Synthesis and Structural Characterization of Three New Inorganic “Host‐guest” Polyoxomolybdates

Abstract

AbstractSince two interesting inorganic “host‐guest” polyoxomolybdates 1 and 2 have been reported previously, we have now succeeded in selectively isolating three new acetated “host‐guest” polyoxomolybdates 3–5, which considerably extend the range of structures in the cyclic polyoxomolybdate catalogue. 3 crystallizes in the triclinic space group P‐1 with a = 1.22235(1) nm, b = 1.52977(2) nm, c = 1.54022(1) nm, a = 113.746(1)°, β = 96.742(1)°, γ = 101.564(1)°, V = 2.51892(4) nm3, Z =1, Dc = 2.568 g. cm−3. 4 and 5 crystallize in the monoclinic system: P2(1)/n, a = 1.08298(2) nm, b = 1.54029(1) nm, c = 2.78893(5) nm, β =94.2730(10)°, V = 4.63929(12) nm3, Z = 2 and Dc = 2.671 g. cm−3 for 4, and C2/c, a =2.59907(8) nm, b = 1.65992(3) nm, c = 2.28473(7) nm, β‐93.4370(10)°, V = 9.8392(5) nm3, Z = 4 and Dc = 2.556 g. cm−3 for 5. The structures of 3, 4 and 5 consist of 18‐membered “host‐guest” polyoxoanions [ Na (X)2| ∈ |(μ3‐OH)4Moy8MoVI1052(μ2‐CH3COO)2]−(R+9 (X = CH3COO−for 3, DMF for 4 and H2O for 5), which are connected via Na* ions or hydrogen bonds into infinite extended frameworks.