[Cu(β-ala)(phen)(H2 O)]·NO3 ·H2O的合成与晶体结构

在pH为3的醇水混合溶剂中合成了β-丙氨酸、1,10-邻菲咯林、铜的三元配合物,测定了配合物的晶体结构.晶体属单斜晶系,Pī空间群,晶胞参数a=1.0045(2) nm, b=1.2132(2) nm, c=0.71682(14) nm, α= 93.88(3)°, β= 94.31(3)°, γ= 99.81(3)°, V=0.8555(3) nm3, Z=2, Dc=1.669 Mg·m-3, μ=1.326 mm-1, F(000)=442, R=0.0457, Rw=0.1179.配合物中铜离子的配位数为5,分子间通过氢键构成三维网状结构.     

A new cation induced chain-like complex [Cu(H2tea)(H2O)(imi)][Cu(H3tea)(imi)][Na{Mo8O26}] · 4H2O

A new complex [Cu(H₂tea)(H₂O)(imi)][Cu(H₃tea)(imi)][Na{Mo₈O₂₆}] · 4H₂O (H₃tea =triethanolamine, imi = imidazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction reveals that β-[Mo₈O₂₆]^4? polyanions are linked by sodium ions to form a chain. The coppers are five- and six-coordinate for [Cu(H₃tea)(imi)]²⁺ and [Cu(H₂O)(H₂tea)(imi)]⁺, respectively. Crystal packing is due to hydrogen bonds and π ··· π stacking interactions, giving a 3-D polymeric network. The magnetic properties of the title compound are also presented.     

Crystal Structure and Interaction with DNA of [Ni(phen)(mal)(H2O)2]·3H2O

A new complex [Ni(phen)(mal)(H2O)2]·3H2O (phen = 1,10-phenanthroline,mal2-= malonic acid) has been synthesized by the reaction of nickel nitrate,phen and malonic acid.EA,IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the title complex.Crystal data:monoclinic system,space group P2/c,a =8.937(3),b = 12.163(5),c = 9.725(3)(A),β = 119.36°,C15H19N2O9Ni,Mr= 430.03,Z = 2,F(000) =446,V = 921.3 (A)3,Dc = 1.550 g/cm3,μ = 1.104 mm-1,-10≤h≤ 10,-12≤k≤ 14,-11 ≤l≤7,R =0.0261 and wR = 0.0609 for 4376 (Rint = 0.0203) independent reflections and 1631 observed ones (I＞ 2σ(I)).Ni(Ⅱ) exhibits an octahedral coordination geometry,with hydrogen bonds and π-π interactions stabilizing the whole structure.UV spectrum of the complex interacting with protamine DNA indicates that the title compound interacts with DNA via insertion mode with bonding constant Kb of 1.11 × 104.     

[RuIII(EDTA)(H2O)]− catalyzed oxidation of biologically important thiols by H2O2

[Ru^III(EDTA)(H₂O)]^? (EDTA^4? = ethylenediaminetetraacetate) catalyzes the oxidation of biological thiols, RSH (RSH = cysteine, glutathione, N-acetylcysteine, penicillamine) using H₂O₂ as precursor oxidant. The kinetics of the oxidation process were studied spectrophotometrically as a function of [Ru^III(EDTA)(H₂O)]^?, [H₂O₂], [RSH], and pH (4–8). Spectral analyses and kinetic data are suggestive of a catalytic pathway in which the RSH reacts with [Ru^III(EDTA)] catalyst complex to form [Ru^III((EDTA)(SR)]^2? intermediate species. In the subsequent reaction step the oxidant, H₂O₂, reacts directly with the coordinated S of the [Ru^III((EDTA)(SR)]^2? intermediate leading to formation of the disulfido (RSSR) oxidation product (identified by HPLC and ESI-MS studies) of thiols (RSH). Based on the experimental results, a working mechanism involving oxo-transfer from H₂O₂ to the coordinated thiols is proposed for the catalytic oxidation.     

