The presence of halogen bonding between a chloroarene and an aldazine C-H bond, i.e. Ph-Cl⋯H-CPh=N-R', makes all the difference in the crystal structure of 4-chlorobenzaldazine (1, R = H) and causes an idioteloamphiphile layer architecture (flat with longitudinal offset) that features multifurcated halogen bonding and that differs drastically from the one in 4-chloroacetophenone azine (2, R = CH3).