Polymeric supertetrahedral InS clusters assembled by new linkages

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 {H(2)dach center dot[Ni(dach)(3)]center dot[In12S20(dach)(2)]center dot 3H(2)O}(n) (1) is a three-dimensional framework assembled by T3 clusters, in which the linkage is a unique In-4(dach)(4)S-6 cluster. The anion of {(Hdach)(2)center dot[Co(dach)(3)](4)center dot[In16Co4S37]center dot dach center dot 5H(2)O}(n) (3) is an unusual two-dimensional framework assembled by T4 clusters, in which the T4 clusters are linked by (S-3)(2-) polysulfide ion. The structures of the other two new compounds are known, and they are {[Ni(dach)(3)]center dot[In2S4]center dot 3H(2)O}(n) (2) and{(Hdach)(4)center dot[Co(dach)(3)](6)center dot{[In16Co4S34](2)[Co(dach)(2)](3)}center dot 6H(2)O}(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.