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Abstract
Two new organic–inorganic composite sandwich-type arsenotungstates [H2dap]6H8[Ni4(H2O)2(B-α-AsW9O34)2]2 · 33H2O (1) and {[Ni(dap)2(H2O)]2[Ni(dap)2]2[Ni4(Hdap)2(B-α-AsW9O34)2]} · 4H2O (2) (dap = 1,2-diaminopropane) have been hydrothermally synthesized by reaction of Na8[A-α-HAsW9O34] · 11H2O with NiCl2 · 6H2O in the presence of 1,2-diaminopropane and characterized by elemental analysis, IR spectra, X-ray single-crystal diffraction, and thermogravimetric analysis. 1 crystallizes in the triclinic P 1 space group with a = 16.351(6) Å, b = 16.423(6) Å, c = 19.894(7) Å, α = 110.630(6)°, β = 92.684(7)°, γ =104.946(7)°, V = 4774(3) Å3, Z = 1, GOOF = 1.033, R 1 = 0.0517, wR 2 = 0.1086. 2 also crystallizes in the triclinic P 1 space group with a = 13.305(4) Å, b = 13.882(4) Å, c = 17.031(5) Å, α = 68.109(5)°, β = 71.511(4)°, γ = 88.407(5)°, V = 2753.5(14) Å3, Z = 1, GOOF = 1.051, R 1 = 0.0491, wR 2 = 0.1150. Notably, 1 is a discrete structure, composed of two tetra-NiII substituted sandwich-type polyoxoanions [Ni4(H2O)2(B-α-AsW9O34)2]10− with different spatial orientation, whereas 2 displays a organic–inorganic composite 2-D sheet architecture constructed by tetra-NiII sandwiched [Ni4(H2O)2(B-α-AsW9O34)2]10− units by means of [Ni(dap)2]2+ bridges. Some previously reported transition-metal-substituted sandwich-type polyoxotungstates have been summarized.
Acknowledgements
This work was supported by the Natural Science Foundation of Henan Province (No. 092300410119), the Natural Science Foundation of Henan University (No. 2008YBZR010), the Postdoctoral Science Foundation of Henan University (No. BH2010003), the Foundation of Education Department of Henan Province (No. 2009A150003, 2010B150006), and Students Innovative Pilot Plan of Henan University (No. 09NB005).