单、双核镍(II)配合物的晶体结构、光谱和磁性

报道2个具有三足四齿配体,三(2-甲基吡啶)胺(缩写TPA)的单、双核镍(II)配合物。X射线晶体结构分析结果表明,双核镍配合物(1)晶体(C~3~6H~3~6N~8Ni~2Cl~2).11/6(ClO~4).1/6(OH).8/6(H~2O)属三方晶系,空间群为R-3,a=2.8425(4)nm,b=2.8425(4)nm,c=1.4385(5)nm,α=β=90.00ⅲ,γ=120.00ⅲ,Z=18,最终因子R=0.078,Rw=0.078。单核配合物晶体C~2~0H~1~8N~6NiS~2.0.5(H~2O),属三斜晶系,空间群P1,a=0.9467(1)nm,b=1.5566(3)nm,c=1.5913(3)nm,α=73.59(4)ⅲ,β=87.37(3)ⅲ,γ=76.27(2)ⅲ,Z=4,最终因子R=0.0784,Rw=0.238。双核配合物的变温磁化率(4-300K)数据表明,用最小二乘法进行理论拟合(H=-2JS~1.S~2),得出交换积分J=6.72cm^-^1,θ=-0.60cm^-^1,表明双核镍之间为弱的铁磁相互作用,分子间为弱的反铁磁相互作用。

Crystal structure, spectra and magnetism of mono-, di-nickel(II) complexes

Two complexes, one is binuclear Ni(II) complex 1, another is mononuclear Ni(II) complex 2 with the ligand TPA TPA=tri(2- pyridylmethyl) amide], have been synthesized. Their structures have determined by single crystal X-ray diffraction method. The binuclear Ni(II) complex, C~3~6H~3~6N~8Ni~2Cl~2).11/6(ClO~4).1/6(OH).8/6(H~2O), is trigonal system, space group R-3, a=2.8425(4)nm, b=2.8425(4)nm, c=1.4385(5)nm, α=β=90.00ⅲ, γ=120.00ⅲ, Z=18, final R=0.078, Rw=0. 078. The crystal of mononuclear Ni(II) complex, C~2~0H~1~8N~6NiS~2 . 0. 5(H~2O) is triclinic system, space group, P1, a=0.9467(1)nm, b=1.5566 (3)nm, c=1.5913(3)nm, α=73.59(4)ⅲ, β=87.37(3)ⅲ, γ=76.27(2)ⅲ, Z=4, R=0.0784, Rw=0.238. The variable temperature magnetic susceptibility (4-300K) of complex 1 indicates there is a ferromagnetic intramolecular interaction (J=6.72cm^-^1) and weak antiferromagnetic intermolecular interaction (θ =-0.60cm^-^1).