以钒为杂原子的Keggin结构阴离子有机-无机复合物[Co(phen)_3]_4[VW_(12)O_(40)](OH)_5的合成及晶体结构

An Organic-inorganic Keggin-type Polyoxometalate with Vanadium Atom as Heteroatom——Synthesis and Crystal Structure of [Co(phen)_3]_4[VW_(12)O_(40)](OH)_5

以NH4VO3、Na2WO4.2H2O、CoCl2.2H2O、C12H8N2.H2O(邻菲啰啉,phen)为原料,用水热合成法制得了分子式为[Co(phen)3]4[VW12O40](OH)5的有机-无机复合物,并对其进行了元素分析、IR及X射线单晶衍射等表征。结构测定表明,该化合物属于三斜晶系,P墿空间群,晶胞参数:a=1.638 9(3)nm,b=1.774 4(4)nm,c=18.275(4)nm,α=61.04(3)°,β=78.49(3)°,γ=64.64(3)°,V=4.201 8(15)nm3,Z=1,R1=0.083 6,wR2=0.222 8。标题化合物分子是由4个手性的[Co(phen)3]2+配阳离子,1个[VW12O40]3-阴离子及5个游离的OH-组成。4个[Co(phen)3]2+配阳离子通过静电引力呈平行四边形分布在[VW12O40]3-阴离子的周围,[VW12O40]3-阴离子位于平行四边形的中心。化合物分子间通过π-π堆积等作用形成三维网状结构。

An organic-inorganic complex [Co（phen）3]4[VW12O40]（OH）5 was synthesized from NH4VO3, Na2WO4.2H2O, CoCl2 2H2O, C12H8N2 H2O（phenanthroline） by hydrothermal method and characterized by elemental analysis, IR and X-ray diffraction. The X-ray crystallography indicates that the title compound crystallized in a triclinic lattice, P1 space group, with a=1.6389（3）nm,b=1.7744（4）nm,c=18.275（4）nm,α=61.04（3）°,β=78.49（3）°,γ=64.64（3）°,V=4.2018（15）nm^3,Z=1,R1=0.0836,ωR2=0.2228. Structural analysis reveals that the molecule of the title compound is composed of four chiral [Co（phen）3]^2＋ coordination cations, one independent [VW12O40]^3- anion and five dissociative OH-anions. The four coordination cations are located around the anion parallelogram-symmetrically by interaction of electrostatic force and the [VW12O40]^3- anion is located in the center of the parallelogram. The molecules form a 3D network structure through π-π stacking interaction.