Fig 1.
Synthesis of (E)-N'-benzylidene-4-((3-fluorobenzyl)oxy)benzohydrazide (C21H17FN2O2) (FBHZ).
Fig 2.
Projection along axis b of the crystal showing the asymmetric unit of embedded FBHZ in the polarization field, the atoms of the molecules of the involved units being treated as point charges.
Fig 3.
The molecular structure of the FBHZ showing the atom-labelling scheme.
Thermal ellipsoids drawn at the 30% probability level. The hydrogen atoms are shown as arbitrary spheres.
Table 1.
Crystallographic information on the FBHZ.
Table 2.
MP2/6-311+G(d) results for the components of the dipole moment (D) as function of the iterative process.
Table 3.
MP2/6-311+G(d) results for the linear polarizability (10−24) esu).
Table 4.
MP2/6-311+G(d) results for the first hyperpolarizability (10−30 esu).
Table 5.
Linear optical susceptibility tensor components χ(1) of FBHZ.
Fig 4.
Crystal packing diagram of FBHZ.
Cyan dashed lines indicate all possible contacts.
Fig 5.
a) UNI intermolecular potential calculation results, showing the three largest lattice contributions of FBHZ in red dashed lines from molecule 0 to each independent molecule [Mol 1: -55.4 kJ.mol-1; Mol 2: -55.3 kJ.mol-1; and Mol 3: -53.8 kJ.mol-1]. b) Bifurcated C−H⋯O/N−H⋯O hydrogen bonds with donor-acceptor distances [d(D⋯A) Å]. c) weak hydrogen bonds C−H⋯O/N−H⋯O and C−H⋯π (localized) contacts with donor-acceptor distances [d(D⋯A) Å]. d) The non-conventional C−H⋯F hydrogen bonds with donor-acceptor distances [d(D⋯A) Å] and C−H⋯F angles [∠(C−H⋯F) °].
Fig 6.
The HS mapped with dnorm property, highlighting regions of contact such as H⋯O (C−H⋯O/N−H⋯O hydrogen bonds), H⋯N (C−H⋯N weak hydrogen bonds) and H⋯C [C−H⋯π (localized on C)] contacts.
Fig 7.
2D fingerprint plots showing the percentage decomposition from each indicatory type of contact related to C−H⋯π [H⋯C 36.9%], C−H⋯O [O⋯H 12.4%], C−H⋯F [H⋯F 9.9%], N−H⋯O [N⋯H 6.4%] and H⋯H 32.5% in HS for FBHZ.
Fig 8.
Heating-cooling-reheating DSC and TGA data for the FBHZ.
The solid-liquid transition via Hot-stage Microscopy analysis is also shown.
Fig 9.
Evolution of values of the dipole moment of the FBHZ with the respective iteration numbers.
A 9×9×9 unit cell assembly was considered (step 0 indicates the isolated molecule and the other steps indicate the embedded molecule).
Table 6.
Second-order nonlinear optical susceptibility tensor components χ(2) (in pm/V) of FBHZ.
Table 7.
CAM-B3LYP/6-311+G(d) results for the second hyperpolarizability (10−36 esu) in the static case.
Fig 10.
Dynamic evolution of the calculated values for the linear polarizability (10−24 esu), first hyperpolarizability (10−30 esu), and second hyperpolarizability (10−36 esu) of FBHZ with the respective number of frequencies.
Table 8.
CAM-B3LYP/6-311+G(d) results for the dynamic linear polarizability (10−24 esu), first hyperpolarizability (10−30 esu), and second hyperpolarizability (10−36 esu) of the isolated and embedded FBHZ at frequency ω = 0.0428 a.u.
Table 9.
MP2/6-311+G d results for the CHELPG atomic charges of isolated and embedded FBHZ.
Table 10.
CAM-B3LYP/6-311+G(d) results for the dynamic linear polarizability (10−24 esu), first hyperpolarizability (10−30 esu) and second hyperpolarizability (10−36 esu) of gas-phase and DMSO solvent FBHZ for the frequency ω = 0.0428 a.u.
Fig 11.
Molecular orbital plots, showing HOMO-LUMO as obtained in the CAM-B3LYP/6-311+G(d) level of theory for DMSO solvent, for the FBHZ molecule.
Fig 12.
Molecular orbital plots, showing HOMO-LUMO as obtained in the CAM-B3LYP/6-311+G(d) level of theory for gas-phase, for the FBHZ molecule.
Table 11.
TDDFT PBE1PBE/6-311+G(2d,p) of the FBHZ molecule in the gas phase and DMSO.