Two trans-4-aminoazoxybenzenes

Two isomeric trans-4-aminoazoxybenzenes, trans-1-(4-aminophenyl)-2-phenyldiazene 2-oxide (alpha, C(12)H(11)N(3)O) and trans-2-(4-aminophenyl)-1-phenyldiazene 2-oxide (beta, C(12)H(11)N(3)O), have been characterized by X-ray diffraction. The alpha isomer is almost planar, having torsion angles along the C(aryl)-N bonds of only 4.9 (2) and 8.0 (2) degrees. The relatively short C(aryl)-N bond to the non-oxidized site of the azoxy group [1.401 (2) A], together with the significant quinoid deformation of the respective phenyl ring, is evidence of conjugation between the aromatic sextet and the pi-electron system of the azoxy group. The geometry of the beta isomer is different. The non-substituted phenyl ring is twisted with respect to the NNO plane by ca 50 degrees, whereas the substituted ring is almost coplanar with the NNO plane. The non-oxidized N atom in the beta isomer has increased sp(3) character, which leads to a decrease in the N-N-C bond angle to 116.8 (2) degrees, in contrast with 120.9 (1) degrees for the alpha isomer. The deformation of the C-C-C angles (1-2 degrees ) in the phenyl rings at the substitution positions is evidence of the different character of the oxidized and non-oxidized N atoms of the azoxy group. In the crystal structures, molecules of both isomers are arranged in chains connected by weak N-H.O (alpha and beta) and N-H.N (beta) hydrogen bonds.