化学学报 ›› 2004, Vol. 62 ›› Issue (13): 1222-1225. 上一篇    下一篇

研究论文

新型杂多阴离子[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-的结构及表征

刘斌1, 薛岗林1,2, 胡怀明1, 王兰英1, 史启祯1, 郑丽敏2, 忻新泉2, 王继武3   

  1. 1. 西北大学化学系, 陕西省物理无机化学重点实验室, 西安, 710069;
    2. 南京大学国家配位化学重点实验室, 南京, 210093;
    3. 延安大学化学化工学院, 陕西省化学反应工程重点实验室, 延安, 716000
  • 投稿日期:2003-10-31 修回日期:2004-01-08 发布日期:2014-02-17
  • 通讯作者: 薛岗林,E-mail:xglin707@163.com E-mail:xglin707@163.com
  • 基金资助:
    高等学校重点实验室访问学者基金和陕西省自然科学基金(No.2003B01)资助项目.

Structure and Characterization of a Novel Heteropolyoxoanion[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-

LIU Bin1, XUE Gang-Lin1,2, HU Huai-Ming1, WANG Lan-Ying1, SHI Qi-Zhen1, ZHENG Li-Min2, XIN Xin-Quan2, WANG Ji-Wu3   

  1. 1. Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Department of Chemistry, Northwest University, Xi'an 710069;
    2. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093;
    3. Department of Chemistry and Chemical Engineering, Yan'an University, Yan'an 716000
  • Received:2003-10-31 Revised:2004-01-08 Published:2014-02-17

在pH=4.5的水溶液中,Na27[NaAs4W40O140]·60H2O与NiCl2·6H2O,NaVO3·4H2O和NH4Cl反应得到了不同过渡金属离子占据S2位的新型杂多钨酸盐(NH4)21[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]·53H2O,用X射线单晶衍射法和元素分析确定了其结构.晶胞参数为:a=2.3305(14) nm,b=2.9467(19) nm,c=1.2671(16) nm,V=8.701(9) nm3,Z=2,空间群Pmmn.在杂多阴离子[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-中,配体{As4W40}的1个中心位和4个S2位可以选择性地被不同的金属离子所占据,其中相对的2个S2位被Ni2+和V5+统计性地占据,每种离子占据的概率为50%;{As4W40}中的另2个S2位分别被2个Na+占据,2个Na+间通过一配位水分子桥连.讨论了标题化合物的IR,TG和磁学性质.

关键词: 杂多钨酸盐, 晶体结构, 钨, 砷,

A novel large polyoxometalate (NH4)21[{Na2(H2O)3}Ni(H2O)VOAs4W140]·53H2O was synthesized by the reaction of Na27[NaAs4W40O140]·60H2O with NiCl 2·6H2O, NaVO3·4H2O and NH4Cl in pH=4.5 aqueous solution.Its structure was determined by single crystal X-ray diffraction.Crystal data for the titled compound are: orthogonal system, Pmmn space group, a=2.3305(14) nm, b=2.9467(19) nm, c=1.2671(16) nm, V=8.701(9) nm3, Z=2, Dc=4.378 g/cm3, μ=27.372 mm-1, R1=0.0596, wR2=0.1056 .The opposite two of four S2 sites of the big cyclic ligand [As4W40O140]28- are disorderly occupied by one V5+ and one Ni2+ with the probability that each transition metal ion occupies the same S2 site being 50%, and the other two S2 sites are occupied by two Na+ which are bridged by a water molecule.IR spectra, TG and magnetic properties of the compound were also discussed.

Key words: polyoxometalate, crystal structure, tungsten, arsenic, vanadium