Synthesis and structure of (NH4)12[Mo36O112(OH)4(H2O)10], the first example of the [Mo36O112]8- molybdate anion cluster to bear a charge of 12.

Abstract

Treatment of [Mo7O24]6- with 0.05 N HNO3 at pH ∼ 1.8 in the presence of seed crystals of the ammonium salt of Mo-13 isopolymolybdate led to the formation of the title salt, which appears to represent the first reported 12- charged form of this com-position. Analysis of the Mo-O-Mo bond distances obtained from single-crystal X-ray diffraction supports the formulation of the anion in the ammonium com-pound as [Mo36O112(OH)4(H2O)10]12-. Charge balance requires 12 ammonium counter-ions, and the presence of 26 cocrystallized water mol-ecules gives the overall formula (NH4)12[Mo36O112(OH)4(H2O)10]·26H2O. This structure differs from previously reported Mo36 isopolymolybdate phases, including K8[Mo36O112(H2O)16]·36H2O, (H2bipy)4[Mo36O112(H2O)16]·28H2O, {(CH3NH3)8[Mo36O112(H2O)14]·19H2O·2.1(CH3NH3·NO3)} n , (CH3NH3)10[Mo36O112(OH)2(H2O)14]·9H2O, and K10[Mo36O110(OH)6(H2O)12]·38H2O.

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