A new coordination complex, [Ag(IIMB)N 3], was prepared by self-assembly of asymmetric ligand 1-(1-imidazolyl)-4-(imidazol-1-ylmethyl)benzene(IIMB) with [Ag(NH 3) 2]N 3. The crystal structural analysis indicates that the structure of the complex contains fifty-two-membered macrometallacyclic rings, and the complex crystallizes in monoclinic system, space group of P2 1/c with a=0.739 8(1) nm, {b=}1.045 1(1) nm, c=1.812 4(2)nm, β=91.65(1)°, V=1.400 7(3) nm3, Z=4, D c=1.774 g/cm3, {F(000)=}744, R=0.050 5, wR=0.084 0. It is notable that the azide ion bridges two silver(Ⅰ) atoms in end-on fashion.