From one-dimensional chains to three-dimensional networks: solvothermal synthesis of thiogallates in ethylenediamine.

Five new thiogallates have been prepared solvothermally in the presence of ethylenediamine and characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. [enH2][Ga4S7(en)2] (1), which crystallizes in the monoclinic space group P2(1)/c with lattice parameters a = 12.8698(12) angstroms, b = 10.4812(9) angstroms, c = 16.5473(14) angstroms and beta = 102.457(4) degrees (Z = 4), exhibits a layered structure in which both covalently and hydrogen-bonded template molecules coexist. The structures of [M(en)3](0.5)[GaS2] (M = Mn (2) (orthorhombic, Cmcm, a = 9.5555(6) angstroms, b = 15.0696(10) angstroms, c = 12.2893(7) angstroms, Z = 8) M = Co (3) (orthorhombic, Cmcm, a = 9.4660(7) angstroms, b = 15.0990(11) angstroms, c = 12.2540(8) angstroms, Z = 8), M = Ni (4) (orthorhombic, Cmcm, a = 9.4510(10) angstroms, b = 15.1416(15) angstroms, c = 12.2387(11) angstroms, Z = 8)) and Mn(en)2Ga2S4 (5) (monoclinic, C2/c, a = 14.3002(11) angstroms, b = 7.9509(5) angstroms, c = 12.1184(6) angstroms, beta = 100.191(4) degrees , Z = 4) are closely related and contain one-dimensional [GaS2]- chains, which are separated by [M(en)3]2+ counterions in 2, 3, and 4, and linked into a three-dimensional structure by [Mn(en)2]2+ units in 5.