化学学报 ›› 2004, Vol. 62 ›› Issue (13): 1260-1264. 上一篇    

研究论文

硝酸钍氧化膦取代杯芳烃配合物的合成与结构

赵明新1, 朱文祥1, 马淑兰1, 袁大强1, 王哲明2   

  1. 1. 北京师范大学化学系, 北京, 100875;
    2. 北京大学化学与分子工程学院, 稀土材料化学与应用国家实验室, 北京, 100871
  • 投稿日期:2003-10-13 修回日期:2004-03-05 发布日期:2014-02-17
  • 通讯作者: 朱文祥,E-mail:wx-zhu@263.net E-mail:wx-zhu@263.net

Synthesis and Crystal Structure of a Thorium(Ⅳ) Nitrate Complex with Phosphinoxide[-CH2P(O)Ph2]-substituted Calix[4]arene

ZHAO Ming-Xin1, ZHU Wen-Xiang1, MA Shu-Lan1, YUAN Da-Qiang1, WANG Zhe-Ming2   

  1. 1. Department of Chemistry, Beijing Normal University, Beijing 100875;
    2. State Key Laboratory of Rare Earth Materials Chemistry and Application, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
  • Received:2003-10-13 Revised:2004-03-05 Published:2014-02-17

合成了一种硝酸钍与氧化膦取代杯芳烃衍生物的配合物,[L·Th(OH2)(NO3)2][Th(NO3)6]·CH2CN {L=四(亚甲基二苯基氧化膦)杯[4]芳烃}.通过元素分析和红外光谱对配合物进行了表征.用X射线单晶衍射法测定了其晶体结构.晶体属三斜晶系,P1空间群,晶胞参数a=1.990(7) nm,b=2.217(8) nm,c=2.890(10) nm; α=104.92(12)°,β=100.76(14)°,γ=93.13(10)°,Z=4; V=12.033(7) nm3,R1=0.0901,wR2=0.1907.此配合物由配阳离子和配阴离子构成.配阳离子中,1个Th4+与杯芳烃中的4个磷氧键上的氧原子,2个双齿配位的硝酸根中的4个氧原子,以及1个水分子的氧原子配位,构成1个九配位的单帽四方反棱柱体;配阴离子中,1个Th4+与6个双齿配位的硝酸根离子配位.

关键词: 硝酸钍配合物, 氧化膦取代杯芳烃, 晶体结构

A thorium(Ⅳ) nitrate complex with phosphinoxide[-CH 2P(O)Ph2]-substituted calixarene [L·Th(OH2)(NO3) 2][Th(NO3) 6]·CH 3CN has been prepared and characterized by elemental analysis and IR spectroscopy.Its crystal structure was determined by X-ray diffraction method.It belongs to triclinic crystal system, space group P1, with a=1.990(7) nm, b=2.217(8) nm, c=2.890(10) nm; α=104.92(12)°, β=100.76(14)°, γ=93.13(10)°, Z=4, V=12.033(7) nm3, R1=0.0901, wR2=0.1907.The complex consists of a coordination cation and a coordination anion.In the cation the thorium(Ⅳ) is coordinated to the four phosphinoxide oxygen atoms of the calixarene, four oxygen atoms from two bidentate nitrate anions and one oxygen from a water molecule forming a nine-coordinate monocapped square antiprism.In the coordination anion, the thorium(Ⅳ) is coordinated to six bidentate nitrate.In addition, an acetonitrile molecule was encapsulated in the cavity of calixarene.

Key words: thorium(Ⅳ)nitrate complex, phosphinoxide[—CH2P(O)Ph2]-substituted calix[4]arene, crystal structure