Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente
{"title":"7-二甲基氨基-4-羟基香豆素及其衍生物：增强的 β 链氢键作用","authors":"Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente","doi":"10.1007/s10870-024-01020-7","DOIUrl":null,"url":null,"abstract":"<div><p>\n The crystal and molecular structure of 7-dimethylamino-4-hydroxycoumarin as its hydrate (<b>1</b>, C<sub>11</sub>H<sub>11</sub>NO<sub>3</sub> • H<sub>2</sub>O) has been determined. Crystals are monoclinic, space group <i>P</i>2(1)/<i>n</i> with <i>a</i> = 7.1435(4) Å, <i>b</i> = 20.1763(6) Å, <i>c</i> = 7.8590(3) Å, <i>β</i> = 110.018(5)<sup>o</sup> and V = 1064.28(8)Å<sup>3</sup> for 4 formula units per cell. Both coumarin enol ester hydroxy and carboxy groups engage in hydrogen-bonding with the water of crystallization. Several 3-substituted derivatives were prepared from this material including 7-dimethylamino-3-benzyl-4-hydroxycoumarin (<b>2</b>) and 7-dimethylaminowarfarin (<b>4</b>). Compound <b>2</b> (C<sub>18</sub>H<sub>16</sub>NO<sub>3</sub>) crystallizes in the triclinic system, space group <i>P</i>-1, with <i>a</i> = 7.0180(7) Å, <i>b</i> = 7.8143(7) Å, <i>c</i> = 14.3158(10) Å, <i>α</i> = 90.586(6)<sup>o</sup>, <i>β</i> = 94.738(5)<sup>o</sup>, <i>γ</i> = 104.639(7)<sup>o</sup>, and V = 756.57(9) Å<sup>3</sup> for 2 molecules in the cell. For compound <b>2</b>, the crystal structure shows infinite hydrogen-bonded translational β-chains linking well aligned hydroxy and ester carboxy groups with a repeat distance of 7.018 Å. The dipolar nature of the substituted 4-hydroxycoumarin strengthens the β-chains compared to unsubstituted systems in which the repeat is longer and weaker at 7.17 Å. Computations (DFT) support the bond length changes due to a dipolar influence of the 7-dimethylamino group (compared to the unsubstituted compounds), and a more negative carboxy oxygen hydrogen-bond acceptor. For compound <b>4</b> (C<sub>21</sub>H<sub>21</sub>NO<sub>4</sub>), a stereoselective synthesis allowed preparation of the (S)-isomer which crystallized in the orthorhombic system, space group <i>P</i>2(1)2(1)2(1), with <i>a</i> = 6.7857(3) Å, <i>b</i> = 14.7140(5) Å, <i>c</i> = 17.4652(7) Å and V = 1743.81(12) Å<sup>3</sup> for 4 molecules in the cell. Compound <b>4</b> forms the <i>trans</i> cyclic hemiketal from methanol in the crystal. In CDCl<sub>3</sub> solution (298 K), <b>4</b> exists as an equilibrium mixture of three tautomers: 12.8% open form, 45.5% <i>cis</i> hemiketal and 41.7% <i>trans</i> hemiketal (coumarin forms).</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>\n Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente-3-Benzyl-4-hydroxy-7-dimethylaminocoumarin forms enhanced translational β-chain hydrogen-bonded arrays in the crystal</p></div></div></figure></div></div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"54 3","pages":"274 - 284"},"PeriodicalIF":0.4000,"publicationDate":"2024-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"7-Dimethylamino-4-Hydroxycoumarin and Derivatives: Enhanced β-Chain Hydrogen-Bonding\",\"authors\":\"Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente\",\"doi\":\"10.1007/s10870-024-01020-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>\\n The crystal and molecular structure of 7-dimethylamino-4-hydroxycoumarin as its hydrate (<b>1</b>, C<sub>11</sub>H<sub>11</sub>NO<sub>3</sub> • H<sub>2</sub>O) has been determined. Crystals are monoclinic, space group <i>P</i>2(1)/<i>n</i> with <i>a</i> = 7.1435(4) Å, <i>b</i> = 20.1763(6) Å, <i>c</i> = 7.8590(3) Å, <i>β</i> = 110.018(5)<sup>o</sup> and V = 1064.28(8)Å<sup>3</sup> for 4 formula units per cell. Both coumarin enol ester hydroxy and carboxy groups engage in hydrogen-bonding with the water of crystallization. Several 3-substituted derivatives were prepared from this material including 7-dimethylamino-3-benzyl-4-hydroxycoumarin (<b>2</b>) and 7-dimethylaminowarfarin (<b>4</b>). Compound <b>2</b> (C<sub>18</sub>H<sub>16</sub>NO<sub>3</sub>) crystallizes in the triclinic system, space group <i>P</i>-1, with <i>a</i> = 7.0180(7) Å, <i>b</i> = 7.8143(7) Å, <i>c</i> = 14.3158(10) Å, <i>α</i> = 90.586(6)<sup>o</sup>, <i>β</i> = 94.738(5)<sup>o</sup>, <i>γ</i> = 104.639(7)<sup>o</sup>, and V = 756.57(9) Å<sup>3</sup> for 2 molecules in the cell. For compound <b>2</b>, the crystal structure shows infinite hydrogen-bonded translational β-chains linking well aligned hydroxy and ester carboxy groups with a repeat distance of 7.018 Å. The dipolar nature of the substituted 4-hydroxycoumarin strengthens the β-chains compared