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Characterization of electronic features of intermolecular interactions involving organic fluorine: Inputs from in situ cryo-crystallization studies on F and CF3 substituted anilines
Journal of Fluorine Chemistry ( IF 1.9 ) Pub Date : 2018-03-30 , DOI: 10.1016/j.jfluchem.2018.03.016
Pradip Kumar Mondal , Venkatesha R. Hathwar , Deepak Chopra

Experimental in situ cryo-crystallization studies performed on aniline derivatives depicts that the molecular packing of these compounds is through the utilization of Csp3/sp2F⋯FCsp3/sp2, NH⋯FCsp3/sp2, and CH⋯FCsp3/sp2 interactions in the presence of strong NH⋯N hydrogen bonds. This exercise has resulted in the identification of frequently occurring supramolecular synthons involving highly electronegative, less polarizable fluorine atoms in the packing of molecules of F and CF3 substituted anilines which are liquids at ambient temperature and pressure in the solid state. These studies demonstrate the nature, energetics and topological properties derived from the electron density in compounds based on F and CF3 substituted anilines (8 anilines) in the solid state. The energetics obtained from PIXELC associated with inclusive intermolecular interactions with significantly high electrostatic contribution is mentionable. The topological analysis brings out the bonding character of these interactions in the crystal packing. It is indeed noteworthy that in situ cryo-crystallization in 2-fluoro-6-(trifluoromethyl)aniline forms unique C(sp2)Fδ+⋯Fδ−C(sp2) contacts stabilized via electrostatics between the two molecules in the asymmetric unit in addition to NH⋯N H-bonds. This feature is also observed in a related isomeric compound, namely 2-fluoro-3-(trifluoromethyl)aniline and establishes the importance of weak fluorine-centered halogen interactions in nucleation and crystal growth.



中文翻译:

涉及有机氟的分子间相互作用的电子特征的表征:F和CF 3取代苯胺的原位低温结晶研究的输入

对苯胺衍生物进行的原位冷冻结晶实验表明,这些化合物的分子堆积是通过利用C sp 3 / sp 2 F⋯F C sp 3 / sp 2,N H⋯F C sp 3 / sp 2进行的。,以及在强N H⋯N氢键存在下C H strongF C sp 3 / sp 2的相互作用。这项工作已导致鉴定出频繁发生的超分子合成子,这些合成子在F和CF分子的堆积中涉及高度电负性,可极化性较低的氟原子3个取代的苯胺,在环境温度和压力下呈固态,呈液体。这些研究证明了基于F和CF 3取代苯胺(8个苯胺)的固态化合物的电子密度所产生的性质,能级和拓扑性质。从PIXELC获得的高能与具有显着高静电贡献的包容分子间相互作用有关。拓扑分析揭示了这些相互作用在晶体堆积中的键合特性。这确实是值得注意的是,在原位低温结晶中的2-氟-6-(三氟甲基)苯胺形式独特C(SP 2˚F δ+ ⋯˚Fδ- C(SP 2)触点经由之间静电稳定两个分子不对称单元中除至N ħ⋯ÑH键。在相关的异构化合物2-氟-3-(三氟甲基)苯胺中也观察到此特征,并确立了弱的以氟为中心的卤素相互作用在成核和晶体生长中的重要性。

更新日期:2018-03-30
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