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An intramolecular 1,5-chalcogen bond on the conformational preference of carbonyl thiocarbamate species
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2020/03/02 , DOI: 10.1039/c9nj06417f Pervaiz Ali Channar 1, 2, 3, 4 , Aamer Saeed 1, 2, 3, 4 , Fayaz Ali Larik 1, 2, 3, 4 , Ulrich Flörke 5, 6, 7, 8, 9 , Hesham El-Seedi 10, 11, 12, 13, 14 , Lucas S. Rodríguez Pirani 15, 16, 17, 18, 19 , Mauricio F. Erben 15, 16, 17, 18, 19
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2020/03/02 , DOI: 10.1039/c9nj06417f Pervaiz Ali Channar 1, 2, 3, 4 , Aamer Saeed 1, 2, 3, 4 , Fayaz Ali Larik 1, 2, 3, 4 , Ulrich Flörke 5, 6, 7, 8, 9 , Hesham El-Seedi 10, 11, 12, 13, 14 , Lucas S. Rodríguez Pirani 15, 16, 17, 18, 19 , Mauricio F. Erben 15, 16, 17, 18, 19
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Two closely related compounds, namely, O-methyl (4-fluorobenzoyl)carbamothioate (I) and O-methyl (4-methylbenzoyl)carbamothioate (II) were prepared in good yields by the reaction of the corresponding benzoyl isothiocyanates and methanol. The structural and conformational properties of both compounds were analyzed using a combined approach including single-crystal X-ray diffraction and quantum chemical calculations. A rich conformational landscape is envisaged for the vacuum-isolated species around the central carbamothioate group, with the pseudo-anti conformation (C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O and CS double bonds pointing toward opposite orientations) being the most stable form. The X-ray molecular structure shows the presence of this form in the crystalline phase for both compounds. The occurrence of a 1,5-O⋯O intramolecular short distance was observed, suggesting the relevance of chalcogen⋯chalcogen interactions in the conformational preference. Natural bond orbital population analysis and quantum chemical calculations through an isodesmic reaction scheme were applied to better understand the conformational preference and the nature of the O⋯O intramolecular interactions. The quantum theory of atoms in molecules was also used to examine the electronic densities around the S(5) pseudo-ring formed through the intramolecular interaction in the carbamothioate moiety. Furthermore, the vibrational features were analyzed by measuring the infrared and Raman spectra.
中文翻译：
分子内的1,5-硫属元素键对羰基硫代氨基甲酸酯种类的构象偏爱
通过使相应的苯甲酰基异硫氰酸酯与甲醇反应以高收率制备两种密切相关的化合物，即O-甲基（4-氟苯甲酰基）氨基甲硫酸酯（I）和O-甲基（4-甲基苯甲酰基）氨基甲硫酸酯（II）。使用包括单晶X射线衍射和量子化学计算在内的组合方法分析了这两种化合物的结构和构象性质。对于中心氨基甲酸酯基团周围的真空隔离物种，构想了丰富的构象景观，具有假反构象（CO和C指向相反方向的S双键是最稳定的形式。X射线分子结构表明两种化合物在结晶相中都存在该形式。观察到1,5-O = O分子内短距离的发生，表明硫族元素⋯硫族元素相互作用在构象偏好中的相关性。通过等离子反应方案进行自然键轨道种群分析和量子化学计算，以更好地理解构象偏好和O⋯O分子内相互作用的性质。分子中原子的量子理论还用于检查通过氨基甲酸酯基部分中的分子内相互作用形成的S（5）伪环周围的电子密度。此外，
更新日期：2020-04-06
O and CS double bonds pointing toward opposite orientations) being the most stable form. The X-ray molecular structure shows the presence of this form in the crystalline phase for both compounds. The occurrence of a 1,5-O⋯O intramolecular short distance was observed, suggesting the relevance of chalcogen⋯chalcogen interactions in the conformational preference. Natural bond orbital population analysis and quantum chemical calculations through an isodesmic reaction scheme were applied to better understand the conformational preference and the nature of the O⋯O intramolecular interactions. The quantum theory of atoms in molecules was also used to examine the electronic densities around the S(5) pseudo-ring formed through the intramolecular interaction in the carbamothioate moiety. Furthermore, the vibrational features were analyzed by measuring the infrared and Raman spectra.
中文翻译：
分子内的1,5-硫属元素键对羰基硫代氨基甲酸酯种类的构象偏爱
通过使相应的苯甲酰基异硫氰酸酯与甲醇反应以高收率制备两种密切相关的化合物，即O-甲基（4-氟苯甲酰基）氨基甲硫酸酯（I）和O-甲基（4-甲基苯甲酰基）氨基甲硫酸酯（II）。使用包括单晶X射线衍射和量子化学计算在内的组合方法分析了这两种化合物的结构和构象性质。对于中心氨基甲酸酯基团周围的真空隔离物种，构想了丰富的构象景观，具有假反构象（C
O和C指向相反方向的S双键是最稳定的形式。X射线分子结构表明两种化合物在结晶相中都存在该形式。观察到1,5-O = O分子内短距离的发生，表明硫族元素⋯硫族元素相互作用在构象偏好中的相关性。通过等离子反应方案进行自然键轨道种群分析和量子化学计算，以更好地理解构象偏好和O⋯O分子内相互作用的性质。分子中原子的量子理论还用于检查通过氨基甲酸酯基部分中的分子内相互作用形成的S（5）伪环周围的电子密度。此外，
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