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 P21/c with lattice parameters a = 12.8698(12) Å, b = 10.4812(9) Å, c =
16.5473(14) Å and β = 102.457(4)° (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) Å, b = 15.0696(10) Å, c = 12.2893(7) Å, Z = 8) M = Co (3) (orthorhombic, Cmcm, a = 9.4660(7) Å,
b = 15.0990(11) Å, c = 12.2540(8) Å, Z = 8), M = Ni (4) (orthorhombic, Cmcm, a = 9.4510(10) Å, b =
15.1416(15) Å, c = 12.2387(11) Å, Z = 8)) and Mn(en)2Ga2S4 (5) (monoclinic, C2/c, a = 14.3002(11) Å, b =
7.9509(5) Å, c = 12.1184(6) Å, β = 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.