Exploiting the ability of the [M(SC{O}Ph)(4)](-) anion to behave like an anionic metalloligand, we have synthesized [Li{Ga(SC{O}Ph)(4)}] (1), [Li{In(SC{O}Ph)(4)}] (2), [Na{Ga(SC{O}Ph)(4)}] (3), [Na(MeCN){In(SC{O}Ph)(4)}] (4), [K{Ga(SC{O}Ph)(4)}] (5), and [K(MeCN)(2){In(SC{O}Ph)(4)}] (6) by reacting MX3 and PhC{O}S(-)A(+) (M = Ga(III) and In(III); X = Cl- and NO3-; and A = Li(I), Na(I), and K(I)) in the molar ratio 1:4. The structures of 2, 4, and 6 determined by X-ray crystallography indicate that they have a one-dimensional coordination polymeric structure, and structural variations may be attributed to the change in the alkali metal ion from Li(l) to Na(l) to K(l). Crystal data for 2.0.5MeCN.0.25H(2)O: monoclinic space group C2/c, a = 24.5766(8) Angstrom, b = 13.2758(5) Angstrom, c = 19.9983(8) Angstrom, beta = 108.426(1)degrees, Z = 8, and V = 6190.4(4) Angstrom(3). Crystal data for 4: monoclinic space group P2(1)/c, a = 10.5774(7) Angstrom, b = 21.9723(15) Angstrom, c = 14.4196(10) Angstrom, beta = 110.121(1)degrees, Z = 4, and V = 3146.7(4) Angstrom(3). Crystal data for 6: monoclinic space group P2(1)/c, a = 12.307(3) Angstrom, b = 13.672(3) Angstrom, c = 20.575(4) Angstrom, beta = 92.356(4)degrees, Z = 4, and V = 3458.8(12) Angstrom(3). The thermal decomposition of these compounds indicated the formation of the corresponding AMS(2) materials.