两个基于双(4-吡啶-4-苯基)胺的钴(Ⅱ)、锌(Ⅱ)配合物的合成和晶体结构（英文）

Syntheses, Crystal Structures of Two Cobalt(Ⅱ)/Zinc(Ⅱ) Complexes Based on Bis(4-(pyridin-4-yl)phenyl)amine

以双(4-吡啶-4-苯基)胺(BPPA)和4,4-(六氟)双(苯甲酸)(H2hfipbb)或对苯二甲酸(p-H2bdc)为配体,采用溶剂热法与M(NO3)2·6H2O(M=Co、Zn)组装合成了2个新的配合物{[Co2(BPPA)(hfipbb)2·(H2O)3]·6H2O}n(1)、{[Zn2(BPPA)2(p-bdc)2]·H2O·DMF}n(2),利用元素分析、X射线粉末衍射(PXRD)、红外光谱等手段分别对它们进行了表征,并用X射线单晶衍射仪测定了配合物的单晶结构。X射线单晶衍射测定结果表明:配合物1和2均为二维结构。配合物1具有新的拓扑结构。配合物2的二维结构又可以组成三维框架结构。配合物1为正交晶系,Pnna空间群,a=2.640 9(2)nm,b=1.715 78(13)nm,c=1.504 11(11)nm,V=6.8154(9)nm3,Z=4,μ=0.571 mm-1,F(000)=2 592,Dc=1.245 g·cm-3,Mr=1 383.76,R1=0.066 6,w R2=0.208 9(I>2σ(I));配合物2为单斜晶系,C2/c空间群,a=2.796 70(9)nm,b=1.814 82(6)nm,c=2.303 13(7)nm,β=102.136 0(10)°,V=11.428 3(6)nm3,Z=8,μ=0.906 mm-1,F(000)=4 944,Dc=1.391 g·cm-3,Mr=1 196.85,R1=0.039 8,w R2=0.106 4(I>2σ(I))。此外,热重分析表明配合物1和2均具有良好的热稳定性。

Two complexes {[Co2（BPPA）（hfipbb）2·（H2O）3]·6H2O}n（1） and {[Zn2（BPPA）2（ p-bdc）2]·H2O·DMF}nwere synthesized by solvothermal method using bis（4-（pyridin-4-yl）phenyl）amine（BPPA）, 4,4′-（hexafluoroisopropylidenene）bis（benzoic acid）（H2hfipbb）, terephthalic acid（ p-H2bdc） and M（NO3）26H2O（M =Co, Zn）, respectively. The complexes were characterized by elemental analysis, IR spectra, XRD and TGA, and the crystal structures were determined by single-crystal X-ray diffraction. Crystal structures were determined by single-crystal X-ray diffraction. Structural analyses reveal that complexes 1 and 2 exhibit a two-dimensional（2D） framework structure.Complex 1 represents new 6-connected net with Point Symbol of（411.64）, and the complex 2 assembles into a 3D supramolecular network. Complex 1 crystallizes in the monoclinic system, space group Pnna, with cell parameter：a=2.640 9（2） nm, b=1.715 78（13） nm, c=1.504 11（11） nm, V=6.815 4（9） nm^3, Z=4, μ=0.571 mm^-1, F（000）=2 592,Dc=1.245 g·cm^-3, Mr=1 383.76, R1=0.066 6, and wR2=0.208 9（I〉2σ（I））; Complex 2 crystallizes in the monoclinic system, space group C2/c, with cell parameter： a=2.796 70（9） nm, b=1.814 82（6） nm, c=2.303 13（7） nm, β=102.136 0（10）°, V=11.428 3（6） nm^3, Z=8, μ=0.906 mm-1, F（000）=4 944, Dc=1.391 g·cm^-3, Mr=1 196.85, R1=0.0398, and wR2=0.106 4（I〉2σ（I））. Additionally, complexes 1 and 2 display good thermal stability.