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. [enH(2)][Ga4S7(en)(2)] (1), which crystallizes in the monoclinic space group P2(1)/c with lattice parameters a = 12.8698(12) angstrom, b = 10.4812(9) angstrom, c = 16.5473(14) angstrom 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) angstrom, b = 15.0696(10) angstrom, c = 12.2893(7) angstrom, Z = 8) M = Co (3) (orthorhombic, Cmcm, a = 9.4660( 7) angstrom, b = 15.0990(11) angstrom, c = 12.2540(8) angstrom, Z = 8), M = Ni (4) ( orthorhombic, Cmcm, a = 9.4510( 10) angstrom, b = 15.1416(15) angstrom, c = 12.2387(11) angstrom, Z = 8)) and Mn(en)(2)Ga2S4 (5) (monoclinic, C2/c, a = 14.3002(11) angstrom, b = 7.9509(5) angstrom, c = 12.1184(6) angstrom, beta = 100.191(4), 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.