具有一维钼-氧螺旋链的[Mo_3O_9(2,2-bpy)_2]_∞的水热合成和晶体结构  

Hydrothermal Synthesis and Crystal Structure of [Mo_3O_9(2,2-bpy)_2]_∞ with One-dimensional Molybdenum-Oxygen Helix

作　　者：岳斌[1] 许静玉[1] 江磊[1] 金松林[1] 谢高阳 陈民勤 

机构地区：[1]复旦大学化学系,上海200433 [2]复旦大学分析测试中心,上海200433

出　　处：《复旦学报（自然科学版）》2002年第4期399-404,共6页Journal of Fudan University：Natural Science

基　　金：国家自然科学基金资助项目 (2 99710 0 72 0 1710 13)

摘　　要：以MoO3 、2 ,2’ 联二吡啶和Ru(DMSO) 4 Cl2 为原料 ,在 2 0 0℃下水热反应 12 0h ,得到蓝色晶体 ,经X 单晶衍射测定 ,晶体属单斜晶系 ,P2 1/n空间群 ,a =1.35 2 9(5 )nm ,b =1.0 12 0 (2 )nm ,c =1.7819(7)nm ,β =10 4 .77(3)° ,V =2 .35 90 (14 )nm3 ,MR =74 4 .15 ,Z =4 ,dc=2 .0 95 (g·cm-3 ) ,F(0 0 0 ) =14 4 8,μ =1.6 30mm-1,用 36 6 8个独立衍射精修结构 ,最终偏离因子R =0 .0 2 86 ,Rw=0 .0 779.结构单元中有 3种Mo原子 ,2个六配位的钼与 1个四配位的钼通过共角桥氧交替联结形成一维无限螺旋链 .六配位的钼除 2个桥氧、2个端氧外 ,还与 2 ,2’ 联二吡啶的 2个N配位 ,同时端氧还与联二吡啶α 碳上的氢形成C—H…O氢键 ;四配位的钼则与 2个桥氧和 2个端氧配位 .相邻链之间存在复杂的氢键网络 。The hydrothermal reaction of MoO 3, 2,2' bipyridine, Ru(DMSO) 4Cl 2 and H 2O at 200 ℃ for 120 h produced blue crystals. The crystal structure was determined by single crystal X ray diffraction, which was in monoclinic system with space group P2 1/ n . The unit cell parameters are as follows: a =1.352 9(5) nm, b =1.012 0(2) nm, c =1.781 9(7) nm, β =104.77(3)°, V =2.359 0(14) nm 3, M R=744.15, Z =4, d c =2.095 g·cm -3 , F (000)=144 8, μ =1.630 mm -1 , structure solution and refinement based on 3668 reflections converged at R =0.028 6, and R w =0.077 9. In the structure unit, there are three kinds of Mo atom, two of them are 6 coordinated and one, 4 coordinated. Through corner sharing bridge oxygen, they link together alternatively, forming one dimensional infinite helical chain. Besides two bridge oxygen and two end oxygen, the 6 coordinated Mo coordinates with the two nitrogen atoms of 2,2' bipynidine; at the same time, the end oxygen also form hydrogen bond C-H...O with the hydrogen on α carbon of bipyridine. The 4 coordinated Mo coordinates with two bridge oxygen and two end oxygen. The complicated hydrogen bond framework exists within the Mo -O chain and among the chains, which constructs the three dimensional structure.

关 键 词：一维螺旋链 钼-氧簇化合物 2 2'-联二吡啶 水热合成 单晶结构 

分 类 号：O614[理学—无机化学]