A new complex constructed from a unit with two As3O6 rings capping Anderson-type moieties,[Ni（en）2（H2O）2]2[（NiO6）Mo6O18（As3O3）2]·2H2O（1,en = ethylenediamine）,has been hydrothermally synthesized and characterized by IR,single-crystal X-ray diffraction and thermogra-vimetric analysis.The compound crystallizes in triclinic,space group P1 with a = 9.1230（16）,b = 11.8078（9）,c = 12.2111（9） ,α = 114.5210（10）,β = 98.0350（10）,γ = 100.0320（10）o,Mr = 2029.80,C8H44As6Mo6N8Ni3O36,V = 1145.0（2） 3,Dc = 2.944 g/cm3,Z = 1,GOF = 0.997,μ = 7.203 mm-1,F（000） = 970,R = 0.0352 and wR = 0.1019.Compound 1 consists of an Anderson-type capped by a two-ring（As3O6） unit [（NiO6）Mo6O18（As3O3）2]4-,two six-coordinate [Ni（en）2（H2O）2]2＋ cations and two water molecules.
The polyoxoanion incorporated {Mn（CO）3^＋} complex, （n-Bu4N）2[Mo6O16（OCH3）2{HOCH2C（CH2O）3}2·{Mn（CO）3}2]（1）, has been synthesized by the reaction of （n-Bu4N）4[Mo8O26] with Mn（CO）5Br in methanol, in the presence of C（CH2OH）4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1：C25H48MnMo3NO16 （1）, Triclinic Pi, a=0.9405（3） nm, b=1.3351（4） nm, c=1.5455（4） nm, α=103.206（5）°, β=102.165（5）°, γ=100.784（5）°, V=1.7896（9） nm^3, Z=2, R1=0.0703, wR2= 0.1495. The structure analysis of complex 1 shows that the complex consists of two tetrabutylammonium cations and a polyoxomolybdate anion that incorporates two fac-Mn（CO）3^＋ units. The anion of complex 1 can be considered as the dimer of two rhomb-like anions by sharing of two comers.
AID zigzag polyoxometalate [（CH3）4N]1.50H3.50[Gd（GeW11O39）（H2O）2]·2.5H2O （1） was synthesized by reaction of the monova- cant polyanion [α-GeW11O39]^8- with Gd^3＋ ions in aqueous solution and characterized by IR, UV spectra, ICP, and X-ray crystallography. X-ray single-crystal structural analysis indicated that the title compound crystallized in a monoclinic lattice, C2/c space group with α= 2.8201（5）, b=2.2885（3）, c=2.4033（4） nm, β=123.875 （2）°, V=12.878（4） nm3, Z=8, R1=0.0623, wR2=0.1287. The solid-state structure of the title compound displayed an infinite one-dimensional arrangement built up of [α-GeW11O39]^8- polyanions connected by Gd^Ⅲ cations.
