亚乙基硫脲配位聚合物[Cu3(etu)3 Br3]n的合成与晶体结构

CuB r2和亚乙基硫脲反应生成Cu(I)配位聚合物Cu3(etu)3B r3]n(etu=亚乙基硫脲),单晶X射线衍射测得该晶体为三斜晶系,Pī空间群.晶胞参数:a=0.762 46(6)nm,b=1.198 48(10)nm,c=1.224 52(7)nm,α=68.202(5),°β=74.607(6),°γ=87.652(7)°,V=0.999 61(13)nm3,Z=2,Mr=736.82,Dc=2.448 g.cm-3,μ=9.477 mm-1,F(000)=708,偏差因子R1=0.030 6,wR2=0.071 0.配合物由环状Cu(etu)B r]3单元聚合而成,形成Cu4S2B r2和Cu2S4B r2聚合体,两聚合体通过μ2-S桥键交替连接,形成平行于晶胞b轴的Cu3(μ3-etu)(μ2-etu)2(μ2-B r)2B r]n一维链.Cu(I)均为变形四面体配位,亚乙基硫脲以S原子与Cu(I)结合,形成μ2-S和μ3-S两种配位方式.

Synthesis and Crystal Structure of Coordination Polymer [ Cu3 (etu) 3 Br3 ] n

A copper(I) coordination polymer,Cu_(3)(etu)_(3)Br_(3)]_(n)(etu = ethylenethiourea),was synthesized by a reaction of CuBr_(2)with etu.It crystallizes in triclinic crystal system,space group Pī,with a= 0.762 46(6) nm,b= 1.198 48(10) nm,c= 1.224 52(7) nm,α = 68.202(5)°,β= 74.607(6)°,γ = 87.652(7)°,V = 0.999 61(13) nm~(3),Z= 2,M_(r)= 736.82,D_(c)=(2.448 )g·cm~(-3),μ=(9.477 mm~(-1)),F(000) = 708,R_(1)= 0.030 6,wR_(2)= 0.071 0.The crystal structure consists of self-assembled Cu_(4)S_(2)Br_(2) and Cu_(2)Br_(2) cores,which are alternately linked by two μ_(2)-S bridges to form Cu_(3)(μ_(3)-etu)(μ_(2)-etu)_(2)(μ_(2)-Br)_(2)Br]_(n) polymeric chains paralleling b axis.The three crystallographically independent copper(I) ions are in distorted tetrahedral coordination geometry.The etu ligands coordinated to Cu(I) through S atom with the coordination modes of μ_(2)-S and μ_(3)-S.