Determination of the Privileged Structure of 8-Hydroxyquinoline

An accurate semi-experimental equilibrium structure of 8-hydroxyquinoline (8-HQ) has been determined combining experiment and theory. The cm-wave rotational spectrum of 8-HQ was recorded in a pulsed supersonic jet using broadband dual-path reflection and narrowband Fabry-Perot-type resonator Fourier-transform microwave spectrometers. Accurate rotational and quartic centrifugal distortion constants and N-14 quadrupole coupling constants are determined. Rotational constants of all C-13, O-18 and N-15 singly substituted isotopologues in natural abundance and those of a chemically synthesized OD isotopologue were used to obtain geometric parameters for all the heavy atoms and the hydroxyl hydrogen from a number of structure determination models. Theoretical approaches allowed for the determination of a semi-experimental equilibrium structure, r(e)(SE) in which computed rovibrational and electronic corrections were utilized to convert vibrational ground state constants into equilibrium constants. Despite the molecule having only a horizontal plane of symmetry and possessing 11 individual heavy atoms, microwave spectroscopy has allowed for a reliable and accurate structure determination. A mass dependent, r(m)((2)) structure was determined and proved to be equally reliable by comparison with the B3LYP-D3(BJ)/aVTZ equilibrium structure.

Automated summary

An accurate semi-experimental equilibrium structure of 8-hydroxyquinoline was determined using a combination of experiment and theory, with the rotational spectrum recorded in a pulsed supersonic jet. Theoretical approaches were used to convert vibrational ground state constants into equilibrium constants, resulting in a reliable structure determination. The mass-dependent structure was found to be equally reliable as the B3LYP-D3(BJ)/aVTZ equilibrium structure.