铜配合物[Cu(2,2'-bipy)(pydco)(H2O)]·4H2O的合成与晶体结构

配合物[Cu(2,2’-bipy)(pydco)(H2O)].4H2O(2,2’-bipy=2,2’联吡啶,pydco=氮氧化-2,6-二甲酸吡啶)的结构由X-射线测定,配合物属三斜晶系,P墿空间群,晶胞参数:a=0.68120(14),b=1.1850(2),c=1.2554(3)nm,α=86.06(3),β=81.60(3),γ=86.16(3)°,V=0.99854(4)nm3,Z=2。2,2’联吡啶提供两个配位原子(N1,N2),氮氧化-2,6-二甲酸吡啶提供两个配位氧原子以及一个配位水提供一个氧原子参与了配位,中心Cu(II)离子是一个畸变的四角锥结构。有趣的是,配合物的结晶水组成了一条条的水带,配合物分子正是由这些水带中的氢键连接在一起的。     

配合物Cu(pico)(4,4′-bipy)(H2O)ClO4·H2O的合成及其晶体结构

利用水热法合成了新型一维配合物Cu(pico)(4,4′-bipy)(H2O)ClO4·H2O(1,bipy=联吡啶,pico=邻吡啶甲酸根),其结构经IR,元素分析和X-射线单晶衍射表征.1属于单斜晶系,P21/n空间群,晶胞参数:a=0.853 57(8)nm,b=1.610 58(14)nm,c=1.416 85(13)nm,β=99.407(2)°,V=1.921 6(3)nm3,Z=4,Mr=477.31 g·mol-1,Dc=1.650 g·cm-3,μ=1.326mm-1,F(000)=972,R1=0.078 1,wR2=0.239 1,S=1.102.1中Cu2 与邻吡啶甲酸配体上一个N原子和一个O原子、两个4,4′-联吡啶的N原子以及一个水分子的O原子配位,形成了四方锥配位几何构型.在a c轴方向,Cu2 与两个4,4′-联吡啶分子经桥联作用形成一维zig-zag链;链与链通过氢键形成三维结构.     

含氢键铜配合物[Cu(mal)(phen)(H2O)]2·3H2O的合成与晶体结构

丙二酸作为桥联配体可以与过渡金属形成形式多样的配合物 ,其结构和磁性已成为近年来人们研究的热点[1～ 8] ,本文报道了丙二酸邻菲罗啉铜配合物 [Cu(mal) (phen) (H2 O) ]2 ·3H2 O(mal=丙二酸根 ,phen =1 1 0 邻菲罗啉 )的合成和晶体结构 ,并探讨了氢键的作用和超分子网络结构。1　实验部分1 .1　试剂与仪器　所有试剂均为分析纯。Perkin Elmer2 4 0C型元素分析仪 (C ,H ,N) ,NicoletAvatar 370FT IR红外光谱仪 ( 4 0 0 0 40 0cm 1 ,KBr压片 ) ,德国耐驰公司STA40 9PC热分析仪 ,RigakuRAXIS IVIP单晶X 射线衍射仪。1 .2…     

Synthesis and Crystal Structure of a Two-dimensional Framework Supramolecular Complex [Mn(phen)(DPZDA)(H2O)]·2H2O

A novel two-dimensional supramolecular complex [Mn(phen)(DPZDA)(H2O)]·2H2Ohas been synthesized by the reaction of Mn(CH3COO)2, 1,10-phenanthroline (phen) and H2DPZDA (3,5-dimethyl-pyrazine-2,6-dicarboxylic acid). Elemental analysis, IR spectra and X-ray singlecrystal diffraction were carried out to determine the composition and crystal structure of the title complex. Crystal data: triclinic system, space group P-1, a = 7.7474(13), b = 9.3381(15), c =15.146(3)(A), α = 93.872(3), β = 102.451(11), γ = 105.261(11)°, C20H20MnN4O7, Mr = 483.34, Z = 2,F(000) = 498, V = 1023.2(3)(A)3, Dc = 1.569 g/cm3, μ = 0.697 mm-1, -9≤h≤9, -11 ≤k≤ 10, -18≤l≤12, R = 0.0365 and wR = 0.0901 for 3585 independent reflections (Rint = 0.0165) and 2923observed reflections (I ＞ 2σ(I)). Structural analysis indicates that Mn(Ⅱ) adopts a distorted octahedral geometry. The 2-D framework supramolecular structure of the title complex is constructed from hydrogen bonds and π…πinteractions.     

