The 2,4,6-trimercaptotriazine (TMT) ligand system is currently being used as a complexing agent for divalent metals although little is known about its chemistry. This report entails a description of the syntheses and structures of TMT complexes having the formula M(TMTH2)(2) . nH(2)O (M = Ca (1), Sr (2), and Ba (3), where n = 11, 11, and 4.5, respectively). In 1 and 2, the structures consist of alternating layers of hydrated metal cations and pi-stacked TMT groups. A wide range of hydrogen-bonding interactions connect these layers. Compound 3 forms as a polymeric molecule with covalent bonds between the Ba atoms and TMT ligands. compounds was structurally characterized. X-ray data : 1, C24H104C4N24O44S24, triclinic, , a = 12.9622(7) Angstrom, b = 15.9874(9) Angstrom, c = 24.516(1) Angstrom, alpha = 81.191(1)degrees, beta = 89.560(1)degrees, gamma = 72.433(1)degrees, Z = 2; 2, C6H26N6O11S6Sr, triclinic , a = 8.7454(5) Angstrom, b = 11.7545(6) Angstrom, c = 13.7292(7) Angstrom, alpha = 66.529(1)degrees, beta = 73.201(1)degrees, gamma = 77.034(1)degrees, Z = 2; 3, C12H18Ba2N12O9S12, monoclinic, P2(1)/c. a = 8.5576(4) Angstrom, b = 21.028(1) Angstrom, c = 20.276(1) Angstrom, beta = 96.440(1)degrees, Z = 2.