Characterization of Gold Clusters by Crystallization with Polyoxometalates: the Intercluster Compounds [Au9(dpph)4][Mo8O26], [Au9(dpph)4][PW12O40] and [Au11(PPh3)8Cl2]2[W6O19]

Four intercluster compounds constituted of different gold clusters and polyoxometalates have been crystallized and their crystal structures been determined. Two crystal structures comprise the new gold cluster [Au9(dpph)4]3+ (dpph = 1,6‐ bis(diphenylphosphino)hexane) and an octamolybdate anion, but differ in the overall packing of the building blocks, which are mutually coordinated distorted square planar (1: Pnna, Z = 4, a = 26.381(2), b = 32.428(2), c = 22.951(2) Å; 2: Pnna, Z = 8, a = 44.182(6), b = 43.138(6), c = 19.631(3) Å). The same gold cluster was found in [Au9(dpph)4][PW12O40], which crystallizes in P 1 , Z = 2, a = 17.450(2), b = 18.833(3), c = 31.590(4) Å, α = 77.967(2)°, β > = 76.724(2)°, γ> = 64.598(2)°. The overall packing can be related to the NaCl‐type structure. The building blocks of [Au11(PPh3)8Cl2]2[W6O19] are packed as in the anti‐CdI2‐type structure. The compound crystallizes in P 1 , Z = 1, a = 17.201(2), b = 18.154(2), c = 27.786(3) Å, α = 88.752(2)°, β = 88.426(2)°, γ = 68.331(2)°.