The synthesis of a water-soluble anionic silver 2-mercaptonicotinate complex having effective antibacterial and antifungal properties is described. Its structure has been confirmed to be a hexameric cluster by an X-ray diffraction analysis of a mixed Na+/Tris(+) salt (Tris(+) = tris(hydroxymethyl)methylammonium cation). The [Ag(mna)](6)(6-) cluster has a Ag6S6 core and an overall shape of twisted hexagonal cylinder with six sulfur atoms and six silver atoms alternating on a puckered drum-like surface. Each Ag atom is trigonally coordinated by one N and two S ligands. The overall [Ag(mna)](6)(6-).4Na(+).2[(HOCH2)(3)CNH3](+).10H(2)O complex has a layered appearance in the crystal packing diagram, with a [Ag(mna)](6-) cluster layer alternating with a solvent layer consisting of sodium atoms, Tris buffer cations, and water molecules, The structure is almost identical to that of a neutral [Ag(Hmna)](6) complex reported earlier. The neutral and charged complexes are both known to possess antimicrobial activities, and some biological properties of these and related compounds are briefly discussed in this paper.