Oxalato complexes of the trinuclear aquo ion of molybdenum(IV), [Mo3O4]4+

The preparations and X-ray crystallographic structure determinations of two compounds containing the complex oxalato anion of Mo3O44+, viz., [Mo3O4(C2O4)3(H2O)3]−, are reported. Compound 1, Cs2[Mo3O4(C2O4)3(H2O)3]·4H2O·H2C2O4 forms monoclinic crystals (space group P21/n) with unit cell dimensions a = 12.82(2) A, b = 16.764(3) A, c = 12.529(2) A, β = 91.31(2)° and Z = 4. Compound 2, Cs3[Mo3O4(C2O4)3]CF3SO3·3H2O, forms hexagonal crystals (space group R3m) with a = 12.955(1) A, c = 14.738(2) A and Z = 3. The [Mo3O4(C2O4)3(H2O)3]2− ion has essentially the same dimensions in each case. In compound 1 no crystallographic symmetry is required while in 2C3v symmetry is imposed. Some important dimensions are the following where we give first the mean value (averaged according to C3v symmetry) for 1 and then the value for 2: MoMo, 2,486(1) A. 2,491(1) A; Mo(μ3-O), 2.0196(6) A, 2.01(1) A; Mo(μ2-O), 1.921(4) A, 1.908(7) A; MoO(H2O), 2.154(7) A, 2.15(1) A; MoO(oxalate), 2.091(4) A, 2.102(8) A; Mo(μ3-O)Mo, 76.0(1)°, 76.6(6)°, Mo(μ2-O)Mo, 80.6(1)°, 81.5(4)°.

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