论文部分内容阅读
合成了通过N-N键桥联的不对称的N2O3席夫碱配体(H3L)的镍髤配合物[Ni2(HL)2]2(DMF)8(H2O)2(1)。配合物晶体属于三斜晶系,空间群为P1,a=1.2735(2)nm,b=1.3604(3)nm,c=1.4276(3)nm,α=85.358(4)°,β=63.513(3)°,γ=79.545(4)°,V=2.1768(7)nm3,Z=1,F(000)=980,R1=0.0736。配合物1的不对称单元中含有两个双核结构Ni2(HL)2(DMF)2(H2O)2(Ⅰ)和Ni2(HL)2(DMF)4(Ⅱ)以及两个DMF溶剂分子。通过酚基氧原子桥联的镍-镍距离分别为:Ni(1)-Ni(1A),0.3084nm;Ni(2)-Ni(2B),0.3103nm(对称操作:A:1-x,2-y,-z;B:1-x,1-y,1-z)。金属镍髤离子采取扭曲的八面体配位构型,一个配体的NO2三齿配位单元和另一个配体的酚基氧原子位于赤道面位置,两个溶剂分子占据轴向位置。晶体中存在着分子内以及分子与溶剂分子间的两种氢键作用。配合物1的变温磁化率测定表明,Ni髤离子之间的反铁磁耦合作用在它的磁性质中起主导作用。
Nickel complexes [Ni2 (HL) 2] 2 (DMF) 8 (H2O) 2 (1) were synthesized by N-N bond asymmetric N 2 O 3 Schiff base ligands (H3L). The complex crystal belongs to the triclinic system with space group P1, a = 1.2735 (2) nm, b = 1.3604 (3) nm, c = 1.4276 (3) nm, α = 85.358 (4) °, β = 63.513 3) °, γ = 79.545 (4) °, V = 2.1768 (7) nm3, Z = 1, F (000) = 980 and R1 = 0.0736. The asymmetric unit of complex 1 contains two dinuclear structures Ni2 (HL) 2 (DMF) 2 (H2O) 2 (Ⅰ) and Ni2 (HL) 2 (DMF) 4 (Ⅱ) and two DMF solvent molecules. Nickel-nickel distances bridged by a phenoxide atom are Ni (1) -Ni (1A), 0.3084 nm, Ni (2) -Ni (2B), 0.3103 nm 2-y, -z; B: 1-x, 1-y, 1-z). Metal nickel 髤 ions take a twisted octahedral coordination configuration, one ligand NO2 tridentate coordination unit and the other ligand phenolic oxygen atoms at the equatorial plane position, the two solvent molecules occupy the axial position. There are two kinds of intramolecular hydrogen bonds between molecules and solvent molecules in the crystal. The change of magnetic susceptibility of complex 1 shows that the antiferromagnetic coupling between Ni 髤 ions plays a dominant role in its magnetic properties.