The syntheses of new compounds of the general formula A4[Nb6Cl18] (A = Ga, In, Tl) and A4[Ta6Cl18] (A = In, Tl) are reported. The indexing of their X-ray powder patterns was performed isotypically with K4Nb6Cl18]- A single-crystal structure refinement on In4[Ta6Cl18] gave the space group C2/m, Z - 2, a = 1077.7(3) pm, b = 1542.3(5) pm, c = 960.2(2) pm, β = 117.68(2) . The structure contains [Ta6Cl12Cl6]4- ions linked via I+ ions . In+ is situated in a strongly distorted coordination sphere of Cl- .
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