5,5′-Bis(3-hydroxyphenyldiazo)-dipyrromethane, compound 3, was synthesized and its crystal structures with methanol, THF and acetone were studied by X-ray crystallography. In all three crystal structures, the 5,5′-bisdiazo-dipyrromethane still assembled into interlocked type dimers through quadruple NH⋯N hydrogen bonds. In the solid state, 3⋅3 dimers assembled into [n]cantane like structure mediated by methanol which act as hydrogen bond donor and acceptor. The 3⋅3 dimers assembled into rotaxane and broken [n]cantane like structures in the cases of THF and acetone, respectively. The solvents effects on the self-assemblies of compound 3 were also witnessed by SEM studies.Highlights► 5,5′-bis(3-hydroxyphenyldiazo)-dipyrromethane was synthesized. ► The 5,5′-bisdiazo-dipyrromethane still assembled into interlocked type dimers through quadruple N-H…N hydrogen bonds. ► [n]cantane, rotaxane and broken [n]cantane like structures were obtained from the self-assemblies of the dimers. ► The solvents effects on the self-assemblies were also witnessed by SEM studies.

A new compound, 1,3-bis[2-(pyrrol-2-carbonyloxy)ethoxy]benzene (1), was synthesized and characterized by X-ray diffraction. The crystal is monoclinic, space group P21/c with a = 6.3571(7), b = 11.0416(11), c = 28.156(3) Å, b = 92.821(2), V = 1974.0(4) Å3, Z = 4, Dc = 1.293 g/cm3, F(000) = 808, μ = 0.097 mm−1. The final R = 0.0395 and wR = 0.0927 for 3478 observed reflections with I > 2 σ(I), and R = 0.0660 and wR = 0.1058 for all reflections. The title compound assembles into 2-D structure through a catemer type N–H⋯O hydrogen bonding motif and further forms 3-D structure through C–H···O hydrogen bonds.

Chlorine, bromine and iodine substituted derivatives of 5,5′-bisdiazo-dipyrromethane have been synthesized and their crystal structures were studied by X-ray crystallography. In the three structures, the 5,5′-bisdiazo-dipyrromethanes form interlocked dimers through quadruple N–H⋯N hydrogen bonds. The halogen⋯π synthons also provide a significant contribution to the resulting supramolecular motifs.