4,4′-联吡啶桥联Ni、Co三维配合物的合成与结构

SYNTHESES AND CRYSTAL STRUCTURES OF THE 4,4′-BIPYRIDINE BRIDGED Ni, Co 3-D COMPLEXES

由 Ni( Cl O4) 2 · 6H2 O和 Co( Cl O4) 2 · 6H2 O分别与 4 ,4′-联吡啶、1 ,4 ,7-三氮杂环壬烷 ( tacn)反应 ,得到两种配合物 [Ni( 4,4′-bpy) 3( H2 O) 2 ]( 4,4′-bpy) ( OH) ( CH3OH) ( Cl O4) ( 1 )与 [Co( 4,4′-bpy) 3( H2 O) 2 ]( 4,4′-bpy) ( OH)( CH3OH) 2 ( Cl O4) ( 2 ) ( 4,4′-bpy:4 ,4′-联吡啶 ) ,并进行了元素分析、红外光谱、X射线单晶衍射等表征 .单晶结构数据表明 ,晶体 ( 1 )属于单斜晶系 ,空间群为 C2 /c,a=1 .7990 ( 9) nm,b=1 .1 4 2 ( 6) nm,c=2 .4 433( 1 2 ) nm,β=91 .936( 1 0 )°,V=5 .0 1 7nm3,Z=4 ,该配合物由 4 ,4′-联吡啶桥联过渡金属形成一维链状结构 .单齿配位的吡啶环上的未配位氮原子与配位水形成了氢键 ,将链连接成二维铁轨型结构 .此结构再通过未配位 4 ,4′-联吡啶、配位水、氢氧根之间形成的氢键而连接成三维网状结构 .未配位的 4 ,4′-联吡啶、甲醇、氢氧根离子、高氯酸根离子被包合在这种网络中 ,展示出一定的包合现象 .此外 ,未配位的 4 ,4′-联吡啶的吡啶环与配位的 4 ,4′-联吡啶的吡啶环之间存在 π-π相互作用 .晶体 ( 2 )与晶体 ( 1 )有相同的结构特性 ,晶体也属于单斜晶系 ,空间群为 C2 /c,a=1 .790 1( 1 7) nm,b=1 .1 5 0 7( 1 1 ) nm,c=2 .

Reactions of Ni(ClO 4) 2·6H 2O and Co(ClO 4) 2·6H 2O with 4,4′ bipyridine and 1,4,7 triazacyclononane gave two complexes [Ni(4,4′ bpy) 3(H 2O) 2](4,4′ bpy)(OH)(CH 3OH)(ClO 4)(1) and [Co(4,4′ bpy) 3(H 2O) 2](4,4′ bpy)(OH)(CH 3OH) 2(ClO 4)(2)(4,4′ bpy:4,4′ bipyridine), respectively, which were characterized by elemental analysis, IR spectroscopy and X ray diffraction. The crystal data showed that complex 1 crystallizes in monoclinic, space group C2/c with a =1.7990(9)nm, b =1.1421(6)nm, c =2.4433(12)nm, β =91.936(10)°, V =5.017nm 3, Z =4. An infinite 1 D chain structure of the complex was built by coordination of nickel to 4,4′ bpy. The 1 D chain formed 2 D roadlike network structure with the assistance of hydrogen bonds between the nitrogen atoms of the monodentate coordinated 4,4′ bpy and H 2O. The 2 D structure was also extended into 3 D network by uncoordinated 4,4′ bpy?H 2O and hydroxyl anion via hydrogen bonds. All the uncoordinated 4,4′ bpy, methanol, hydroxyl anion and perchlorate anion are clathrated in the network, exhibiting a certain inclusion phenomenon. Furthermore, the π π interaction existed between uncoordinated 4,4′ bpy and coordinated 4,4′ bpy. Complex 2 had the same structure feature which crystallizes in monoclinic, space group C2/c with a =1.7901(17)nm, b =1.1507(11)nm, c =2.442(2)nm, β =91.68(2)°, V =5.029(8)nm 3, Z =4.$$$$