The compounds (Me4N)[A{M(SC{O}Ph)(3)}(2)] (A = K, M = Cd (2); A = Na, M = Hg (3); and A = K, M = Hg (4)) were synthesized by reacting the appropriate metal chloride with A(+)PhC(O)S- and Me4NCl in the ratios 1:3:1 and 2:6:1. The structures of these compounds were determined by single-crystal X-ray diffraction methods. All the compounds are isomorphous, isostructural, and crystallized in the space group P (1) over bar with Z = 1. Single-crystal data for 2: a = 10.6670(2) Angstrom, b = 11.1522(2) Angstrom, c = 11.9294(2) Angstrom, alpha = 71.782(1)degrees, beta = 85.208(1)degrees, gamma = 69.418(1)degrees, V = 1261.40(4) Angstrom(3), D-calc = 1.528 g cm(-3). Single-crystal data for 3: a = 10.840(2) Angstrom, b = 10.946(4) Angstrom, c 12.006(3) Angstrom, alpha = 72.18(2)degrees, beta = 86.75(2)degrees, gamma = 67.43(2)degrees, V = 1249.3(6) Angstrom(3), D-calc = 1.756 g cm(-3). Single-crystal data for 3: a = 10.4780(1) Angstrom, b = 11.2563(2) Angstrom, c = 11.9827(2) Angstrom, a 71.574(1)degrees, beta = 85.084(1)degrees, gamma = 70.705(1)degrees, V = 1265.23(3) Angstrom(3), D-calc = 1.755 g cm(-3). In the [A{M(SC{O}Ph)(3)}(2)](-) anions, each M(II) atom is bonded to three thiobenzoate ligands through sulfur atoms, giving a trigonal planar MS3 geometry. The carbonyl oxygen atoms from the two [M(SC{O}Ph)(3)](-) anions are bonded to the alkali metal atom, providing an octahedral environment. Solution metal NMR studies showed the concentration-dependent dissociation of the alkali metal ions in the trinuclear anions.