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, PÄ«, 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, PÄ«, 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, PÄ«, 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, PÄ«, 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, PÄ«, 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.