三元配合物[Cu(hmta){SSP(OC_6H_(11))_2}_2]的合成、谱学性质与晶体结构  

Synthesis,spectroscopic properties and crystal structure of ternary complex [Cu(hmta)·｛SSP(C_6H_(11))_2｝_2]

作　　者：谢斌[1] 邹立科[1] 毛治华[2] 洪洲[2] 

机构地区：[1]四川理工学院化学系,四川自贡643033 [2]四川大学分析测试中心,四川成都610064

出　　处：《化学研究与应用》2005年第2期172-175,共4页Chemical Research and Application

摘　　要：合成了含饱和四氮杂大环hmta(hmate =meso 5 ,7,7,12 ,14 ,14 六甲基1,4 ,8,11 四氮杂环十四烷)和O ,O 二环己基二硫代磷酸的铜(Ⅱ)的三元配合物[Cu(hmta) {SSP(OC6H11) 2 } 2 ],通过元素分析、摩尔电导、红外光谱、1H核磁共振谱和电子光谱对其进行了表征,并用单晶X ray衍射法测定了它的晶体结构。配合物属三斜晶系,空间群为P - 1,晶胞参数为:a =8 174 ( 2 ) ,b =10 381( 3) ,c =15 4 19( 3) ,α=10 1 5 9( 2 )°,β=93 34( 2 )°,γ=10 3 76 ( 2 )°,V =12 37 3( 6 ) 3 ,Z =2 ,Dc =1 2 19mg/cm3 ,F( 0 0 0 ) =4 77,μ(MoKα) =0 714mm-1,最终偏离因子(I>2σ(Ⅰ) )R =0 0 382 ,wR =0 0 991,相应的可观测反射数为2 76 3。测定结果表明:配合物中的配体(C6H11) 2 PSS-为单齿配体,金属铜离子与(C6H11) 2 PSS-的S( 2 )原子和hmta的N原子形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性;同时晶胞中配合物的两配体之间形成了两种N -H…We reported the synthesis of ternary complex [Cu(hmta)·｛SSP(C_6H_(11))_2｝_2](where hmta is meso-(5,7,7,12,14,14-hexamethyl-1,4,,8,11-tetraazacyclotetradecane),and,group C_6H_(11)-is cyclohexyl).The complex was characterized by elemental analysis,molar conductivity,IR spectra,electronic spectra and ()~1HNMR spectra,and its crystal structure was determined by single-crystal X-ray diffraction method.The complex belongs to triclinic system,space group P-1 with the following crystallographic parameters:a=8.174(2)?,b=10.381(3)?,c=15.419(3)?,α=101.59(2)°,β=93.34(2)°,γ=103.76(2)°,V=1237.3(6)?~3,Z=2,Dc=1.219mg/cm^3,F(000)=477,μ(MoKα)=7.14cm^(-1),S=1.035,(△/σ)_(max)=0.000,and final R=0.0382,wR=0.0991 for 2763 observed reflections (I>2σ(Ⅰ)).The analytical results of crystal structure and spectroscopic properties show that the ligand (C_6H_(11))_2PSS^-is monodentate ligand which coordinates to copper ion,and copper ion has a formal six-coordination number.The complex exists as a centrosymmetric lengthened octahedron geometry.There are two N-H…S hydrogen bonds between tetraazamacrocycle hmta and (C_6H_(11)O)_2PSS^-ligands in the complex.

关 键 词：四氮杂大环 O O’-二环己基二硫代磷酸 三元配合物 晶体结构 

分 类 号：O614[理学—无机化学] O627[理学—化学]