双核钒希夫碱配合物[VO(μ_2-OCH_3)(salen)]_2的合成、表征及晶体结构

Synthesis, Characterization and Crystal Structure of Binuclear Vanadium Schiff Base Complex[VO(μ_2-OCH_3)(salen)]_2

用水热 (溶剂热 )法合成了新型双核钒 (Ⅳ )配合物 [VO( μ2 OCH3 ) (salen) ]2 (salen为希夫碱水杨醛单缩乙二胺 ) ,其结构经元素分析、IR ,X 射线衍射等表征。X 射线单晶衍射结果表明该配合物属于三斜晶系 ,空间群P 1。晶胞参数 :a =6.83 1 8( 1 5 ) ,b=7.80 2 3 ( 1 0 ) ,c=1 1 .1 695 ( 1 7) ,α=71 .71 ( 7) ,β =74.81 7( 4 ) ,γ =80 .3 5 8( 5 )°,V =5 43 .2 1 ( 1 6) 3 ,R1=0 .1 3 3 5 ,wR2 =0 .3 61 0 [I>2σ(I) ],Z =1 ,Dc=1 .5 97mg·m-3 ,μ =0 .90 6mm-1,F( 0 0 0 ) =2 70 ,S =1 .1 63。中心钒 (Ⅳ )原子采取六配位的变形八面体构型 ,V(Ⅳ )与V(Ⅳ )原子之间通过甲氧基中的氧原子桥联形成二聚体。V(Ⅳ )与salen上氨基氮和亚氨氮两个氮原子配位形成稳定的五元螯合环 ,同时V(Ⅳ )和salen中的羟基氧原子配位形成另一稳定的共边六元螯合环。

A new binuclear vanadium(IV) complex｛[VO(μ 2-OCH 3)(salen)] 2 , Schiff base ligand (salen) derived from salicylaldehyde and ethylenediamine｝ has been hydro(solv)thermally synthesized and characterized by elemental analysis, IR spectroscopy and X-ray diffraction. Single crystal X-ray analysis indicates that the complex crystallizes in triclinic system, space group P-1 with parameters: a=6.8318(15), b=7.8023(10), c=11.1695(17), α=71.71(7), β=74.817(4), γ =80.358(5)°, V=543.21(16)  3, R 1=0.1335, wR 2=0.3610[I> 2σ(I)], Z=1, Dc = 1.597mg·m -3 , μ=0.906mm -1 , F(000) =270, S=1.163. The central metal vanadium(Ⅳ) adopts six-coordinated distorted octahedral geometry, in which a dimeric structure is formed through O atom from two methoxy groups bridging two vanadium(Ⅳ) atoms.Simultaneously, the N atoms of the amino and imine from salen coordinate to V(Ⅳ) ion to form a stable five-membered ring, and the O atom of the hydroxy from salen ligand contacts the V(Ⅳ) ion too, which forms another stable co-edged six-numbered chelate ring.