Egor M. Novikov , Jesus Guillen Campos , Javier Read de Alaniz , Marina S. Fonari , Tatiana V. Timofeeva
{"title":"4-氨基-3,5-二氟苯甲腈、4-氨基-3,5-二氟苯甲酸乙酯和 4,4'-(二氮烯-1,2-二基)双-(3,5-二氟苯甲酸)二乙酯的合成、分子结构和晶体结构。","authors":"Egor M. Novikov , Jesus Guillen Campos , Javier Read de Alaniz , Marina S. Fonari , Tatiana V. Timofeeva","doi":"10.1107/S2056989024006819","DOIUrl":null,"url":null,"abstract":"<div><p>Two intermediates, 4-amino-3,5-difluorobenzonitrile, C<sub>7</sub>H<sub>4</sub>F<sub>2</sub>N<sub>2</sub> (<strong>I</strong>), and ethyl 4-amino-3,5-difluorobenzoate, C<sub>9</sub>H<sub>9</sub>F<sub>2</sub>NO<sub>2</sub> (<strong>II</strong>), along with a visible-light-responsive azobenzene derivative, diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate), C<sub>18</sub>H<sub>14</sub>F<sub>4</sub>N<sub>2</sub>O<sub>4</sub> (<strong>III</strong>), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. In the crystals of <strong>I</strong> and <strong>II</strong>, the molecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking interactions. In the crystal of <strong>III</strong>, only stacking interactions between the molecules are found.</p></div><div><p>The crystal structures of two intermediates, 4-amino-3,5-difluorobenzonitrile, C<sub>7</sub>H<sub>4</sub>F<sub>2</sub>N<sub>2</sub> (<strong>I</strong>), and ethyl 4-amino-3,5-difluorobenzoate, C<sub>9</sub>H<sub>9</sub>F<sub>2</sub>NO<sub>2</sub> (<strong>II</strong>), along with a visible-light-responsive azobenzene derivative, diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate), C<sub>18</sub>H<sub>14</sub>F<sub>4</sub>N<sub>2</sub>O<sub>4</sub> (<strong>III</strong>), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. The molecules of <strong>I</strong> and <strong>II</strong> demonstrate the quinoid character of phenyl rings accompanied by the distortion of bond angles related to the presence of fluorine substituents in the 3 and 5 (<em>ortho</em>) positions. In the crystals of <strong>I</strong> and <strong>II</strong>, the molecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking interactions. In crystal of <strong>III</strong>, only stacking interactions between the molecules are found.</p></div>","PeriodicalId":7367,"journal":{"name":"Acta Crystallographica Section E: Crystallographic Communications","volume":"80 8","pages":"Pages 867-872"},"PeriodicalIF":0.5000,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11299740/pdf/","citationCount":"0","resultStr":"{\"title\":\"Synthesis, molecular and crystal structures of 4-amino-3,5-difluorobenzonitrile, ethyl 4-amino-3,5-difluorobenzoate, and diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate)\",\"authors\":\"Egor M. Novikov , Jesus Guillen Campos , Javier Read de Alaniz , Marina S. Fonari , Tatiana V. Timofeeva\",\"doi\":\"10.1107/S2056989024006819\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Two intermediates, 4-amino-3,5-difluorobenzonitrile, C<sub>7</sub>H<sub>4</sub>F<sub>2</sub>N<sub>2</sub> (<strong>I</strong>), and ethyl 4-amino-3,5-difluorobenzoate, C<sub>9</sub>H<sub>9</sub>F<sub>2</sub>NO<sub>2</sub> (<strong>II</strong>), along with a visible-light-responsive azobenzene derivative, diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate), C<sub>18</sub>H<sub>14</sub>F<sub>4</sub>N<sub>2</sub>O<sub>4</sub> (<strong>III</strong>), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. In the crystals of <strong>I</strong> and <strong>II</strong>, the molecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking interactions. In the crystal of <strong>III</strong>, only stacking interactions between the molecules are found.</p></div><div><p>The crystal structures of two intermediates, 4-amino-3,5-difluorobenzonitrile, C<sub>7</sub>H<sub>4</sub>F<sub>2</sub>N<sub>2</sub> (<strong>I</strong>), and ethyl 4-amino-3,5-difluorobenzoate, C<sub>9</sub>H<sub>9</sub>F<sub>2</sub>NO<sub>2</sub> (<strong>II</strong>), along with a visible-light-responsive azobenzene derivative, diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate), C<sub>18</sub>H<sub>14</sub>F<sub>4</sub>N<sub>2</sub>O<sub>4</sub> (<strong>III</strong>), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. The molecules of <strong>I</strong> and <strong>II</strong> demonstrate the quinoid character of phenyl rings accompanied by the distortion of bond angles related to the presence of fluorine substituents in the 3 and 5 (<em>ortho</em>) positions. In the crystals of <strong>I</strong> and <strong>II</strong>, the molecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking interactions. In crystal of <strong>III</strong>, only stacking interactions between the molecules are found.</p></div>\",\"PeriodicalId\":7367,\"journal\":{\"name\":\"Acta Crystallographica Section E: Crystallographic Communications\",\"volume\":\"80 8\",\"pages\":\"Pages 867-872\"},\"PeriodicalIF\":0.5000,\"publicationDate\":\"2024-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11299740/pdf/\",\"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/S2056989024001622\",\"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/S2056989024001622","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
摘要
4-amino-3,5-di-fluoro-benzo-nitrile, C7H4F2N2 (I)和 4-amino-3,5-di-fluoro-benzoate, C9H9F2NO2 (II)这两种中间体的晶体结构，以及一种可见光响应的偶氮苯衍生物、用单晶 X 射线衍射法研究了通过四步合成法获得的 4,4'-（重氮-1,2-二基）双（3,5-二氟苯甲酸）二乙酯 C18H14F4N2O4（III）。I 和 II 的分子结构显示出苯基环的喹啉特征，同时伴有与 3 和 5（正交）位上存在的氟取代基有关的键角变形。在 I 和 II 晶体中，分子结构通过 N-H⋯N、N-H⋯F 和 N-H⋯O 氢键、C-H⋯F 短接触和 π 堆积相互作用连接。在 III 晶体中，只发现了分子结构之间的堆叠相互作用。
Synthesis, molecular and crystal structures of 4-amino-3,5-difluorobenzonitrile, ethyl 4-amino-3,5-difluorobenzoate, and diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate)
Two intermediates, 4-amino-3,5-difluorobenzonitrile, C7H4F2N2 (I), and ethyl 4-amino-3,5-difluorobenzoate, C9H9F2NO2 (II), along with a visible-light-responsive azobenzene derivative, diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate), C18H14F4N2O4 (III), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. In the crystals of I and II, the molecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking interactions. In the crystal of III, only stacking interactions between the molecules are found.
The crystal structures of two intermediates, 4-amino-3,5-difluorobenzonitrile, C7H4F2N2 (I), and ethyl 4-amino-3,5-difluorobenzoate, C9H9F2NO2 (II), along with a visible-light-responsive azobenzene derivative, diethyl 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoate), C18H14F4N2O4 (III), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. The molecules of I and II demonstrate the quinoid character of phenyl rings accompanied by the distortion of bond angles related to the presence of fluorine substituents in the 3 and 5 (ortho) positions. In the crystals of I and II, the molecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking interactions. In crystal of III, only stacking interactions between the molecules are found.
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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