二{氧桥-二[N,N-二甲基(或乙基)氨荒酸基乙酸二丁基锡(Ⅳ)]}的合成及结构  

Synthesis and Crystal Structure of Bis{oxo-bis[N,N-dimethylthiocarbamoylthioacetatodi-n-butyltin(Ⅳ)]} and Bis{oxo-bis[N,N-diethylthiocarbamoylthioacetato Di-n-butyltin(Ⅳ)]}

作　　者：尹汉东[1] 薛绳才[1] 刘国富[2] YIN Han-Dong;XUE Sheng-Cai;LIU Guo-Fu(College of Chemistry and Chemical Engineering,Liaocheng University.Liaocheng 252059;Department of Biology,Liaocheng University.Liaocheng 252059)

机构地区：[1]聊城大学化学化工学院,聊城252059 [2]聊城大学化学化工学院生物系,聊城252059

出　　处：《化学学报》2004年第6期603-609,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20271025);山东省自然科学基金(No.L2003B01)资助项目

摘　　要：利用二丁基氧化锡与N,N二甲基氨荒酸基乙酸以及N,N二乙基氨荒酸基乙酸反应,合成了二聚体有机锡化合物{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NMe_(2))]_(2)O}_(2)(1)和{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NEt_(2))]_(2)O}_(2)(2).通过元素分析,红外光谱及核磁共振谱对它们进行了表征.并用X射线单晶衍射法测定了这两个化合物的晶体结构,结果表明:1为单斜晶系,C2/m空间群,晶胞参数为:a=13584(5)nm,b=19242(7)nm,c=14640(5)nm,β=102505(5)°,Z=2,V=3736(2)nm^(3),μ=1490g/cm3,F(000)=1704,R_(1)=00492,wR_(2)=01159.2为三斜晶系,P1—空间群,晶胞参数为:a=11960(14)nm,b=13612(16)nm,c=13684(16)nm,α=90969(18)°,β=105241(17)°,γ=103954(16)°,Z=1,V=2078(4)nm^(3),μ=1429g/cm^(3),F(000)=916,R_(1)=00459,wR_(2)=00957.它们都是以Sn_(2)O_(2)四元环为中心对称的二聚体结构.但锡原子的配位方式不同,在1中,内外环锡原子均为五配位的畸变三角双锥构型;而在2中,内环锡原子为五配位的畸变三角双锥构型,而外环锡原子为六配位的加帽三角双锥构型.Two organotin compounds{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NMe_(2))]_(2)O}_(2)(1)and{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NEt_(2))]_(2)O}_(2)(2)were synthesized by the reaction of n-dibutyltin oxide with N,N-dimethylthiocarbamoylthioacetic acid and N,N-diethylthiocarbamoylthioacetic acid in 1∶1 molar ratio,respectively.They were characterized by elemental analysis,IR,1H and 119Sn NMR spectra and X-ray single crystal diffraction.The results showed that the compound 1 belongs to a monoclinic system with space group C2/m,and unit cell dimensions:a=1.3584(5)nm,b=1.9242(7)nm,c=1.4640(5)nm,β=102.505(5)°,Z=2,V=3.7362(2)nm^(3),μ=1.490 g/cm^(3),F(000)=1704,R_(1)=0.0492,wR_(2)=0.1159.The compound 2 belongs to a triclinic system with space group P1—,and unit cell dimensions:a=1.1960(14)nm,b=1.3612(16)nm,c=1.3684(16)nm,α=90.969(18)°,β=105.241(17)°,γ=103.954(16)°,Z=1,V=2.078(4)nm^(3),μ=1.429 g/cm^(3),F(000)=916,R_(1)=0.0459,wR_(2)=0.0957.The two compounds belong to centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn 2O 2 unit in which the bridging oxygen atoms are tri-coordinated.Each bridging oxygen atom also connects with an exo-cyclic tin atom.In the compound 1,the endo-and exo-cyclic tin atoms are all five-coordinated and have coordination geometry of distorted trigonal bipyramid.In the compound 2 the endo-cyclic tin atoms are five-coordinated and the exo-cyclic tin atoms are six-coordinated,and the two kinds of tin atoms have coordination geometry of distorted trigonal bipyramid and monocapped trigonal bipyramid respectively.

关 键 词：有机锡化合物 氨荒酸基乙酸 合成 晶体结构 

分 类 号：O627[理学—有机化学]