【作者】 周健；

【导师】 梁宏； 陈振锋；

【作者基本信息】 广西师范大学 ， 无机化学， 2004， 硕士

【摘要】 近几十年来,人们在设计和合成席夫碱配合物方面付出了相当大的努力,因为它有很强的配位能力,良好的生物活性及各方面优越的性能,使其成为很有潜力的治疗药物和功能材料,所以席夫碱配合物吸引了人们极大的兴趣,并且成为热门研究课题之一。本文以吡啶醛类席夫碱为配体与金属离子作用,合成了7个配合物,并测定了它们的单晶结构,研究了它们的谱学性质。通过N-氧化吡啶―2―甲醛、氨基脲与NaAc在无水乙醇中按1:1:1摩尔比进行的反应,合成了希夫碱N-氧化吡啶―2―甲醛缩氨基脲,希夫碱与高氯酸钴在乙醇中按1:3摩尔比进一步反应。合成了配合物N-氧化吡啶―2―甲醛缩氨基脲钴(II),并获得单晶。晶体属三斜晶系,空间群为P-1, 晶胞参数a=9.180(2) A, b=12.908(3) A, c=14.265(4) A ,Dc=1.678Mg/m3,α=100.340(5)°,β=102.817(5)°,γ=92.411(5)°,V=1615.5(7) ?3, Z=2, Mr=816.37 ,μ=0.786mm-1, F(000)=834, 结构偏离因子R=0.0728 和 ωR=0.1354。配合物为离子型配合物,配合物(1)的中心金属离子Co(Ⅱ)采取六配位的变形的八面体几何结构,晶体中Co(Ⅱ)与2个配体希夫碱中N(-CH=N),O(N→O),O(C=O)的原子配位。分子间通过配阳离子、自由配体、结晶水和抗阴离子(ClO4 )之间形成氢键(N-H…O,O-H…O)以及弱的氢键(C-H…O)使配合物分子组装成三维网状结构。高氯酸镍和高氯酸钴分别与吡啶―2―甲醛缩氨基脲席夫碱作用,获得了镍(II)、钴(II)的吡啶―2―甲醛缩氨基脲席夫碱配合物单晶,X-射线单晶结构分析显示配合物NiL2(2),分子式 C14H14N8NiO2,属四方晶系,空间群P 43,晶胞参数:a=8.2766(12) A,b=8.2766(12) A, c=23.648(4) A ,Dc=1.579Mg/m3, α=90°,β=90°,γ=90°,V=1619.9(4) A3,Z=4, μ=1.225mm-1, F(000)=792, 结构偏离因子R=0.0261 和ωR=0.0556,配合物(2)的中心金属离子配位数为6,变形八面体空间构型。晶体中Ni(II)与配体希夫碱中的N(C=N) 、N(吡<WP=5>吡啶醛类过渡金属希夫碱配合物的合成、晶体结构及谱学表征啶) 、O(C-O)原子配位形成变形的八面体构型,由于分子间,存在大量的强氢键(N-H…O)和弱氢键(C-H…O),这些氢键的交互作用使得该配合物形成二维网状结构。配合物[CoL2]·(ClO4)2·H2O(3),分子式C14H18Cl2CoN8O11,Mr=604.19,属三斜晶系,空间群P-1,晶胞参数:a=9.984(3) A, b=11.082(4) A, c=12.196(5) A ,Dc=1.769Mg/m3, α=112.954(4)°,β=110.050(4)°,γ=94.017(3)°,V=1134.4(7) A3, Z=2, μ=1.067mm-1, F(000)=614, 结构偏离因子R=0.0501 和ωR=0.1028,配合物(3)的中心金属离子采取六配位的变形八面体。钴(II)的周围被两个配体吡啶N、N(C=N)、O(C=O)原子所包围,分子间通过H2O,抗阴离子(ClO4 )与配阳离子的氮原子形成氢键,使配合物分子堆积成三维超分子结构。在70℃的条件下 ,通过吡啶-3(或4)-甲醛缩氨基脲分别与[Cu(CH3CN)2(PPh3)]·(ClO4) 、CoAc2·4H2O、NiAc2·4H2O 、Co(ClO4)·6H2O溶剂热反应制得化合物 (4) 、(5) 、(6) 、(7)。配合物(4)晶体属三斜晶系,空间群为P-1,晶胞参数:a=7.5444(6) A, b=8.7190(7)(4) A, c=16.2409(13) A ,Dc=1.687Mg/m3, α=76.601(2))°,β=84.352(2)°,γ=68.560(1)°,V=967.2(1) ?3, Z=1, μ=1.687mm-1, F(000)=500, 结构偏离因子R=0.0720 和 ωR=0.1346; 配合物(5)属三斜晶系,空间群为P-1,晶胞参数:a=7.8694(13)A, b=8.8660(13) A, c=10.2643(11) A ,Dc=1.576Mg/m3, α=65.788(11)°,β=69.511(12)°,γ=81.816(14)°,V=611.83(15)A3, Z=1, μ=1.567mm-1, F(000)=301, 结构偏离因子R=0.0279 和 ωR=0.0677. 配合物(6)晶体属三斜晶系,空间群为P-1,晶胞参数:a=7.8498(19) A, b=8.836(2) A, c=10.2711(17) A ,Dc=1.573Mg/m3, α=65.822(15)°,β=69.678(16)°,γ=82.14(2)°,V=609.5(2) A3, Z=1, μ=0.866mm-1, F(000)=302, 结构偏离因子R=0.0376 和 ωR=0.0753.