New Metalloligands [M(SC{O}Ph)4]-: Synthesis and Characterization of Polymeric [A(MeCN)x{M(SC{O}Ph)4}] Compounds (A = Li, Na and K; M = Ga and In;x= 0−2)

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Abstract
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(I) to Na(I) to K(I). Crystal data for 2·0.5MeCN·0.25H2O: monoclinic space group C2/c, a = 24.5766(8) Å, b = 13.2758(5) Å, c = 19.9983(8) Å, β = 108.426(1)°, Z = 8, and V = 6190.4(4) Å3. Crystal data for 4: monoclinic space group P21/c, a = 10.5774(7) Å, b = 21.9723(15) Å, c = 14.4196(10) Å, β = 110.121(1)°, Z = 4, and V = 3146.7(4) Å3. Crystal data for 6: monoclinic space group P21/c, a = 12.307(3) Å, b = 13.672(3) Å, c = 20.575(4) Å, β = 92.356(4)°, Z = 4, and V = 3458.8(12) Å3. The thermal decomposition of these compounds indicated the formation of the corresponding AMS2 materials.