氰根桥连的异金属配位聚合物{[Ni(pn)2][Fe(CN)4(bipy)]}2·3H2O(pn=1,3-丙二胺,bipy=2,2′-联吡啶)的合成与结构

以[Fe(CN)₄(bipy)]^2-为建筑块和[Ni(pn)₂]²⁺在水溶液中反应,合成了{[Ni(pn)₂][Fe(CN)₄(bipy)]}₂·3H₂O(pn=1,3-丙二胺)。通过X-射线单晶衍射确定了其晶体结构。该配合物属单斜晶系,P2₁/n空间群,晶胞参数为:a     

氰根桥连的异金属配位聚合物{[Ni(pn)_2][Fe(CN)_4(bipy)]}_2·3H_2O(pn=1,3-丙二胺,bipy=2,2''''-联吡啶)的合成与结构

以犤Fe(CN)4(bipy)犦2-为建筑块和犤Ni(pn)2犦2+在水溶液中反应,合成了狖犤Ni(pn)2犦犤Fe(CN)4(bipy)犦狚2·3H2O(pn=1,3-丙二胺)。通过X-射线单晶衍射确定了其晶体结构。该配合物属单斜晶系,P21/n空间群,晶胞参数为:a=16.0317(3)?,b=18.6175(2)?,c=18.5124(3)?,α=90.00°,β=115.2447(9)°,γ=90.00°,V=4997.7(17)?3,Z=4,Dc=1.462g·cm-3,μ=1.369mm-1,F(000)=2296.0,R1=0.0359,wR2=0.0514。配合物中Ni-CN-Fe的连接存在直线型和弯折型两种构型,从而产生氰根桥连的一维螺旋链结构。     

具有双螺旋链的新型镉(II)大豆甙元衍生物配位聚合物[Cd(L)(H2O)3]•2H2O的合成与晶体结构研究

合成新型大豆甙元衍生物Cd(II)配合物[Cd(L)(H₂O)₃]•2H₂O (H₂L＝3'-磺酸钠-4'-羟基-7-羧甲基异黄酮), 采用单晶X射线衍射、元素分析和IR对其进行表征. 该配合物属单斜晶系, 空间群为P2₁/a, 晶胞参数a＝1.3691(3) nm, b＝0.72157(16) nm, c＝2.0163(5) nm, α＝90°, β＝93.501(4)°, γ＝90°, V＝1.9882(8) nm³, M_r＝592.79, Z＝4, D_c＝1.980 g•cm^－3, F(000)＝1192, μ＝1.283 mm^－1, R₁＝0.0387, wR₂＝0.1224. X射线单晶衍射分析结果表明, 该单晶中Cd(II)为六配位, 它除了与配体L中羧基和磺酸基上的氧原子配位外, 还与溶剂中的3个水分子发生配位, 形成了以Cd(II)为中心的八面体配位构型. 该晶体结构中存在着平行于b轴的双螺旋链, 左手螺旋Cd-L链和右手螺旋Cd-L链的交替排列构成了二维层状结构. 由于配位水和晶格水以及配体中CO₂, SO₃, O, CO, OH等的存在, 该晶体中存在着丰富而复杂的氢键, 二维层状结构之间依靠这些复杂的氢键作用形成三维超分子结构.     

具有双螺旋链的新型镉(II)大豆甙元衍生物配位聚合物[Cd(L)(H_2O)_3]·2H_2O的合成与晶体结构研究

合成新型大豆甙元衍生物Cd(II)配合物[Cd(L)(H2O)3]·2H2O(H2L=3'-磺酸钠-4'-羟基-7-羧甲基异黄酮),采用单晶X射线衍射、元素分析和IR对其进行表征.该配合物属单斜晶系,空间群为P21/a,晶胞参数a=1.3691(3)nm,b=0.72157(16)nm,c=2.0163(5)nm,α=90°,β=93.501(4)°,γ=90°,V=1.9882(8)nm3,Mr=592.79,Z=4,Dc=1.980g·cm-3,F(000)=1192,μ=1.283mm-1,R1=0.0387,wR2=0.1224.X射线单晶衍射分析结果表明,该单晶中Cd(II)为六配位,它除了与配体L中羧基和磺酸基上的氧原子配位外,还与溶剂中的3个水分子发生配位,形成了以Cd(II)为中心的八面体配位构型.该晶体结构中存在着平行于b轴的双螺旋链,左手螺旋Cd-L链和右手螺旋Cd-L链的交替排列构成了二维层状结构.由于配位水和晶格水以及配体中CO2,SO3,O,CO,OH等的存在,该晶体中存在着丰富而复杂的氢键,二维层状结构之间依靠这些复杂的氢键作用形成三维超分子结构.     