配合物(7)晶体属三斜晶系,空间群为P-1,晶胞参数:a=6.9015(13) A, b=10.2030(19) A, c=11.136(2) A ,Dc=1.613Mg/m3, α=104.960(3)°,β=90.090(3)°,γ=108.177(4)°,V=716.9(2) A3, Z=1, μ=0.868mm-1, F(000)=359, 结构偏离 2<WP=6>吡啶醛类过渡金属希夫碱配合物的合成、晶体结构及谱学表征因子R=0.0857 和 ωR=0.2361。配合物(4)的中心金属离子Cu(I)的配位数为3,Cu(I)与配体中吡啶N,末端中NH2的N配位,形成双核配合物,其中,N(C=N) 、O(C=O)没有参加配位。配合物(5) 、(6) 、(7)的中心金属离子均被两个配体中的吡啶氮原子和四个配位水分子的氧原子所包围,形成拉长的八面体构形。在配合物(4)中,配合物分子通过抗阴离子(ClO4 ) -与配阳离子之间的氢键作用,使配合物分子组装成三维网状结构。在配合物(5)、(6)中,通过抗阴离子(CH3COO-)和配阳离子之间氢键作用,使配合物分子堆积成三维层状结构。在配合物(7)中,配合物分子通过抗阴离子(ClO4 )、结晶水和配阳离子之间的氢键作用,使 -配合物分子形成三维网状结构。更多还原

【Abstract】 In the last decades, considerable efforts have been made to design and synthesize the Schiffbase complexes for they have strong coordination ability, good biological activities and otherexcellent properties, make them to be potential drugs and functional materials, the Schiff basecomplexes have attacted considerable interest and become one of the subjects of intensiveresearch. Seven crystal structures have been obtained by treatment pyridinecarbaldehydesemicarbazones with the transition metal salts, [(Cu(CHCN)2(PPh3)2)]ClO4, Co(CLO4)2.6H2O,Ni(ClO4)2.6H2O, CoAc2.4H2O, NiAc2.4H2O, respectiverly. The complexes have beencharacterized by a variety of spectroscopic techniques and the crystal and molecular structures aredetermined by single crystal X-ray diffraction techniques.The reaction of pyridinecarbaldehyde N-oxide semicarbazide and NaAc in ethanol in the<WP=8>molar ratio of 1:1:1 gave the ligand. The reaction of Schiff base and Co(ClO4)2.6H2O In 50%ethanol in the molar ratio of 3:1, compound [Co(PNOS )(ClO4)2·(PNOS)·H2O was furthersynthesized and red single crystal was obtained, compound (1) crystal belongs to triclinic system,space group p –1, with Unit cell parameters: a=9.180(2) A, b=12.908(3) A, c=14.265(4)A ,Dc=1.678Mg/m3 α=100.340(5)°,β=102.817(5)°,γ=92.411(5)°,V=1615.5(7) A3, Z=2,Mr=816.37 , μ=0.786mm-1, F(000)=834, final R=0.0728 and ωR=0.1354, the crystal is ioniccomplex, the centeral metal Co(II) of complex 1 adopts six-coordinated distorted octahedralgeometry, In the complex(1), PNOS is coordinated to cobalt(II) via the oxygen(N-O),nitrogen(C=N) and oxygen(C=O) atoms. In addition, there are a large number of strong hydrogenbondings(N-H…O,O-H…O) and