Structural Investigation
of Weak Intermolecular Interactions in Fluorine Substituted Isomeric <i>N</i>‑Benzylideneanilines
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Abstract
The study of the influence of aromatic C–F group
in directing crystal packing is an important area of current research.
The role of the aromatic C–F group in the formation of weak
intermolecular interactions in the absence of strong hydrogen bond
donors and acceptors has been analyzed in a series of 15 newly synthesized
fluorine substituted (mono- and di-) isomeric <i>N-</i>benzylideneanilines.
It was observed that five compounds (out of a total number of 15)
were liquids at room temperature, while others have low melting points
(<60 °C). <i>In situ</i> crystallization, using
an optical heating and crystallization device (OHCD), has been used to crystallize
and determine the crystal structures of three out of five compounds
which were found to be liquids at 25 °C. A detailed investigation
of the molecular conformation and the crystal packing in these compounds
reveals that the presence of organic fluorine acts as a significant
contributor in the construction of various supramolecular synthons,
essentially using a variety of C–H···F intermolecular
interactions. These have been found to generate different three-dimensional
arrangements of molecules in the crystalline framework. In order to
realize the stabilizing influence exerted by such weak interactions,
intermolecular C–H···F interaction energies
have been calculated using Firefly to quantify the strength of such
interactions. Lattice energy calculations have been performed and
the individual energies, namely, the Coulombic, polarization, dispersion,
and repulsive contributions to the lattice energy have been determined
using the CLP program. In addition to these, theoretical calculations
have been performed at the density functional theory level, and the
experimental geometry has been compared with the optimized geometry
to highlight the importance of molecular conformation in the solid
and gas phase. It is of interest to note that stabilization resulting
from the presence of C–H···F interactions, albeit
less, is not negligible and does contribute toward crystal packing