Accurate, low temperature X-ray crystal structure determinations show that 3,3'-biquinoline (6), 2,2'-biquinazoline (7), 2,2'-biquinoxaline (8), 2,2'-bibenzoxazole (10) and 2,2'-bibenzothiazole (11) all exist in the solid state in centrosymmetric, planar conformations that minimise their dipole moments and maximise both conjugation between the rings and various types of attractive intermolecular associations. In contrast, 4,4'-biquinazoline (9) and 1,1'-bibenzotriazole (12) display non-planar conformations due to repulsive intramolecular interactions.