一种包含二核镍簇和四核镍簇的有机-无机复合的新型砷钨酸盐(enH_2)_3[Ni_2(H_2O)_10][Ni_4(H_2O)_2(α-As~VW_9O_(34))_2]·en·8H_2O

在水热条件下,利用三缺位Keggin多钨氧酸盐前驱体Na_8α-HAs~VW_9O_(34)]·11H_2O与NiCl_2·6H_2O、乙二胺反应,合成了一种包含二核镍簇和四核镍簇的有机-无机复合的新型砷钨酸盐(enH_2)_3Ni_2(H_2O)_(10)]Ni_4(H_2O)_2(α-As~VW_9O_(34))_2]·en·8H_2O,并经IR光谱、元素分析、热重分析和X射线单晶衍射等测试手段进行了表征.标题化合物属于三斜晶系,P-1空间群,晶胞参数:α=1.204 23(19),b=1.258 5(2),c=1.593 8(4) nm,α=97.472(3),β=108.229(3),γ=114.779(2)°,V=1.985 2(7) nm~3,Z=1,D_c=4.589g/cm3,GOOF=1.023,R_1=0.044 3,wR_2=0.113 8.X-射线单晶结构分析表明,标题化合物分子由3个质子化乙二胺阳离子enH_2]~(2+)、1个二核镍簇阳离子Ni_2(H_2O)_(10)]~(4+)、1个四核镍簇取代的夹心型多阴离子Ni_4(H_2O)_2(α -As~VW_9O_(34))_2]~(10-)、1个游离的乙二胺分子和8个结晶水分子组成.

An Organic-Inorganic Composite Novel Arsenotungstate Containing Di-/Tetra-Nuclear Nickel Clusters (enH_2)_3[Ni_2(H_2O)_(10)][Ni_4(H_2O)_2(α-As~VW_9O_(34))_2]·en·8H_2O

An organic-inorganic composite novel arsenotungstate containing diVtetra-nuclear nickel clusters(enH2 )3 Ni_2 (H_2O)_(10)] Ni_4 (H_2O)_2 (a-As~vW_9O_(34) )_2 ]·en ·8H_2O is synthesized by reaction of trivacant Keggin polyoxotungstate precursor Na_8 rHAs_v W_9O_(34) ]·11H_2O·NiCl_2 ·6H_2O and ethylenediamine (en) under hydrothermal conditions and characterized by IR spectrum, elemental analysis, thermogravimetric analysis and X-ray single-crystal diffraction. The title compound crystallizes in the triclinic space group P-1 with α= 1. 204 23(19) , b= 1.258 5(2),c=1.593 8(4) nm, α=97.472(3),β= 108. 229(3), γ= 114. 779(2),V = 1. 985 2(7) nm~3,Z=l,D_c= 4.589 g/cm~3, GOOF= 1. 023,R_1 =0.044 3, wR_2 =0.1138. X-ray single-crystal structural analysis indicates that the title compound consists of 3 diprotonated enH_2]~(2+) cations, 1 di-nickel cluster cation Ni_2 (H_2O)_(10)]~(4+) , 1 tetra-nickel substituted sandwich-type polyoxoanion Ni_4 (H_2O)_2 (a -As~vW_9O_(34) )_2]~(10-) , 1 free en molecule and 8 crystal water molecules.