The reaction of AgNO3 with bulky anthracene-9-carboxylic acid (HL1) in the presence of 2,6-dimethylpyridine (dmp) afforded a photoluminescent hexanuclear discrete AgI complex [Ag6(L1)6(dmp)2] exhibiting C–H⋯Ag interactions whose total interaction energy were further estimated by DFT calculations. The relevant results reveal that the steric bulk of the anthracene ring skeleton of L1 may play important roles in the formation of the final structure.