Charge density matching in templated molybdates

The role of charge density matching in the formation of templated molybdates under mild hydrothermal conditions was investigated through the use of a series of structurally related amines: piperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine and 2,6-dimethylpiperazine. A series of reactions was conducted in which the relative mole fractions of each component were fixed at 2.5 MoO3:1 amine:330 H2O:2 H2SO4 in order to isolate the effects of the amine, the only variation between reactions was the structure of the amine. Four distinct polyoxomolybdates anions were observed, ranging from zero-dimensional β-[Mo8O26]4− molecular anions to [Mo3O10]n2n− and [Mo8O26]n4n− chains and [Mo5O16]n2n− layers. The primary influence over the structure of the molybdate anion is charge density matching with the protonated amine, which was quantified through surface area approximations based upon both calculated molecular surfaces and polyhedral representations of each anion. Secondary influences include amine symmetry and hydrogen-bonding preferences. The synthesis and characterization of two new compounds are reported. Crystal data: [C6H16N2][Mo3O10]·H2O (1), triclinic, P-1 (no. 2), a=8.0973(7) Å, b=8.8819(9) Å, c=11.5969(11) Å, α=71.362(9)°, β=82.586(8)°, γ=74.213(8)°, Z=2, R/Rw=0.0262/0.0564, and [C6H16N2]2[Mo8O26] (2), monoclinic, P21/n (no. 14), a=7.9987(11) Å, b=12.5324(19) Å, c=16.003(3) Å, β=97.393(14)°, Z=2, R/Rw=0.0189/0.0454.