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Quantitative Investigation of Weak Intermolecular Interactions of −F and −CF3 Substituted in Situ Cryocrystallized Benzaldehydes

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journal contribution
posted on 16.11.2020, 19:13 by Avantika Hasija, Rohit Bhowal, Deepak Chopra
Extensive research in the field of noncovalent interactions has shown that hydrogen bonds are responsible for the association of molecules leading to the formation of different crystal structures. The relevance of weak bonds has been realized only in recent years by exploring crystal structures of compounds that are liquids at room temperature via the technique of in situ cryocrystallization. As a part of our ongoing investigation on fluorine centered interactions, in particular, C–H···F H-bonds, a series of −F and/or −CF3 substituted benzaldehydes, which are liquids in ambient conditions, has been crystallized under nonambient conditions using an in situ cryocrystallization technique via an optical heating and crystallization device. The compounds primarily consist of relatively weaker hydrogen bond donors and acceptors. To unravel the rationale behind the stabilization of their crystalline assembly, the study of the nature and energetics of various types of hydrogen bonds involving C–H···O/F and stacking interactions has been explored in-depth through different computational tools wherein the role of both electrostatics and dispersive forces is of relevance in the formation of the H-bond. This includes the evaluation of the Hirshfeld surface analysis along with two-dimensional fingerprint plots, enrichment ratios, molecular electrostatic surface potential, energy frameworks, and lattice energy calculations from the Crystal Explorer 17.5 suite to assess the overall trends in stability. The purpose of performing this challenging crystallization technique followed by computational evaluation is to appraise the cumulative role of weaker hydrogen bonds in the presence of stronger noncovalent interactions.