A new hexanuclear silver(I) compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523(9),b = 24.7519(11),c = 22.4542(15) ,β = 93.4960(10)°,V = 10347.4(10)3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ(MoKα) = 1.293 mm-1,F(000) = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections(I 〉 2σ(I)).In the structure,two Ag6L36(L3 = pyridine-3-carboxaldehyde thiosemicarbazone) clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered(CC) electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.