Structural Study of Organic−Inorganic Hybrid Thiogallates and Selenidogallates in View of Effects of the Chelate Amines

Four new gallium chalcogenides [H 2 dap] 4 Ga 4 Se 10 ( 1 ), [Mn(dap) 3 ] 0.5 GaSe 2 ( 2 ), {[Ni(tepa)] 2 SO 4 }[Ni(tepa)(Ga 4 S 6 (SH) 4 )] ( 3 ) and [Mn(atep)]Ga 2 S 4 ( 4 ) (dap = 1,2-diaminopropane, tepa = tetraethylenepentamine, atep = 4-(2-aminoethyl)triethylenetetramine) have been synthesized by solvothermal methods and structurally characterized. The effects of the strong chelating amines on the topology of gallium chalcogenidometalates have been enumerated. First, in the absence of transition metal ions, the chelating amine can offer more N−H groups than the monoamines to form hydrogen bonds; therefore, compound 1 takes a 2-D polymeric structure constructed by supertetrahedral clusters ([Ga 4 Se 10 ] 8−, T 2 ). Second, when transition metals are incorporated into the chelating amine system, larger [M(dap) 3 ] 2+ complex cations are formed, which force the anions of compound 2 to adopt a 1-D structure ([GaSe 2 ] − chain). Third, when an appropriate chelating amine (e.g., tepa) is selected, unsaturated transition metal complex cations can be obtained, which not only act as a large cation but also form the covalently linked organic−inorganic hybrid compounds 3 and 4 . The anion in 3 is a T 2 {[Ga 4 S 6 (SH) 4 ] 4− } cluster connected to a [Ni(tepa)] 2+ complex cation, while the structure of 4 consists of 1-D sinusoidal [Ga 4 S 8 4− ] n anion combined with [Mn(atep)] 2+ complex cations.