Sulfur-Bridged Sandwich Cubane-Type Molybdenum−Antimony Cluster. Synthesis, X-ray Structure, and <sup>121</sup>Sb Mössbauer Spectra of [(H<sub>2</sub>O)<sub>9</sub>Mo<sub>3</sub>S<sub>4</sub>SbS<sub>4</sub>Mo<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub>](CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>)<sub>8</sub>·24H<sub>2</sub>O
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A sulfur-bridged sandwich cubane-type molybdenum−antimony cluster [(H2O)9Mo3S4SbS4Mo3(H2O)9]8+ (2) has been synthesized through the reaction of incomplete cubane-type molybdenum cluster [Mo3S4(H2O)9]4+ (1) with antimony metal, and has been isolated as 2(pts)8·24H2O (2·pts) (Hpts = p-toluenesulfonic acid), whose structure has been characterized by X-ray crystallography. Crystal data of 2·pts: triclinic, space group P1̄, a = 14.468(3) Å, b = 18.531(5) Å, c = 13.713(6) Å, α = 105.26(2)°, β = 119.71(1)°, γ = 72.48(3)°, V = 3016(1) Å3, Z = 1, Dcalcd = 1.696 g cm-3, Dobsd = 1.72 g cm-3, R (Rw) = 4.7 (7.5) for 6593 reflections (I > 2.0σ(I)). The Mo−Sb distances (3.68[2]) Å) are much longer than the Mo−Mo (2.717[7] Å) distances. Peak positions and ε values (λmax, nm (ε, M-1 cm-1)) of the electronic spectrum of 2·pts in 2 M HCl are 384 (13 220), 625 (10 440), and 700 (10 080). The 121Sb Mössbauer parameters (δ = −2.64 mm s-1, e2qQ = 18.1 mm s-1, η = 0.29), and the binding energies (eV) and full widths at half-maximum (in parentheses, eV) obtained from XPS spectrum (Sb3d3/2, 540.3(2.3); Mo3d3/2, 233.2(2.1); Mo3d5/2, 230.2(1.9); (C1s = 285.0)) of 2·pts indicate that the oxidation number of antimony is III, and the mean oxidation number of molybdenum is +3.5.
