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Praziquanamine enantiomers: Crystal structure, Hirshfeld surface analysis, and quantum chemical studies
Journal of Molecular Structure ( IF 4.0 ) Pub Date : 2023-03-11 , DOI: 10.1016/j.molstruc.2023.135343
Alberto Cedillo–Cruz , Diana Cecilia Villalobos–López , María Isabel Aguilar , Pedro Josué Trejo–Soto , Alicia Hernández–Campos , Helgi Jung–Cook

In this work, we report a microwave–assisted method to perform an acid hydrolysis using 26 praziquanamides as substrate to produce both praziquanamine (1) enantiomers: (R)–(–)–praziquanamine (1a) or (S)–(+)–praziquanamine (1b). This method provides very good yields and short reaction times (twenty minutes). A structural characterization of praziquanamine and its enantiomers was performed by using X–ray diffraction, spectroscopic and spectrometric techniques, thermal analysis, and powder X–ray diffraction. Computational calculations were also carried out, such as density functional theory (DFT), as it yields suitable geometries for the optimized structures. We also performed frontier molecular orbital (LUMO–HOMO) and electrostatic potential (ESP) analyses. Theoretical values were calculated for electronic transitions, vibration frequencies, and chemical shifts for nuclear magnetic resonances (NMR), and they were later compared to the experimental results. Additionally, the Hirshfeld Surface Analysis was performed to evaluate intermolecular interactions. Crystal structures of both 1a and 1b enantiomers were obtained as an orthorhombic system in the non-centrosymmetric P212121 space group. Conversely, the 1 compound crystallized as a monoclinic system in the centrosymmetric P21/n space group. The following interactions define the crystal packing: N–H···O, N–H···N, C–H···O, C–H···N, C–H···π, and π–π. They all establish an infinite one-dimensional chain. The crystal architectures of praziquanamine enantiomers may be used as resolution agents to discriminate chiral topologies.



中文翻译:

吡喹胺对映异构体:晶体结构、Hirshfeld 表面分析和量子化学研究

在这项工作中,我们报告了一种微波辅助方法,使用26 种吡喹酰胺作为底物进行酸水解,以产生两种吡喹胺 ( 1 ) 对映体:( R )–(–)–吡喹胺 ( 1a ) 或 ( S )–( +)–吡喹胺 ( 1b). 这种方法提供了非常好的产率和较短的反应时间(二十分钟)。使用 X 射线衍射、光谱和光谱测定技术、热分析和粉末 X 射线衍射对吡喹胺及其对映体进行了结构表征。还进行了计算计算,例如密度泛函理论 (DFT),因为它为优化结构产生了合适的几何形状。我们还进行了前沿分子轨道 (LUMO–HOMO) 和静电势 (ESP) 分析。计算了核磁共振 (NMR) 的电子跃迁、振动频率和化学位移的理论值,随后将它们与实验结果进行了比较。此外,还进行了 Hirshfeld 表面分析以评估分子间相互作用。1a1b对映异构体作为非中心对称P 2 1 2 1 2 1空间群中的斜方晶系获得。相反,1化合物在中心对称的P 2 1 /n空间群中结晶为单斜晶系。以下相互作用定义了晶体堆积:N–H···O、N–H···N、C–H···O、C–H···N、C–H···π 和 π –π。它们都建立了一个无限的一维链。吡喹胺对映体的晶体结构可用作拆分剂来区分手性拓扑结构。

更新日期:2023-03-16
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