由Pb-O螺旋链构筑具有罕见ecl拓扑结构的铅(Ⅱ)配位聚合物

Under hydrothermal condition, a novel coordination polymer [Pb(C₄H₄O₆)]_n has been successfully synthesized by reaction flexible racemic ligand D,L-tartaric acid (C₄H₄O₆) and Pb(Ⅱ)(NO₃)₂. Its structure is determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, IR, CHN and TG analyses. It crystallizes in tetragonal, space group I4₁/acd with a=1.569 0(2) nm, c=1.009 5(2) nm, V=2.485 0(7) nm³, Z=16. Its structure contains left- and right-handed helical chains. Such helical chains with opposite chirality are alternatively arranged and further connected to form a three-dimensional framework. Topology analysis shows that it presents rare ecl topological structure. CCDC: 771026.     

One—dimensional Zigzag Chain Coordination Polymer [Zn（μ—phth）（imi）2]∞ Bridged by o—Phthalato

The reaction of zinc carbonate with o-phthalic acid and imidazole in an aqueous-alcohol solution led to the formation of colorless crystals of [Znμ-phthimi2]∞. Single-crystal X-ray analysis has revealed that the complex crystallizes in a monoclinic system, space group Pn with a = 8.394(2), b = 9.976(3), c = 9.959(3)A, β = 104.409(4)°, V = 807.6(4)A3, Z = 2, C14H12N4O4Zn, Mr = 365.6(5), Dc = 1.504 g/cm3, μ = 1.544 mm-1, F000 = 372, the final R = 0.0466 and wR = 0.1171 for 1834 reflections with I>2σ(I). The complex displays a zigzag infinite chain structure in which each zinc(Ⅱ)center is coordinated by two oxygen atoms and two nitrogen atoms to generate a ZnN2O2 distorted tetrahedral geometry. The neighboring zinc atoms are bridged by the o-phthalate ligand. Each chain is linked by hydrogen bonds with its neighbors to form a three-dimensional coordination polymer.     

A three‐dimensional cadmium(II) coordination polymer with unequal homochiral double‐stranded concentric helical chains

A homochiral helical three‐dimensional coordination polymer, poly[[(μ₂‐acetato‐κ³O,O′:O)(hydroxido‐κO)(μ₄‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁵N¹,O:N²:N⁴:N⁵)(μ₃‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁴N¹,O:N²:N⁴:N⁵)dicadmium(II)] 0.75‐hydrate], {[Cd₂(C₇H₅N₆O)₂(CH₃COO)(OH)]·0.75H₂O}_n, was synthesized by the reaction of cadmium acetate, N‐(1H‐tetrazol‐5‐yl)isonicotinamide (H‐NTIA), ethanol and H₂O under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated 5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ide (NTIA⁻) ligands, one acetate anion, one hydroxide anion and three independent partially occupied water sites. The two Cd^II cations, with six‐coordinated octahedral and seven‐coordinated pentagonal bipyramidal geometries are located on general sites. The tetrazole group of one symmetry‐independent NTIA⁻ ligand links one of the independent Cd^II cations into 6₁ helical chains, while the other NTIA⁻ ligand links the other independent Cd^II cations into similar but unequal 6₁ helical chains. These chains, with a pitch of 24.937 (5) Å, intertwine into a double‐stranded helix. Each of the double‐stranded 6₁ helices is further connected to six adjacent helical chains through an acetate μ₂‐O atom and the tetrazole group of the NTIA⁻ ligand into a three‐dimensional framework. The helical channel is occupied by the isonicotinamide groups of NTIA⁻ ligands and two helices are connected to each other through the pyridine N and carbonyl O atoms of isonicotinamide groups. In addition, N—H...O and O—H...N hydrogen bonds exist in the complex.     

