Evaluation of the Role of Isostructurality in Fluorinated Phenyl Benzoates

In this report, the occurrence of three-, two-, and one-dimensional (3D, 2D, and 1D) isostructurality in phenyl benzoate (D00) and their fluorinated analogues was investigated in terms of their molecular assembly in solid state structures. A one-dimensional C-H center dot center dot center dot O=C chain is observed as a robust motif (similar to 21 kJ/mol) in the formation of the supramolecular architectures in these isostructural compounds. The isomorphous crystal structures exhibit 3D isostructurality or.vice versa. The crystal packing shows that weak intermolecular C-H center dot center dot center dot F, C-H center dot center dot center dot O, C-H center dot center dot center dot pi interactions, and pi center dot center dot center dot pi stacking are the main contributors providing stability toward the crystal lattice. The nature and energetics of all the geometrically or energetically equivalent building blocks associated with similar or different intermolecular interactions delineate the role of different molecular pairs in the crystal structures. The fingerprint plots of the isostructural set of crystal structures help to understand the similarities and the differences in the various interatomic contacts. A comparison of these crystal structures with fluorinated N-phenyl benzarnides shows the change in supramolecular assembly in terms of intermolecular interactions as well as the lattice energy due to the participation of a strong donor (N-H).