Crystal structure, Hirshfeld surface analysis, interaction energy and DFT calculations and energy frameworks of methyl 6-chloro-1-methyl-2-oxo-1,2-dihydroquinoline-4-carboxylate

Abstract

In the title compound, C12H10ClNO3, the dihydroquinoline moiety is not planar with a dihedral angle between the two ring planes of 1.61(6)°. An intramolecular C-H..O hydrogen bond helps to establish the rotational orientation of the carboxyl group. In the crystal, sheets of molecules parallel to (10) are generated by C-H..O and C-H..Cl hydrogen bonds, and are stacked through slipped π-stacking interactions between inversion-related dihydroquinoline units. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H..H (34.2%), H..O/O..H (19.9%), H..Cl/Cl..H (12.8%), H..C/C..H (10.3%) and C..C (9.7%) interactions. Computational chemistry indicates that in the crystal, the C-H..Cl hydrogen-bond energy is-37.4kJmol-1, while the C-H..O hydrogen-bond energies are-45.4 and-29.2kJmol-1. An evaluation of the electrostatic, dispersion and total energy frameworks revealed that the stabilization is dominated via the dispersion energy contribution. Density functional theory (DFT) optimized structures at the B3LYP/6-311G(d,p) level are compared with the experimentally determined molecular structure in the solid state, and the HOMO-LUMO behaviour was elucidated to determine the energy gap.