weak hydrogen bondings(C-H…O) in involving the cations,perchlorate counter-ions,PNOS and water molecules, which result in formation 3-D networkstructure.The reactions of pyridine-2-carbaldehyde semicarbazone with transition metal (Ni(II),Co(II))salts afford two pyridine-2-carbaldehyde semicarbazone transition metal compounds. CompoundNi(H-pysc)2, C14H14N8NiO2, Mr=385.04, belongs to Tetragonal system, space group p 43, withUnit cell parameters: a=8.2766(12) A, b=8.2766(12) A, c=23.648(4) A ,Dc=1.579Mg/m3, α=90°,β=90°,γ=90°,V=1619.9(4) A3, Z=4, μ=1.225mm-1, F(000)=792, final R=0.0261 and ωR=0.0553, In the compound (2), the coordination geometry is a distorted octahedron and Ni(II)center chelates N atom of pyridine、 the nitrogen (C=N) and oxygen (C-O) atoms. A large numberof hydrogen bonding(N-H…O、C-H…O) interactions in the pack of compound 2 forms two-Dnetwork structure. Compound [Co(H-pysc)2](ClO4)2(H2O), C14H18Cl2CoN8O14, Mr=604.19,belongs to triclinic system, space group p –1, with Unit cell parameters: a=9.984(3) A, b=11.082(4)A, c=12.196(4) A , Dc=1.769Mg/m3,α=112.954(4)°,β=110.050(4)°,γ=94.017(3)°,V=1134.4(7)A3, Z=2, μ=1.067mm-1, F(000)=614, final R=0.0501 and ωR=0.1028, H-pysc is coordinated tocobalt(II) by the N atom of pyridine, the nitrogen(C=N) and oxygen(C=O) atoms, the coordinationgeometry is a distorted octahedron. The three-dimensional supramolecular architecture is formedby a number of hydrogen bonds(O-H…O and N-H…O) involving the cations,perchloratecounter-ions and water molecules.A dinuclear complex [CuL2]2.(ClO4)2 (4) and three mononuclear complexes (5) 、(6) 、(7)<WP=9>have been synthesized respectively,through the reaction of pyridine-3(or4)-carbaldehydesemicarbazone by hydro(solvo)thermal treatment at 70℃. Compound 4 belongs to triclinic system,space group p –1, with Unit cell parameters: a=7.5444(6) A, b=8.7190(7)(4) A, c=16.2409(13)A ,Dc=1.687Mg/m3, α =76.601(2)) ° , β =84.352(2) ° , γ =68.560(1) ° ,V=967.2(1) A3, Z=1,μ=1.687mm-1, F(000)=500, final R=0.0720 and ωR=0.1346; Compound (5) belongs to triclinicsystem, space group p –1, with Unit cell parameters: a=7.8694(13) A, b=8.8660(13) A,c=10.2643(11) A ,Dc=1.576Mg/m3, α =65.788(11) ° , β =69.511(12) ° , γ =81.816(14)° ,V=611.83(15) A3, Z=1, μ更多还原