title: Substituent effects in trans-p,p'-disubstituted azobenzenes: X-ray structures at 100 K and DFT-calculated structures.
abstract: The crystal and molecular structures of two para-substituted azobenzenes with π-electron-donating -NEt2 and π-electron-withdrawing -COOEt groups are reported, along with the effects of the substituents on the aromaticity of the benzene ring. The deformation of the aromatic ring around the -NEt2 group in N,N,N',N'-tetraethyl-4,4'-(diazenediyl)dianiline, C20H28N4, (I), may be caused by steric hindrance and the π-electron-donating effects of the amine group. In this structure, one of the amine N atoms demonstrates clear sp(2)-hybridization and the other is slightly shifted from the plane of the surrounding atoms. The molecule of the second azobenzene, diethyl 4,4'-(diazenediyl)dibenzoate, C18H18N2O4, (II), lies on a crystallographic inversion centre. Its geometry is normal and comparable with homologous compounds. Density functional theory (DFT) calculations were performed to analyse the changes in the geometry of the studied compounds in the crystalline state and for the isolated molecules. The most significant changes are observed in the values of the N=N-C-C torsion angles, which for the isolated molecules are close to 0.0°. The HOMA (harmonic oscillator model of aromaticity) index, calculated for the benzene ring, demonstrates a slight decrease of the aromaticity in (I) and no substantial changes in (II).
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Gajda
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
authors.forename: Bartosz
authors.initials: B
authors.lastname: Zarychta
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
authors.forename: Zdzisław
authors.initials: Z
authors.lastname: Daszkiewicz
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
authors.forename: Andrzej A
authors.initials: AA
authors.lastname: Domański
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Ejsmont
keywords: 4,4′-(diazenediyl)dianiline; 4,4′-(diazenediyl)dibenzoate; DFT calculations; HOMA index; azobenzenes; crystal structure; electron-donating effects; electron-withdrawing effects