Galvez Carolina E, Rocha Mariana, Villecco Margarita B, Echeverría Gustavo A, Piro Oscar E, Loandos María Del H, Gil Diego M
Cátedra de Química Orgánica II. Instituto de Química Orgánica. Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, T4000INI, San Miguel de Tucumán, Argentina.
INBIOFAL (CONICET-UNT). Instituto de Química Orgánica. Facultad de Bioquímica, Química y Farmacia, Ayacucho 471, T4000INI, San Miguel de Tucumán, Argentina.
J Mol Model. 2021 Jan 5;27(1):13. doi: 10.1007/s00894-020-04633-9.
The compound 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-9-ol (9-hydroxyeucaliptol) has been prepared and characterized by single-crystal X-ray diffraction analysis, infrared, Raman, and UV-visible spectroscopies. The molecular geometry of the title compound was also investigated theoretically by density functional theory (DFT) calculations to compare with the experimental data. The substance crystallizes in the trigonal crystal system, space group P3 with Z = 9 molecules per unit cell. There are three independent molecules in the crystal asymmetric unit having the same chirality and showing some differences in the orientation of the H-atom of the hydroxyl group. The crystal structure of 9-hydroxyeucaliptol shows that the hydroxyl group presents an anti-conformation with respect to the O-atom of the ether group. The crystal packing of 9-hydroxyeucaliptol is stabilized by intermolecular O-H···O hydrogen bonds involving the hydroxyl groups of different molecules, which play a decisive role in the preferred conformation adopted in solid state. The intermolecular interactions observed in solid state were also studied through the Hirshfeld surface analysis and quantum theory of atoms in molecules (QTAIM) approaches. Energy framework calculations have also been carried out to analyze and visualize the topology of the supramolecular assembly, and the results indicate a significant contribution from electrostatic energy over the dispersion.
化合物1,3,3-三甲基-2-氧杂双环[2.2.2]辛烷-9-醇（9-羟基桉叶油素）已通过单晶X射线衍射分析、红外光谱、拉曼光谱和紫外可见光谱进行了制备和表征。还通过密度泛函理论（DFT）计算对标题化合物的分子几何结构进行了理论研究，以与实验数据进行比较。该物质结晶于三方晶系，空间群为P3，每个晶胞中有Z = 9个分子。晶体不对称单元中有三个独立分子，具有相同的手性，并且羟基氢原子的取向存在一些差异。9-羟基桉叶油素的晶体结构表明，羟基相对于醚基的氧原子呈反式构象。9-羟基桉叶油素的晶体堆积通过涉及不同分子羟基的分子间O-H···O氢键得以稳定，这些氢键在固态中采用的优选构象中起决定性作用。还通过Hirshfeld表面分析和分子中的原子量子理论（QTAIM）方法研究了固态中观察到的分子间相互作用。还进行了能量框架计算，以分析和可视化超分子组装体的拓扑结构，结果表明静电能对色散的贡献很大。
