L. E. Salvador Vallejo, J. L. Jios, S. E. Ulic, G. A. Echeverría, O. E. Piro, R. Pis Diez, C. Vázquez and C. Merlo
{"title":"Structural and spectroscopic study and intermolecular chalcogen bonding interactions in 1,3-dicarbonyl compounds†","authors":"L. E. Salvador Vallejo, J. L. Jios, S. E. Ulic, G. A. Echeverría, O. E. Piro, R. Pis Diez, C. Vázquez and C. Merlo","doi":"10.1039/D4NJ02508C","DOIUrl":null,"url":null,"abstract":"<p >Two new 1,3-dicarbonyl compounds bearing an <em>o</em>-hydroxyphenyl moiety (for short, <strong>I</strong> and <strong>II</strong>) were synthesized and subjected to structural, experimental and theoretical studies. Vibrational spectroscopy (IR and Raman) and X-ray diffraction were used for solid phase studies, while NMR and electron spectroscopy allowed analysis in solution. The crystal structures of <strong>I</strong> and <strong>II</strong>, determined by X-ray diffraction methods, are closely related to each other (rms deviation of homologous atoms from their best fit is 0.147 Å). The observed planarity of β-hydroxyphenylcarbonyl enols fragment in the compounds is enforced by both extended π-bonding and intramolecular OH⋯O bonds. Molecules in <strong>I</strong> are arranged in the lattice as center-symmetric dimers held by relatively weak intermolecular OH⋯O bonds. Hirshfeld surface (HS) analysis, atoms in molecules (QTAIM), and natural bonding orbitals (NBO) approaches were employed to study theoretically selected dimers constructed from X-ray data. The results were combined with experimental ones to obtain deep insight into the strength and type of intermolecular interactions. A chalcogen bond interaction was detected in <strong>I</strong>. Although the O⋯O interaction is unusual, it participates in the attractive forces that stabilize the crystal lattice. The title compounds are present in the solid state only as the keto–enol tautomer, while in solution the diketo tautomer is also detected at concentrations of 5%. <em>In vitro</em> studies showed that <strong>I</strong> have better antimicrobial properties than <strong>II</strong>, mainly against the <em>S. aureus</em> strain.</p>","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Journal of Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj02508c","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Two new 1,3-dicarbonyl compounds bearing an o-hydroxyphenyl moiety (for short, I and II) were synthesized and subjected to structural, experimental and theoretical studies. Vibrational spectroscopy (IR and Raman) and X-ray diffraction were used for solid phase studies, while NMR and electron spectroscopy allowed analysis in solution. The crystal structures of I and II, determined by X-ray diffraction methods, are closely related to each other (rms deviation of homologous atoms from their best fit is 0.147 Å). The observed planarity of β-hydroxyphenylcarbonyl enols fragment in the compounds is enforced by both extended π-bonding and intramolecular OH⋯O bonds. Molecules in I are arranged in the lattice as center-symmetric dimers held by relatively weak intermolecular OH⋯O bonds. Hirshfeld surface (HS) analysis, atoms in molecules (QTAIM), and natural bonding orbitals (NBO) approaches were employed to study theoretically selected dimers constructed from X-ray data. The results were combined with experimental ones to obtain deep insight into the strength and type of intermolecular interactions. A chalcogen bond interaction was detected in I. Although the O⋯O interaction is unusual, it participates in the attractive forces that stabilize the crystal lattice. The title compounds are present in the solid state only as the keto–enol tautomer, while in solution the diketo tautomer is also detected at concentrations of 5%. In vitro studies showed that I have better antimicrobial properties than II, mainly against the S. aureus strain.
我们合成了两种带有邻羟基苯基的新型 1,3-二羰基化合物(简称 I 和 II),并对其进行了结构、实验和理论研究。固相研究使用了振动光谱(红外光谱、拉曼光谱、漫反射光谱和 X 射线衍射光谱),溶液分析则使用了核磁共振和电子显微镜。通过 X 射线衍射方法确定的 I 和 II 晶体结构彼此密切相关(同源原子与最佳拟合的均方根偏差为 0.147 Å)。通过扩展的 π 键和分子内 OH∙∙∙O 键,可以观察到化合物中 β-羟基苯基羰基烯醇片段的平面性。I 中的分子在晶格中排列成中心对称的二聚体,由相对较弱的分子间 OH∙∙∙O 键保持。我们采用了希尔斯菲尔德表面(HS)分析、分子中的原子(QTAIM)和自然成键轨道(NBO)等方法,对根据 X 射线数据构建的理论选定二聚体进行了研究。研究结果与实验结果相结合,深入了解了分子间相互作用的强度和类型。虽然 O-O 相互作用并不常见,但它参与了稳定晶格的吸引力。标题化合物在固态中仅以酮烯醇同分异构体的形式存在,而在溶液中,当浓度为 5%时也能检测到二酮同分异构体。体外研究表明,I 的抗菌性能优于 II,主要针对金黄色葡萄球菌菌株。