Polymeric structures containing self-assembled Lidioxane networks; syntheses and crystal structures of [{Li(dioxane)2.5TaCl4S}n]·n/2 dioxane and [{Li2(dioxane)3Cl}n][TaCl6]n

The preparation and X-ray structure analyses of the compounds [{Li(dioxane)2.5TaCl4S}n]·n/2 dioxane (1) and [{Li2(dioxane)3Cl}n][TaCl6]n (2) are described. The title compounds were isolated from a refluxed solution of TaCl5 and Li2S in dioxane/CH3CN. The compounds both crystallize in the monoclinic space group C2/c and contain a network of dioxane bridged Li+ cations. In 1, the polymeric network is further extended by TaCl4S units. The sixth coordination site of the central metal in these TaCl4S units is occupied by an O-atom of one of the Li coordinating dioxane molecules. In contrast, the [TaCl6]− complex anion in 2 is isolated within a three-dimensional LiCldioxane network.