The molecular structure of 5-X-isatines where (X = F, Cl, and Br) determined by gas-phase electron diffraction with theoretical calculations

Abstract

The molecular structures of 5-X-isatines where X = F (1), Cl (2), and Br (3) were studied by gas-phase electron diffraction (GED) and theoretical calculations at M062X/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels. The best fit of the experimental scattering intensities was obtained for a molecular model of Cs symmetry. The small differences between similar geometric parameters were constrained at the values calculated at the M062X level. The bond distances in the benzene ring are in agreement with their standard values. The (O)CC(O) carbon-carbon bonds of the pyrrole moiety in title compounds (1.581(11), 1.578(8), 1.574(12) Å, respectively) are remarkably lengthened in comparison with standard C(sp2)–C(sp2) value, 1.425(11) Å for N-methylpyrrole. According to NBO analysis this lengthening cannot be attributed to the electrostatic repulsion of oxygen lone pairs alone and is, mainly, due to the hyperconjugation, that is delocalization of oxygen lone pairs of π-type into the corresponding carbon-carbon antibonding orbital, nπ(O)→σ*(CC). Deletion of σ*(CC) orbital followed by subsequent geometry optimization led to shortening of the corresponding CC bond by 0.05–0.06 Å. Electronegative halogen atoms led to increase of CCXC endocyclic bond angles at ipso carbon atom as compared with the value of 120° in regular hexagon. According to different aromaticity descriptors, aromaticity of benzene moiety of title compounds is smaller in comparison with benzene molecule. External magnetic field induces diatropic ring current in benzene moiety. Local reactivity descriptors that indicate sites in a molecule that are susceptible to nucleophilic, electrophilic and radical attack are calculated.