2D and 3D supramolecular assemblies of double cyclopalladated azobenzenes realized by C–H⋯Cl–Pd, π⋯π and C–H⋯π interactions

The double cyclopalladated complex with azobenzene, μ-[(E)-1,2-diphenyldiazene-C2,8, N1,2]-di-[chloro(dimethylsulfoxide)palladium(II)]; (DMSO)PdCl(μ-C6H4Ndouble bond; length as m-dashNC6H4)(DMSO)PdCl (1) and its analogous complex with DMF as ancillary ligand, (DMF)PdCl(μ-C6H4Ndouble bond; length as m-dashNC6H4)(DMF)PdCl; μ-[(E)-1,2-diphenyldiazene-C2,8,N1,2]-di-[chloro(dimethylformamide)palladium(II)] (2a) were synthesized and the function of cyclopalladated moiety in molecular assembling in the solid state is illustrated by their crystal packings. The polymorphism of 2a and 2b is discussed. The crystal structures reveal assemblies with molecular components self-organized by C–H⋯Cl–Pd hydrogen bonds, π⋯π, and C–H⋯π interactions. The double cyclopalladated complexes of azobenzene, with two Pd–Cl moieties participating in the hydrogen bond formation and π-conjugated system involved in the π⋯π or C–H⋯π interactions, represent a new class of building blocks for construction of solid state supramolecular assemblies.