Out-of-plane deformation of the azulene ring in crystal structures of simply substituted azulene derivatives

The crystal structures of 1,3-bis(4-bromophenyl)- and 1,3-di(2-thienyl)azulenes (5 and 6) were elucidated by X-ray analysis. Two aryl groups connect to the azulenyl core with dihedral angles of 34.9-41.6° and the two aryl planes of the groups slant against the azulene ring toward different ways in their crystal structures. It was also found that the azulene rings of 5 and 6 showed a slight out-of-plane deformation in the way that the hydrogen atoms at the 4- and 8-positions are apart from the neighboring aryl ortho-hydrogen atoms to fill in the vacant space made by the slanting aryl planes.