Polymeric supertetrahedral InS clusters assembled by new linkages

Abstract

Four new indium chalcogenide compounds 1–4 were prepared by a similar solvothermal synthetic method in 1,2-diaminocyclohexane (dach) medium with or without the auxiliaries of germanium oxide or ionic liquid 1-butyl-3-methyl imidazolium bromide. Among them, two unusual polymeric structures assembled by Tn clusters were found. The anion of {H₂dach·[Ni(dach)₃]·[In₁₂S₂₀(dach)₂]·3H₂O}_n (1) is a three-dimensional framework assembled by T3 clusters, in which the linkage is a unique In₄(dach)₄S₆ cluster. The anion of {(Hdach)₂·[Co(dach)₃]₄·[In₁₆Co₄S₃₇]·dach·5H₂O}_n (3) is an unusual two-dimensional framework assembled by T4 clusters, in which the T4 clusters are linked by (S₃)²⁻ polysulfide ion. The structures of the other two new compounds are known, and they are {[Ni(dach)₃]·[In₂S₄]·3H₂O}_n (2) and{(Hdach)₄·[Co(dach)₃]₆·{[In₁₆Co₄S₃₄]₂[Co(dach)₂]₃}·6H₂O}_n (4). The auxiliaries play an important role in the structural assembly of the Tn clusters, mainly due to their effects on acidity of the reaction system and solubility of the reactants or products.