[{Zn(3-SBA)(2,2''''-bipy)(H2O)2}·H2O]n的合成和晶体结构研究

具有层状结构的无机-有机杂化复合聚合物材料有广泛的应用前景,它引起化学工作者的浓厚兴趣,成为一个热门的研究领域[1～3].众所周知,这类聚合物具有许多特殊的性能,在新功能材料(如选择性催化材料、分子识别材料、超高纯度分离材料、光电材料、新型半导体材料、磁性材料)开发中显示了诱人的应用前景[4～6].类似于有机磷酸化合物,有机磺酸已被报道易同多种金属形成各种各样具有层状或者柱层状的化合物,这些金属包括碱金属、碱土金属、过渡金属及镧系金属[7～9].多种官能团如-NH2、-OH、-COOH和-SO3H一起形成一类新型的无机-有机杂化复合聚合物材料.文献中报道的配体有4-羧基苯磺酸[7]、3,5-二羧基苯磺酸[10]、1,4-苯二磺酸[11].到目前为止,使用3-羧基苯磺酸作为配体的还未见报道,本文使用3-羧基苯磺酸作为配体与ZnSO4·H2O和2,2'-联吡啶反应合成了一个层状Zn配合物.用IR和元素分析对配合物进行了表征,用X-射线单晶衍射测定了该配合物的单晶结构,并对该配合物的荧光性质进行了研究.     

[Ni(bpy)(mal)(H2O)3]·H2O and [Ni(4,4′-dmbpy)(mal)(H2O)3]·1.5H2O: syntheses,crystal structures,magnetic properties,and computational study of stacking interactions

[Ni(bpy)(mal)(H₂O)₃]·H₂O and [Ni(4,4′-dmbpy)(mal)(H₂O)₃]·1.5H₂O (mal = maleato; bpy = 2,2′-bipyridine; 4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) exhibit molecular crystal structures. The Ni(II) central ions in both complexes are six-coordinate by one chelate bonded L–L ligand, three aqua ligands, and one position is occupied by a maleato oxygen donor atom. Hydrogen bonded ribbon-like supramolecular structural motifs are present in both studied complexes; these are linked by weaker C–H?O hydrogen bonds in [Ni(bpy)(mal)(H₂O)₃]·H₂O, whereas in [Ni(4,4′-dmbpy)(mal)(H₂O)₃]·1,5H₂O the hydrogen bonded ribbons are linked by O?H-O-H?O hydrogen bonds with the participation of the additional water solvate molecule positioned on the twofold axis. In both structures, π–π stacking interactions with different patterns in respective structures were found. The role of dispersion energy and many-body effects in the stabilization of bpy and 4,4′-dmbpy stacking interactions were investigated using methods of computational chemistry. Those confirm the dispersion-dominated stabilization of the 4,4′-dmbpy supramolecular chain-like structure, with only marginal impact of cooperativity effects. Thermal decompositions of both complexes start with dehydration. Magnetic susceptibility studies performed from 2 to 300 K revealed a dominant effect of the zero-field splitting of the Ni(II) ion, governing the low-temperature magnetic properties of both compounds.     

