The synthesis and characterization of the tetrameric lithium thiolate (LiSC6H2-2,4,6-Ph(3))(4).C7H8 (1), the trimeric lithium thiolate (LiSC6H3-2,6-Mes(2))(3).C6H14 (2) (Mes=2,4,6-Me(3)C(6)H(2)), the thiol HSC6H3-2,6-Trip(2) (3) (Trip=2,4,6-i-Pr3C6H2), and the complete alkali metal series of dimeric thiolates (MSC(6)H(3)-2,6-Trip(2))(2) (M=Li (4, 5), Na 6), K (7), Rb (8), Cs (9) are described. The compounds were characterized by H-1, Li-7, and C-13 NMR and IR spectroscopy and by x-ray crystallography. The compounds 1 and 2 crystallize as four- and three-rung ladder framework structures. The compounds 4-9 crystallize as dimers with M(2)S(2) cores. In addition, the metal ions interact with the ortho aryl groups to varying degrees in all the structures. The extent of these interactions appears to be determined mainly by ionic sizes and geometric factors. The coordination geometry of the thiolato sulfurs also varies from pyramidal in 1, 2, 4, 5, and 6 and one planar and one slightly pyramidal sulfur geometry in 7 to both sulfurs being planar coordinated in 8 and 9.