A novel anionic heptadecanuclear silver(I) cluster, (NH4)(17)[(mu(6)-S)@Ag-17(mba)(16)]center dot 22H(2)O (1; H(2)mba = 2-mercaptobenzoic acid), was obtained by the reaction of equivalent molar silver oxide and 2,2'-dithiodibenzoic acid (H(2)dtba) under ultrasonic conditions at 50 degrees C. Complex 1 is a discrete cluster comprised of unexpected mba ligands on the shell and a mu(6)-S2- ion in the core, suggesting the occurrence of in situ S-S and S-C(sp(2)) bond cleavages of the H(2)dtba ligand. This novel cluster displays moderate orange-red emission in the solid state at room temperature.