Synthesis and structure of the first propeller-shaped helical coordination polymer { [ Ag( S , S) -bis( oxazoline) ] (OTf)}_∞

A mixture of (S,S)-bis(oxazoline) ligand (1) with silver tri-fluoromethane sulfonate afforded a helical coordination polymer (2). Its structure was determined by X-ray single-crystal diffraction.     

一维交替链状稀土配位聚合物[Er(dpa)(pya)(H2O)]n和[Nd2(pya)6(H2O)4]n的水热合成及结构表征

在水热条件下,稀土氧化物与2,2′-联苯二甲酸及异烟酸反应得到了两个新颖的一维交替链状配位聚合物[Er(dpa)(pya)(H₂O)]_n和[Nd₂(pya)₆(H₂O)₄]_n(H₂dpa=2,2′-联苯二甲酸;Hpya=异烟酸)。测定了它们的晶体结构,并进行了红外光谱和元素分析等 性质的表征。晶体结构测定表明这两个化合物同属单斜晶系,并具有相同的空间群P2₁/n, 晶体学参数分别为配合物1：a= 0.8830(3) nm,b=1.058 5(3) nm,c=2.089 1(6) nm,β=98.429(4)°,D_c=1.883g·cm^-3, V=1.931 4(10) nm³,Z=4; 配合物2：a=0.968 9(4) nm,b=1.978 3(9) nm,c=1.164 2(6) nm,β=112.106(7)°,D_c=1.756 g·cm^-3,V=2.067 5(17) nm³,Z=4。     

含有双螺旋链的配位聚合物[Co(dpa)prz0.5]n的合成、晶体结构及磁性质

A coordination polymer [Co(dpa)prz_0.5]_n(1) with double-helix chains has been constructed hydrothermally using H₂dpa (H₂dpa=diphenic acid), prz (prz=piperazine) and Co(NO₃)₂·6H₂O. The structure and magnetic properties of the complex were investigated. The complex crystallizes in triclinic system and P1 space group. Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry. Two carboxylates of the H₂dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical -C-O-Co- chains. The two types of helical chains are interconnected to each other through the Co(Ⅱ) centers to produce double-helix chains. The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains. The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks. Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions. CCDC: 709275.     

一维链状2-氧-1(4H)-吡啶乙酸桥联钙配位聚合物[Ca(2-OPA)2(H2O)2]n的合成、晶体结构及热稳定性研究

A novel coordination polymer of [Ca(2-OPA)₂(H₂O)₂]_n (2-OPA-=2-oxo-1(4H)-pyridineacetate anion) was synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in orthorhombic with space group Pna2₁, a=0.799 96(16) nm, b=0.823 77(16) nm, c=2.415 3(5) nm, V=1.591 6(6) nm³, Z=4, R=0.030 3, wR=0.070 0. The Ca atom is eight-coordinated by six O atoms of four 2-OPA^- ligands and two water molecules, and displays a dodecahedron coordination geometry. Each 2-OPA^- ligand bridges two adjacent Ca atoms, forming a infinite chain along the a direction. The Ca…Ca distance is 0.4102 2(8)nm. A two-dimensional supramolecular framework is further constructed by the hydrogen bonds and the weak π-π interactions. The results of TG analysis show the chain structure of the title complex was stable under 297.5 ℃. CCDC: 251669.     

