Binuclear [{(DMOX)CdCl} 2 (μ-Cl) 2 ] (DMOX=4,5-dihydro-2-(4,5-dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyl-oxazole) (1) and mononuclear [(Dm-Pybox)CdCl 2 ] (Dm-Pybox=2,6-bis[4′,4′-dimethyloxazolin-2′-yl]pyridine) (2) were obtained by reacting CdCl 2 with DMOX and Dm-Pybox ligands, respectively. In the solid state, the supramolecular structures of 1 and 2 feature helical chains fabricated by C–H⋯Cl hydrogen bond interactions. The C–N cross-coupling reactions catalyzed by the two complexes were also investigated in homogeneous system. The results show that binuclear complex 1 exhibit significantly enhanced catalytic activity for C–N cross-coupling reactions.