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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...