In situ single‐crystal to single‐crystal (SCSC) transformation of the one‐dimensional polymer catena‐poly[[diaqua(sulfato)copper(II)]‐μ2‐glycine] into the two‐dimensional polymer poly[μ2‐glycine‐μ4‐sulfato‐copper(II)]

The one‐dimensional coordination polymer catena‐poly[diaqua(sulfato‐κO)copper(II)]‐μ₂‐glycine‐κ²O:O′], [Cu(SO₄)(C₂H₅NO₂)(H₂O)₂]_n, (I), was synthesized by slow evaporation under vacuum of a saturated aqueous equimolar mixture of copper(II) sulfate and glycine. On heating the same blue crystal of this complex to 435 K in an oven, its aspect changed to a very pale blue and crystal structure analysis indicated that it had transformed into the two‐dimensional coordination polymer poly[(μ₂‐glycine‐κ²O:O′)(μ₄‐sulfato‐κ⁴O:O′:O′′:O′′)copper(II)], [Cu(SO₄)(C₂H₅NO₂)]_n, (II). In (I), the Cu^II cation has a pentacoordinate square‐pyramidal coordination environment. It is coordinated by two water molecules and two O atoms of bridging glycine carboxylate groups in the basal plane, and by a sulfate O atom in the apical position. In complex (II), the Cu^II cation has an octahedral coordination environment. It is coordinated by four sulfate O atoms, one of which bridges two Cu^II cations, and two O atoms of bridging glycine carboxylate groups. In the crystal structure of (I), the one‐dimensional polymers, extending along [001], are linked via N—H...O, O—H...O and bifurcated N—H...O,O hydrogen bonds, forming a three‐dimensional framework. In the crystal structure of (II), the two‐dimensional networks are linked via bifurcated N—H...O,O hydrogen bonds involving the sulfate O atoms, forming a three‐dimensional framework. In the crystal structures of both compounds, there are C—H...O hydrogen bonds present, which reinforce the three‐dimensional frameworks.     

Construction of a 2D Cd(Ⅱ) Network with Homohelical Chains Based on 1,3-Dipyridyl Benzene(Dpb) and 4,4'-Sulfonyldibenzoic Acid(H_2sdb)

A two-dimensional(2D) coordination polymer {[Cd2(sdb)2(dpb)2]·3H2O}n(1) was prepared by solvothermal reaction of two types of V-shaped ligands: 1,3-dipyridyl benzene(dpb) and deprotonated 4,4'-sulfonyldibenzoic acid(H2sdb). It was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group Fdd2 with a = 46.247(10), b = 9.994(2), c = 24.267(6) , V = 11216(4) 3, C60H46Cd2N4O15S2, Mr = 1387.97, Dc = 1.559 g/cm3, F(000) = 5296.0, μ = 0.902 mm-1 and Z = 8. Each [Cd(COO)]2 cluster links four sdb2- anions to form infinitely ABAB stacked 2D wave-like sheets, in which each sheet contains the same helical chains, and the helical directions of sheets A and B are reversed. Dpb links the rest coordinated sites of [(COO)Cd]2 cluster to form a 2D network. In addition, the solid fluorescence of 1 and dpb is also studied.     

一维链状2-氧-1(4H)-吡啶乙酸桥联钙配位聚合物[Ca(2-OPA)_2(H_2O)_2]_n的合成、晶体结构及热稳定性研究

由于吡啶乙酸及其衍生物具有多种的键合模式和广泛的生物学特性,近十年来由其与金属离子所形成的配合物研究已引起了人们的极大关注[1]。目前的研究多集中于过渡金属和稀土金属离子体系[2￣5],而对于主族金属离子所形成的配合物报道较少。镁钙离子在调节细胞壁的功能、控制半透     

Synthesis and Crystal Structure of a 2D Coordination Polymer： [Nd2（PDB）2（CH3COO）2（H2O）3]

A novel coordination polymer [Nd2（PDB）2（CH3COO）2（H2O）3] （H2PDB = pyridine3,4-dicarboxylic acid） has been synthesized by the reaction of Nd（CH3COO）3 with pyridine3,4-dicarboxylic acid under hydrothermal conditions. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the composition and crystal structure of the title complex which belongs to the triclinic system, space group P^-1 with a = 6.9409（14）, b = 7.5497（15）, c = 22.530（5）A, α = 84.79（3）, β = 88.15（3）, γ= 75.55（3）^o, C18H18N2O15Nd2, Mr = 790.82, Z = 2, V = 1138.5（4） A^3, Dc = 2.307 g/cm^3,μ = 4.593 mm^-1, -6≤h≤8, -5≤k ≤8, -26≤l≤ 26, F（000） = 760, Rint = 0.0298, R= 0.0314 and wR= 0.0695 （I〉 2σ（I））. Nd（1） and Nd（2） are linked into zigzag chains by carboxylate groups of acetate with interesting μ3-η^2：η^2 fashion. The zigzag chains are bridged by PDB to form a 2D framework, and a 3D supramolecular network is further constructed via π-π stacking.     