Syntheses and structures of seven-coordinate K3[Cd(Dtpa)], K2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O, and Na2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O complexes

The title complexes, K₃[Cd(Dtpa)] (H₅Dtpa = diethylenetriamine-N,N,N,N′,N′-pentaacetic acid, (I)), K₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid, (II)), and Na₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (III), were prepared, and their compositions and structures were determined by elemental analyses, IR spectra, and single-crystal X-ray diffraction techniques, respectively. In complex I, the Cd is seven-coordinated by one Dtpa ligand yielding a pseudo-monocapped trigonal prism conformation, and the complex crystallizes in the triclinic crystal system with the Pi space group. The crystal data are as follows: a = 8.7300(17), b = 9.1200(18), c = 15.110(3) Å, α = 95.52(3)°, β = 96.59(3)°, γ = 99.63(3)°, V = 1170.0(4) ų, Z = 2, ρ = 1.754 g/cm³, μ = 1.519 mm^?1, F(000) = 616, R = 0.0644 and wR = 0.1712 for 3842 observed reflections with I ≥ 2σ(I). For complex II, in the [Cd(Edta)(H₂O)]^2? complex anion the Cd²⁺ ion is seven-coordinated by one Edta ligand and one water molecule, yielding a pseudo-pentagonal bipyramid conformation. In the [Cd(H₂O)₄]²⁺ cation, the bridged Cd is six-coordinated, yielding an almost standard octahedral conformation. The complex crystallizes in the monoclinic system with P2₁/n space group. The crystal data are as follows: a = 9.098(3), b = 16.442(6), c = 12.023(4) Å, β = 91.053(6)°, V = 1798.3(12) ų, Z = 2, ρ = 2.098 g/cm³, μ = 2.086 mm^?1, F(000) =1124, R = 0.0406 and wR = 0.1152 for 3680 observed reflections with I ≥ 2σ(I). In complex III, the conformations of Cd²⁺ ions are similar to those of the potassium salt complex, and the complex also crystallizes in the monoclinic crystal system with the P2₁/n space group. The crystal data are as follows: a = 9.134(7), b = 16.500(13), c = 12.075(10) Å, β = 91.054(12)°, V = 1820(2) ų, Z = 2, ρ = 2.015 g/cm³, μ = 1.856 mm^?1, F(000) = 1092, R = 0.0363 and wR = 0.0879 for 3707 observed reflections with I ≥ 2σ(I).     

Vanadium Haloperoxidases Model Compounds: Synthesis,Structural Characterization and Mimic Catalytic Bromination Activity of [VO(C2O4)(2,2′-bipy)(H2O)]·C2H5OH and VO(C2O4)(phen)(H2O)

Two oxo-vanadium(IV) complexes, [VO(C₂O₄)(2,2′-bipy)(H₂O)]·C₂H₅OH(1) and VO(C₂O₄)(phen)(H₂O) (2), where 2,2′-bipy=2,2′-bipyridyl, phen=1,10-phenanthroline, were synthesized as potential functional models of vanadium haloperoxidases(VHPOs) in mixed solvent of ethanol and water at room temperature. The complexes were characterized by elemental analysis, infrared(IR), UV-Vis and X-ray crystallography. Structural analyses showed that vanadium atom was coordinated by a terminal oxygen, one oxygen atom from coordinated water, two oxygen atoms from the carboxylate group of oxalic acid, and two nitrogen atoms(N1 and N2) from 2,2′-bipy/phen. Central vanadium atoms in complexes 1 and 2 were both in a distorted-octahedral environment, and some intermolecular hydrogen bonding linkages were also observed in each complex. Bromination reaction activity of the two complexes was evaluated with phenol red as organic substrate in the presence of H₂O₂, Br^- and phosphate buffer, indicating that they can be considered as a potential functional model of VHPO. In addition, thermal analysis was also performed and discussed in detail.     

