N-对R苯基氮杂15冠5八钼多酸钠超分子配合物的合成与结构  

Synthesis and Crystal Structure of {Na[N-(p-RPh)15C5](Et_2O)}_2Na_2Mo_8O_(26)

作　　者：鲁晓明[1] 刘顺诚[1] 刘育[2] 卜显和[2] 洪少良 

机构地区：[1]首都师范大学化学系,北京100037 [2]南开大学化学系,天津300071 [3]北京微量化学所,北京100091

出　　处：《化学学报》1997年第10期1009-1018,共10页Acta Chimica Sinica

基　　金：北京市教委基金资助

摘　　要：为研究大环化合物对客体分子的选择性,合成了通式为[NaL(Et_2O)]_2Na_2Mo_8O_(26)的三种新型N-对R苯基氮杂15冠5八钼多酸钠超分子配合物(其中L分别为:N-苯基氮杂15冠5、N-对氯苯基氮杂15冠5和N-对甲苯基氮杂15冠5),进行了元素分析,红外光谱与核磁共振等结构参数的表征,对R基为CH_3的标题配合物作了X射线四圆衍射测定,该晶体属单斜晶系,空间群为P2_1/α,α=1.4590(4)nm,b=1.3817(3)nm,c=1.7639(5)nm,β=112.67(2)°,Ⅴ=3.281(1)nm^3,M_r=2021.3,D_c=2.11g/cm^3, μ=2.37mm,F(000)=2048,R=0.045和R_w=0.057.与[Na·(DB18C6)(CH_3OH)]_2M_6O_(19)和[Na(DB24C8)]_2M_6O_(19)进行比较,结果表明:大环化合物不仅对客体金属离子有分子识别性,而且对与之抗衡的多酸阴离子上具有影响.Three new supermolecular complexes of {Na [ N - ( p - RPh ) 15C5 ] (Et2O) )2Na2Mo8O26(R =H,Cl,CH3) were synthesized by reaction of N - (para- substituted phenyl) - aza - 15 - crown - 5 with [ ( n - Bu)4N]4Mo8O26, and Na+ in mixed solvent of CH3OH and CH3CN and crystallized in Et2O. The supermolecular complexes were characterized by C/H analysis, IR,and 1H NMR spectra and X- ray structure determination of {Na[N - (p- CH3Ph) 15C5](Et2O) }2Na2Mo8O26.This crown ether octamolybdate is monoclinic, space group P21/a ,a = 1.4590(4)nm,b=l.3817(3)nm, c = 1. 7639(5)nm,β = 112. 67(2)°, V = 3. 281 (1)nm3,Mr = 2021.3, Dc = 2. 11g/cm3, μ = 2.37mm-1, F(000) = 2048, R =0.045 and Rw = 0.057. Comparison with [ Na (DB18C6) (CH3OH)]2M6O19 and [Na (DB24C8)]2M6O19 (M = W and Mo) ,it was indicated that the host crown ether compounds could not only recongnize the guest -metal cations, but also choose counterion anions of polymolybdates with defferent degree of polymerization to combine into the crystals.

关 键 词：氮杂15冠5 八钼多酸钠 超分子配合物 大环 合成 

分 类 号：O614.112[理学—无机化学]