Syntheses, Crystal Structure and Properties of Polyoxometalates Based on Chromic/Aluminousmolybdate Anderson Structure Building Blocks

On the basis of molecular design and assembly, a series of polyoxometalates supported by B-Anderson anions [CrMo6O24H6]3- and [Al（OH）6（Mo6O18）]3- as building blocks were successfully synthesized in aqueous （or mixed solvent） in virtue of metal- coordination ions as bridging ligands, and characterized by X-ray crystallography, spectroscopic and thermal properties.I. Four novel B-Anderson polyoxometalates with Cr atom as central atom were synthesized by reaction of Na₂MoO₄·2H₂O, CrCl3·6H₂O, ZnCl2 and 2, 2’-bipyridine in the mixed solvent （DMSO-water, methanol-water）.1. [Na（H₂O）4]H2[Cr（OH）6（Mo6O18）]·6H₂O: monoclinic, P21/n, a = 11.121 （2） ?, b = 20.944 （4） ?, c = 12.838 （3） ?,β= 99.78 （3）°, V = 2946.8 （10） ?3, Z = 4, Dc = 2.756 Mg/m3, T = 293 （2） K,μ= 2.962 mm-1, R1 = 0.0498, wR2 = 0.1273.2. [Na3（H₂O）11][Cr（OH）6（Mo6O18）]·2H₂O: triclinic, Pī, a = 10.968 （2） ?, b = 11.686 （2） ?, c = 14.895 ?,α= 72.10 （3）°,β= 70.99 （3）°,γ= 66.90 （3）°, V = 1624.5 （6） ?3, Z = 2, Dc = 2.700 Mg/m3, T = 293 （2） K,μ= 2.727 mm-1, R1 = 0.0359, wR2 = 0.0974.3. {Na1/2[Na（H₂O）3]}2[Cr（OH）6（Mo6O18）]·2H₂O: triclinic, Pī, a = 6.463 （13） ?, b = 10.896 （2） ?, c = 10.899 （2） ?,α= 109.07 （3）°,β= 95.53 （3）°,γ= 106.78 （3）°, V = 678.9 （2） ?3, Z = 1, Dc = 3.011 Mg/m3, T = 293 （2） K,μ= 3.238 mm-1, R1 = 0.0363, wR2 = 0.0881.4. [Zn（2, 2’-bipy）（H₂O）4]H[Cr（OH）6（Mo6O18）]·13H₂O: triclinic, Pī, a = 10.439 （2） ?, b = 14.888 （3） ?, c = 16.084 （3） ?,α= 71.27 （3）°,β= 72.11 （3）°,γ= 87.07 （3）°, V = 2249.7 （8） ?3, Z = 2, Dc = 2.273 Mg/m3, T = 293 （2） K,μ= 2.485 mm-1, R1 = 0.0342, wR2 = 0.0936.II. Two B-Anderson polyoxometalates with Al atom as central atom were synthesized by reaction of Na₂MoO₄·2H₂O, AlCl₃·6H₂O and 2, 2’-bipyridine in the mixed methanol-water solvent.5. {Na[Na2（H₂O）6]}[Al（OH）6（Mo6O18）]·2H₂O: triclinic, Pī, a = 6.4341 （13） ?, b = 10.879 （2） ?, c = 10.992 （2） ?,α= 67.49（3）°,β= 73.00（3）°,γ= 84.72（3）°, V = 679.5 （2） ?3, Z = 1, Dc = 2.932 Mg/m3,μ= 2.888 mm-1, R1 = 0.0305, wR2 = 0.0811.6. [Co（2, 2’-bipy）3]H[Al（OH）6（Mo6O18）]·17H₂O: monoclinic, C2/c, a = 37.292 （8） ?, b = 14.214 （3） ?, c = 25.050 （5） ?,β= 120.62 （3）°, V = 11426 （4） ?3, Z = 8, Dc = 2.116 Mg/m3, T = 293 （2） K,μ= 1.685 mm-1, R1 = 0.0748, wR2 = 0.1853.III.β-octamolybdate-supported organic-inorganic compound was synthesized by reaction of Na₂MoO₄·2H₂O, NiCl2·6H₂O and 2, 2’-bipyridine in the mixed methanol-water solvent.7. [Ni（H₂O）（2, 2’-bipy）2]2[Mo8O26]·4H₂O·2CH3COOH: triclinic, Pī, a = 10.356 （2） ?, b = 12.386 （3） ?, c = 13.640 （3） ?,α= 84.96 （3）°,β= 86.57 （3）°,γ= 66.11 （3）°, V = 1593.1 （6） ?3, Z = 1, Dc = 2.245 Mg/m3, T = 293 （2） K,μ= 2.197 mm-1, R1 = 0.0379, wR2 = 0.0979.