Group 2 Complexes of 2,4,6-Trimercaptotriazine (TMT)

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(TMTH 2 ) 2 · n H 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 π-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. Each of the compounds was structurally characterized. X-ray data: 1, C 24 H 104 Ca 4 N 24 O 44 S 24, triclinic, P 1̄, a = 12.9622(7) Å, b = 15.9874(9) Å, c = 24.516(1) Å, α = 81.191(1)°, β = 89.560(1)°, γ = 72.433(1)°, Z = 2; 2, C 6 H 26 N 6 O 11 S 6 Sr, triclinic P 1̄, a = 8.7454(5) Å, b = 11.7545(6) Å, c = 13.7292(7) Å, α = 66.529(1)°, β = 73.201(1)°, γ = 77.034(1)°, Z = 2; 3, C 12 H 18 Ba 2 N 12 O 9 S 12, monoclinic, P 2 1 / c, a = 8.5576(4) Å, b = 21.028(1) Å, c = 20.276(1) Å, β = 96.440(1)°, Z = 2.