Crystal structure determination by single-crystal X-ray diffraction (SCXD) revealed that <strong>1</strong>·OTf crystallizes in the space group <em>P</em>2<sub>1</sub>/<em>c</em>. The asymmetric unit contains half a porphyrin molecule, two trifluoromethanesulfonate anions and two water molecules of crystallization. The macrocycle of tetrapyrrole moieties is planar and unexpectedly it has coordinated Ca<sup>II</sup> ions in occupational disorder. This Ca<sup>II</sup> ion has only 10% occupancy (C<sub>72</sub>H<sub>61.80</sub>Ca<sub>0.10</sub>F<sub>12</sub>N<sub>8</sub>O<sub>16</sub>S<sub>4</sub>). The pyridinium rings bonded to methylene groups from porphyrin are located in two different arrangements in almost orthogonal positions between the plane formed by the porphyrin and the pyridinium rings. The crystal structure features cation⋯π interactions between the Ca<sup>II</sup> atom and the π-system of the phenyl ring of neighboring molecules. Both trifluoromethanesulfonate anions are found at the periphery of <strong>1</strong>, forming hydrogen bonds with water molecules.</p></div>","PeriodicalId":7367,"journal":{"name":"Acta Crystallographica Section E: Crystallographic Communications","volume":"80 6","pages":"Pages 625-629"},"PeriodicalIF":0.5000,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21H,23H-porphyrin and its CaII complex\",\"authors\":\"María K. Salomón-Flores , Josue Valdes-García , Diego Martínez-Otero , Alejandro Dorazco-González , N. Alvarez Failache (Editor)\",\"doi\":\"10.1107/S205698902400447X\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The synthesis and crystallization of a trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21<em>H</em>,23<em>H</em>-porphyrin, C<sub>68</sub>H<sub>54</sub>N<sub>8</sub> <sup>4+</sup>·4CF<sub>3</sub>O<sub>3</sub>S·4H<sub>2</sub>O, <strong>1</strong>·OTf, are reported. The asymmetric unit contains half a porphyrin molecule, two trifluoromethanesulfonate anions and two water molecules of crystallization. The macrocycle of tetrapyrrole moieties is planar and unexpectedly it has coordinated Ca<sup>II</sup> ions in occupational disorder. This Ca<sup>II</sup> ion has only 10% occupancy (C<sub>72</sub>H<sub>61.80</sub>Ca<sub>0.10</sub>F<sub>12</sub>N<sub>8</sub>O<sub>16</sub>S<sub>4</sub>).</p></div><div><p>The synthesis, crystallization and characterization of a trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21<em>H</em>,23<em>H</em>-porphyrin, C<sub>68</sub>H<sub>54</sub>N<sub>8</sub> <sup>4+</sup>·4CF<sub>3</sub>SO<sub>3</sub> <sup>−</sup>·4H<sub>2</sub>O, <strong>1</strong>·OTf, are reported in this work. The reaction between 5,10,15,20-tetrakis(pyridin-4-yl)-21<em>H</em>,23<em>H</em>-porphyrin and benzyl bromide in the presence of 0.1 equiv. of Ca(OH)<sub>2</sub> in CH<sub>3</sub>CN under reflux with an N<sub>2</sub> atmosphere and subsequent treatment with silver trifluoromethanesulfonate (AgOTf) salt produced a red–brown solution. This reaction mixture was filtered and the solvent was allowed to evaporate at room temperature for 3 d to give <strong>1</strong>·OTf. Crystal structure determination by single-crystal X-ray diffraction (SCXD) revealed that <strong>1</strong>·OTf crystallizes in the space group <em>P</em>2<sub>1</sub>/<em>c</em>. The asymmetric unit contains half a porphyrin molecule, two trifluoromethanesulfonate anions and two water molecules of crystallization. The macrocycle of tetrapyrrole moieties is planar and unexpectedly it has coordinated Ca<sup>II</sup> ions in occupational disorder. This Ca<sup>II</sup> ion has only 10% occupancy (C<sub>72</sub>H<sub>61.80</sub>Ca<sub>0.10</sub>F<sub>12</sub>N<sub>8</sub>O<sub>16</sub>S<sub>4</sub>). The pyridinium rings bonded to methylene groups from porphyrin are located in two different arrangements in almost orthogonal positions between the plane formed by the porphyrin and the pyridinium rings. The crystal structure features cation⋯π interactions between the Ca<sup>II</sup> atom and the π-system of the phenyl ring of neighboring molecules. Both trifluoromethanesulfonate anions are found at the periphery of <strong>1</strong>, forming hydrogen bonds with water molecules.</p></div>\",\"PeriodicalId\":7367,\"journal\":{\"name\":\"Acta Crystallographica Section E: Crystallographic Communications\",\"volume\":\"80 6\",\"pages\":\"Pages 625-629\"},\"PeriodicalIF\":0.5000,\"publicationDate\":\"2024-05-01\",\"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/S2056989024001257\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CRYSTALLOGRAPHY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section E: Crystallographic Communications","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2056989024001257","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CRYSTALLOGRAPHY","Score":null,"Total":0}
Trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21H,23H-porphyrin and its CaII complex
The synthesis and crystallization of a trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21H,23H-porphyrin, C68H54N84+·4CF3O3S·4H2O, 1·OTf, are reported. The asymmetric unit contains half a porphyrin molecule, two trifluoromethanesulfonate anions and two water molecules of crystallization. The macrocycle of tetrapyrrole moieties is planar and unexpectedly it has coordinated CaII ions in occupational disorder. This CaII ion has only 10% occupancy (C72H61.80Ca0.10F12N8O16S4).
The synthesis, crystallization and characterization of a trifluoromethanesulfonate salt of 5,10,15,20-tetrakis(1-benzylpyridin-1-ium-4-yl)-21H,23H-porphyrin, C68H54N84+·4CF3SO3−·4H2O, 1·OTf, are reported in this work. The reaction between 5,10,15,20-tetrakis(pyridin-4-yl)-21H,23H-porphyrin and benzyl bromide in the presence of 0.1 equiv. of Ca(OH)2 in CH3CN under reflux with an N2 atmosphere and subsequent treatment with silver trifluoromethanesulfonate (AgOTf) salt produced a red–brown solution. This reaction mixture was filtered and the solvent was allowed to evaporate at room temperature for 3 d to give 1·OTf. Crystal structure determination by single-crystal X-ray diffraction (SCXD) revealed that 1·OTf crystallizes in the space group P21/c. The asymmetric unit contains half a porphyrin molecule, two trifluoromethanesulfonate anions and two water molecules of crystallization. The macrocycle of tetrapyrrole moieties is planar and unexpectedly it has coordinated CaII ions in occupational disorder. This CaII ion has only 10% occupancy (C72H61.80Ca0.10F12N8O16S4). The pyridinium rings bonded to methylene groups from porphyrin are located in two different arrangements in almost orthogonal positions between the plane formed by the porphyrin and the pyridinium rings. The crystal structure features cation⋯π interactions between the CaII atom and the π-system of the phenyl ring of neighboring molecules. Both trifluoromethanesulfonate anions are found at the periphery of 1, forming hydrogen bonds with water molecules.
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.
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