一维链状铜配位聚合物[Cu(m-BDOA)(bipy)·H2O]n的合成与晶体结构

A novel coordination polymer, [Cu(m-BDOA)(bipy)·H₂O]_n (m-BDOA^2-=benzene-1,3-dioxyacetate), was synthesized and characterized by elemental analysis, IR spectra, X-ray single crystal structure analysis. Crystallographic data are as follows: orthorhombic, space group Pna2₁, a=1.606 9(3) nm, b=1.685 9(3) nm, c=0.699 7(1) nm, V=1.8955(7) nm³, Z=4, D_c=1.619 g·cm^-3, μ=1.200 mm^-1, F(000)=948,R=0.038 1, wR=0.038 6. The copper atom is five-coordinated involving two oxygen atoms of different m-BDOA^2- ligand, two nitrogen atoms of 2,2′-bipy ligand and one coordinated water, there is a distorted square pyramidal environment. Two copper atoms are bridged by m-BDOA^2- ligand, forming a one-dimensional chain along a axis. The adjacent distance of Cu…Cu atoms is 0.877 3nm. The crystal network was formed by the intermolecular hydrogen bond and π-packing interactions.     

The double‐stranded ladder‐like structure of poly[[bis(μ2‐acetato‐κ2O:O′)bis(acetato‐κO)bis(μ‐4,4′‐bipyridine‐κ2N:N′)dicopper(II)] 4‐nitrophenol disolvate tetrahydrate]

The reaction of 4,4′‐bipyridine with copper acetate in the presence of 4‐nitrophenol led to the formation of the title compound, {[Cu(CH₃COO)₂(C₁₀H₈N₂)]·C₆H₅NO₃·2H₂O}_n. The complex forms a double‐stranded ladder‐like coordination polymer extending along the b axis. The double‐stranded polymers are separated by 4‐nitrophenol and water solvent molecules. The two Cu^II centres of the centrosymmetric Cu₂O₂ ladder rungs have square‐pyramidal coordination environments, which are formed by two acetate O atoms and two 4,4′‐bipyridine N atoms in the basal plane and another acetate O atom at the apex. The ladder‐like double strands are separated from each other by one unit‐cell length along the c axis, and are connected by the water and 4‐nitrophenol molecules through a series of O—H...O and C—H...O hydrogen‐bonding interactions and two unique intermolecular π–π interactions.     

新型苯二甲酸和咪唑衍生物构筑的混配型镉配位聚合物的合成及其热稳定性

以硝酸镉、4-硝基邻苯二甲酸(4-NPAH2)和1,4-二咪唑二甲苯(1,4-bimb)为原料,通过水热反应合成了一个新的混配型配位聚合物{[Cd(4-NPA)(1,4-bimb)0.5]n(1)},其结构和热性能经IR,元素分析,X-射线单晶衍射及TGA表征。1属三斜晶系,P-1空间群,晶胞参数a=7.587(2),b=9.696(3),c=10.376(3),α=87.059(3)°,β=77.998(3)°,γ=89.859(3)°,V=745.6(4)3,Z=2,Dc=1.963 g·cm-3,μ=1.506mm-1,F(000)=434,R1=0.028 6,wR2=0.071 1。中心Cd(Ⅱ)与来自三个4-NPA2-配体的五个氧原子以及一个1,4-bimb分子的一个氮原子构成一个扭曲的八面体构型{Cd O5N}单元。两个相邻的八面体单元通过边共享的方式连接进而通过羧酸基团沿着a-轴方向形成一维双链结构。1,4-bimb分子采用顺式方式桥联相邻双链的Cd(Ⅱ)在ac-平面上形成zigzag层状结构。1的初始分解温度约310℃。