to unsubstituted systems in which the repeat is longer and weaker at 7.17 Å. Computations (DFT) support the bond length changes due to a dipolar influence of the 7-dimethylamino group (compared to the unsubstituted compounds), and a more negative carboxy oxygen hydrogen-bond acceptor. For compound <b>4</b> (C<sub>21</sub>H<sub>21</sub>NO<sub>4</sub>), a stereoselective synthesis allowed preparation of the (S)-isomer which crystallized in the orthorhombic system, space group <i>P</i>2(1)2(1)2(1), with <i>a</i> = 6.7857(3) Å, <i>b</i> = 14.7140(5) Å, <i>c</i> = 17.4652(7) Å and V = 1743.81(12) Å<sup>3</sup> for 4 molecules in the cell. Compound <b>4</b> forms the <i>trans</i> cyclic hemiketal from methanol in the crystal. In CDCl<sub>3</sub> solution (298 K), <b>4</b> exists as an equilibrium mixture of three tautomers: 12.8% open form, 45.5% <i>cis</i> hemiketal and 41.7% <i>trans</i> hemiketal (coumarin forms).</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>\\n Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente-3-Benzyl-4-hydroxy-7-dimethylaminocoumarin forms enhanced translational β-chain hydrogen-bonded arrays in the crystal</p></div></div></figure></div></div>\",\"PeriodicalId\":615,\"journal\":{\"name\":\"Journal of Chemical Crystallography\",\"volume\":\"54 3\",\"pages\":\"274 - 284\"},\"PeriodicalIF\":0.4000,\"publicationDate\":\"2024-05-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Crystallography\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10870-024-01020-7\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CRYSTALLOGRAPHY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Crystallography","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10870-024-01020-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CRYSTALLOGRAPHY","Score":null,"Total":0}
7-Dimethylamino-4-Hydroxycoumarin and Derivatives: Enhanced β-Chain Hydrogen-Bonding
The crystal and molecular structure of 7-dimethylamino-4-hydroxycoumarin as its hydrate (1, C11H11NO3 • H2O) has been determined. Crystals are monoclinic, space group P2(1)/n with a = 7.1435(4) Å, b = 20.1763(6) Å, c = 7.8590(3) Å, β = 110.018(5)o and V = 1064.28(8)Å3 for 4 formula units per cell. Both coumarin enol ester hydroxy and carboxy groups engage in hydrogen-bonding with the water of crystallization. Several 3-substituted derivatives were prepared from this material including 7-dimethylamino-3-benzyl-4-hydroxycoumarin (2) and 7-dimethylaminowarfarin (4). Compound 2 (C18H16NO3) crystallizes in the triclinic system, space group P-1, with a = 7.0180(7) Å, b = 7.8143(7) Å, c = 14.3158(10) Å, α = 90.586(6)o, β = 94.738(5)o, γ = 104.639(7)o, and V = 756.57(9) Å3 for 2 molecules in the cell. For compound 2, the crystal structure shows infinite hydrogen-bonded translational β-chains linking well aligned hydroxy and ester carboxy groups with a repeat distance of 7.018 Å. The dipolar nature of the substituted 4-hydroxycoumarin strengthens the β-chains compared to unsubstituted systems in which the repeat is longer and weaker at 7.17 Å. Computations (DFT) support the bond length changes due to a dipolar influence of the 7-dimethylamino group (compared to the unsubstituted compounds), and a more negative carboxy oxygen hydrogen-bond acceptor. For compound 4 (C21H21NO4), a stereoselective synthesis allowed preparation of the (S)-isomer which crystallized in the orthorhombic system, space group P2(1)2(1)2(1), with a = 6.7857(3) Å, b = 14.7140(5) Å, c = 17.4652(7) Å and V = 1743.81(12) Å3 for 4 molecules in the cell. Compound 4 forms the trans cyclic hemiketal from methanol in the crystal. In CDCl3 solution (298 K), 4 exists as an equilibrium mixture of three tautomers: 12.8% open form, 45.5% cis hemiketal and 41.7% trans hemiketal (coumarin forms).
Graphical Abstract
Elisei Cosovan, Victor Cosovan, Daniel A. Osborne, David H. Magers, Edward J. Valente-3-Benzyl-4-hydroxy-7-dimethylaminocoumarin forms enhanced translational β-chain hydrogen-bonded arrays in the crystal
期刊介绍：
Journal of Chemical Crystallography is an international and interdisciplinary publication dedicated to the rapid dissemination of research results in the general areas of crystallography and spectroscopy. Timely research reports detail topics in crystal chemistry and physics and their relation to problems of molecular structure; structural studies of solids, liquids, gases, and solutions involving spectroscopic, spectrometric, X-ray, and electron and neutron diffraction; and theoretical studies.
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