The Scent of Maibowle - π Electron Localization in Coumarin from Its Microwave-Determined Structure.

The microwave spectra of the natural substance coumarin, a planar aromatic molecule with the specific scent of maibowle, a popular fruit punch served in spring and early summer, were recorded using a molecular jet Fourier transform microwave spectrometer working in the frequency range from 4.0 to 26.5 GHz. The rotational constants and centrifugal distortion constants were determined with high precision, reproducing the spectra to experimental accuracy. The spectra of all singly-substituted C and O isotopologues were observed in their natural abundances to determine the experimental heavy atom substitution r and semi-experimental equilibrium r structures. The experimental bond lengths and bond angles were compared to those obtained from quantum chemical calculations and those of related molecules reported in the literature with benzene as the prototype. The alternation of the C-C bond lengths to the value of 1.39 Å found for benzene reflects the localization of π electrons in coumarin, where the benzene ring and the lactone-like chain -CH=CH-(C=O)-O- are fused. The large, negative inertial defect of coumarin is consistent with out-of-plane vibrations of the fused rings.