新型四胺大环锌（Ⅱ）配合物的晶体结构

Crystal Structure of the Zinc(Ⅱ) Complex of a New Macrocyclic Tetraamine Ligand Bearing Four 2-MethylPyridyl Groups

１，４，７，１０－四氮杂环十二烷（ｃｙｃｌｅｎ）与２－氯甲基吡啶反应获得新型八齿配体１，４，７，１０－四（２－甲基吡啶基）－１，４，７，１０－四氮杂环十二烷（Ｌ）。该配体与Ｚｎ（ＣｌＯ＿４）＿２在水溶液中反应生成无色晶体ＺｎＬ（ＣｌＯ＿４）＿２（１）。晶体结构测定表明：化合物１，Ｃ＿３２Ｈ＿４０－Ｃｌ＿２Ｎ＿８Ｏ＿８Ｚｎ，属单斜晶系，空间群Ｐ２＿１／ｃ，α＝９．８２２（５），ｂ＝１０．７２１（３），ｃ＝３３．９００（２）Ａ，β＝９０．５４（４）°，Ｖ＝３５７０（４）Ａ３，Ｄ＿ｃ＝１．４９ｇ／ｃｍ￣３，Ｚ＝４，Ｆ（０００）＝１６６４，Ｍｒ＝８０１．０。１８８８个可观测衍射点参与修正，Ｒ＝０．０６９，Ｒｗ＝０．０７２。在化合物１中，Ｚｎ原子采取六配位的变形八面体构型，在４个吡啶侧臂之中，只有相对的两个参与配位，而另外的两个有一个远离配位中心，另一个吡啶上的氮原子与锌原子之间存在因二级化学键而引起的弱相互作用。

A novel macrocyclic tetraamine ligand functionalized with four 2-methyl pyridyl groups ,1,4, 7, 10-tetrakis (2-methylpyridyl)-1, 4, 7,10-tetraazacyclododecane (L) , has been synthesized and characterized. The zinc(Ⅱ) complex of this octadentate ligand has been prepared and isolated as single crystal.The structure of complex ZnL (ClO_4)_2 (1) was determined by X-ray crystal diffraction method. The crystal of 1, C_32H_40Cl_2N_8O_8Zn , belongs to monoclinic system, space group P2_1/c ,α=9. 822(5), b=10. 721(3) , c=33. 900(1) A, β=90. 54(4)°, V=3570(4) A￣3, D_c=1. 49g/cm￣3, Z=4, F(000)= 1664,M_r= 801. 0. The final R(R_w) is 0. 069(0. 072) for 1888 observed reflections (I≤3σ(I)). In complex 1, zinc(Ⅱ) is six-coordinated with N(1) , N(2) , N (3) , N(4) of the four nitrogens of cyclen and N (11) , N (21) of two pendant pyridyl. to form a distorted octahedral configuration. Only two of the four pendant pyridyl groups are coordinated to Zn(Ⅱ).