配合物[MnL(2,2''''-bipy)(H2O)]·2H2O的合成及其晶体结构

N-苯基亚氨基二乙酸(H2L),Mn(Ⅱ)和2,2'-联吡啶(2,2'-bipy)在50%甲醇中组装得标题配合物[MnL(2,2'-bipy)(H2O)]·2H2O(1),其结构经IR,元素分析和X-射线单晶衍射表征.1属单斜晶系,空间群P2(1)/n,晶胞参数:a=0.885 9(3)nm,b=1.826 9(6)nm,c=1.385 7(5)nm,β=106.200(6)°,V=2.153 6(13)nm3,Z=4,F(000)=980,Dc=1.457 Mg·m-3.在1的晶体结构中,Mn(Ⅱ)为六配位的畸变八面体构型,其中2,2'-bipy的2个氮原子和羧基的2个氧原子位于赤道平面,L的氮原子和一个配位水分子处于轴向位置.1分子之间存在的氢键与π-π芳香堆积作用将其连接成三维超分子结构.     

[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C10H10N2O4,简作H3L)、1,10-菲啰啉C12H8N2,简作phen)与Eu(NO3)3·4H2O反应,首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O.该晶体属三斜晶系,P1空间群,晶胞参数a=1.378 6(12) nm,b=1.398 8(12) nm,c=1.759 7(16) nm,α=73.977(11)°,β=68.598(12)°,γ=71.224(12)°,V=29.42(4) nm3,Z=2,μ=2.208 mm-1,Dc=1.746 Mg/m3,F(000)=1 556,R=0.037 7,ωR=0.074 4,GOF=0.916.每个配合物晶体中均有两个相似的结构单元,每个结构单元中铕(Ⅲ)配位数为9,分别与两个2-羰基丙酸水杨酰腙和3个水分子配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和CN中的氮与Eu3+配位,形成两个共边的稳定的五元环,另3个配位原子则分别来自3个水分子中的氧原子,该结构单元在空间呈扭曲的单帽四方反棱柱,而在每两个铕的九配位单元周围还有一个游离的1,10-菲啰啉分子和4个水分子.IR,1H NMR及热分解结果佐证了配合物的组成.该配合物具有很好的荧光特性.     

多元混配合物[Ni(NPA)2(Phen)(Ac)(H2O)]·H2O的合成、晶体结构

0引言镍是生物体中必须的痕量元素,常成为一些酶的活性中心,因而模拟镍酶并研究其结构,一直是生物无机化学等领域的重要研究课题,近年来镍配     

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n · n H2O

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

Two-Dimensional Coordination Polymer {[Zn(Pht)(4.4′-Bipy)(H2O)2] · 2H2O} n : Synthesis and Structure

The coordination polymer {[Zn(Pht)(4,4-Bipy)(H₂O)₂] · 2H₂O} _n (where Pht is a doubly deprotonated phthalic acid residue and 4,4-Bipy is 4,4-bipyridine) was synthesized and studied by X-ray diffraction. It was shown that both ligands perform a bridging function and unite the Zn atoms into a two-dimensional network with a periodicity of 11.302(2) Å (with 4,4-Bipy as the bridge) or 7.627(2) Å (with Pht as the bridge). The coordination polyhedron of Zn is a distorted octahedron with C ₂ symmetry. The Zn–N distances in the coordination polyhedron are 2.117(3) and 2.131(3) Å; the Zn–O_carb distance is 2.171(2) Å and the Zn–O(w) distance is 2.129(2) Å. The O–H···O hydrogen bonds involving the outer-sphere water molecules combine the polymer layers into a framework.     

Crystal Structure and Magnetic Properties of A One-Dimensional Polymer [Mn(im2-py)(tp)(H2O)2]·1.25H2O

A new manganese(II) complex [Mn(im2-py)(tp)(H₂O)₂]·1.25H₂O (im2-py=2-(2'-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and tp=terephthalato dianion) has been synthesized and characterized structurally and magnetically. The crystal structure consists of neutral chains of manganese(II) ions linked by the terephthalate ligand. Variable temperature magnetic susceptibility data exhibit a weak antiferromagnetic coupling between the manganese(II) ion and the imino nitroxide radical.