The acid dissociation constants of 2,4,6-trimercaptotriazine (H(3)TMT, 1) were determined and now can be employed in the preparation of complexes having specific M-TMT (M = divalent metal; TMT = 2,4,6-trimercapto-1,3,5-triazinide, C(3)N(3)S(3)(3-)) ratios. For example, the combination of H(3)TMT (1) with Mg(OH)(2) at pH 7.1 leads to the crystallization of Mg(H(2)TMT)(2).6H(2)O (4). With the appropriate pH adjustment, the contiguous series of compounds Ba(3)(TMT)(2).8H(2)O (3), Ba(H(2)TMT)(2).7H(2)O (5), and BaHTMT.3H(2)O (6) can be isolated. The compounds were characterized by mp, IR, TGA, elemental analysis, and, in the cases of 4, 5, and 6, crystallography. The comparison of 4 with 5 and 6 offers an interesting view of the difference in hard and soft bonding with TMT. In the saltlike Mg structure of 4, there is extensive hydrogen bonding, but in the Ba structures, 5 and 6, covalent Ba-S bonding dominates.