Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]· [Co_2(4,4'-bipy)3O(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2 and [Co(4,4'-bipy)_2(H_2O)_4]DSNT'4,4'-bipy

Two new cobalt(Ⅱ) supramolecular complexes [Co(4,4'-bipy)_2(H_2O) _4]·[Co_2(4,4'-bipy)3-(H_2O) _8]·2TST-2(4,4'-bipy)·4H_2O 1 and [Co(4,4'-bipy) _2(H_2O) _4]DSNT·4,4'-bipy 2 based upon the assembly of Co(Ⅱ), 4,4'-bipyridine (4,4'-bipy) and two new multifunctional organic ligands, 2,4,6-tris(4-sulfophenyl-amino)-1,3,5-triazine (H_3TST) and 2,4-bis(p-sulfanilato)-6-diethylamino-1,3,5-triazine (H_2DSNT), have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P2_(1/n) with α= 13.599(4), b = 18.988(6), c = 22.995(7) A, β = 90.273(6)°, V= 5938(3) A~3, Z = 4, C_(56)H_(59)CO_(1.5)N_(13)O_(17)S_3, M_r = 1370.74, D_c = 1.533 g/cm~3,μ = 0.613 mm~(-1), F(000) = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I > 2o(I). The crystal structure of 2 belongs to the monoclinic system, space group C2/c with α = 18.864(6), b = 14.283(5), c = 20.246(7) A, β = 107.799(6)°, V = 5194(3) A~3, Z = 4, C_(49)H_(52)CoN_(12)O_(10)S_2, M_r = 1092.08, D_c = 1.397 g/cm~3, μ= 0.480 mm~(-1), F(000) = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I> 2σ(I). The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

配位聚合物[Mn(4,4′-bpy)_(1.5)(H_2O)_3](ClO_4)·(4,4′-bpy)(L)·H_2O的水热合成和晶体结构(英文)

The title compound, [Mn(4,4'-bpy)1.5(H2O)3](ClO4)·(4,4'-bpy)(L)·H2O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm3, Z=2, Mr=780.10, Dc=1.375 g·cm-3, μ=0.483 mm-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4'-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4'-bipyridine molecules. CCDC: 615707.     

Hydrothermal synthesis and structure characterization of a new organic–inorganic composite (4,4′-H2bipy)2(4,4′-hbipy)2(ZnW12O40)·6H2O

A new organic–inorganic composite (4,4′-H₂bipy)₂(4,4′-Hbipy)₂(ZnW₁₂O₄₀)·6H₂O has been prepared by hydrothermal reaction and characterized by elemental analysis, IR and UV spectra, thermal analysis and single-crystal X-ray structural analysis. It belongs to the monoclinic system, space group P2₁/c, with a?=?18.637(4), b?=?14.003(3), c?=?26.470(5)?Å, β?=?104.78(3)°, V?=?6680(2)?ų, Z?=?4. Structural analysis indicates that the title complex consists of a Keggin anion [ZnW₁₂O₄₀]^6?, 4,4′-bipyridine and water of crystallization, constructing a supramolecular system through hydrogen bonding interactions. Thermal analysis shows that the heteropolyanion [ZnW₁₂O₄₀]^6? starts to decompose at 587.0°C.     

Synthesis, Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate: [Co(4,4'-bipy)2(H2O)4](4,4'-H2bipy)2[H2W12O40]·5.5H2O

A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'- H2bipy)2[H2W12O40]·5.5H2Ohas been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses, IR and UV spectroscopy, and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic, space group C2/c, with a = 21.315(9), b = 15.303 (7), c = 24.139(10) (A), β = 105.170(5)o, V = 7599(6) (A)3, Mr = 3706.99, Z = 4, F(000) = 6616, Dc = 3.231, μ = 18.395 mm-1, R = 0.0652 and wR = 0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2 cation, two diprotonated 4,4'-bipyridine molecules, 5.5 water molecules of crystallization, and one metatungstate polyoxoanion [H2W12O40]6-, which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.     

超分子化合物[M(4,4''''-bipy)2(H2O)4]·(4,4''''-bipy)2·(3,5-diaba)2·8H2O](M=Co,Ni,Cd)的合成及晶体结构

合成了3个超分子化合物[M(4,4'-bipy)2(H2O)4]·(4,4'-bipy)2·(3,5-diaba)2·8H2O(M=Co(1),Ni(2),Cd(3);4,4'-bipy=4,4'-联吡啶;3,5-diaba=3,5-二氨基苯甲酸阴离子),用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系,空间群为P2/c。晶体学参数:化合物1:a=0.9389(2)nm,b=0.7751(1)nm,c=3.9284(6)nm,β=90.14(2)°,V=2.85880(69)nm3,Z=4,Dc=1.397g·cm-3,F(000)=1266,μ=0.380mm-1,R1=0.0349,wR2=0.0829;化合物2:a=0.9383(2)nm,b=0.7753(1)nm,c=3.9218(6)nm,β=90.09(1)°,V=2.85280(68)nm3,Z=2,Dc=1.399g·cm-3,F(000)=1268,μ=0.420mm-1,R1=0.0366,wR2=0.0805;化合物3:a=0.94091(13)nm,b=0.77885(11)nm,c=3.9712(5)nm,β=90.10°,V=2.9102(7)nm3,Z=2,Dc=1.433g·cm-3,F(000)=1308,μ=0.454mm-1,R1=0.0468,wR2=0.0964。3,5-diaba未参与配位,在配位阳离子[M(4,4'-bipy)2(H2O)4]2 中,金属离子M髤与来自2个4,4'-bipy的2个氮原子和4个水分子的氧原子配位,呈八面体的几何构型。分子中还存在未配位的4,4'-bipy。通过配位阳离子、游离4,4'-bipy及未配位的3,5-diaba间的丰富氢键,构建成具有三维结构的超分子化合物。     

｛[Co(4,4′-bipy)(ambdc)(H_2O)_2](4,4′-bipy)(DMF)｝_n合成与晶体结构

近年来,取代在5位上的间苯二甲酸(取代基为:-SO3H,-NH2,-OH,-NO2等)衍生物与过渡金属形成的配位聚合物,由于其具有新奇的结构,而且是潜在的功能材料而备受关注[1￣4]。Yaghi等人认为,取代基对配位聚合物的结构和性能具有重要的修饰作用[5]。因此我们在研究5-硝基间苯二甲酸、5-羟基间苯二甲酸与过渡金属形成的配位聚合物结构的同时[6,7],选择了5-氨基间苯二甲酸作为酸性配体,氨基不仅能用其氮原子与金属配位,还能形成氢键,能够提供丰富的配位方式。我们曾经报道了｛[Co(4,4′-bipy)(hmbdc)(H2O)2](4,4′-bipy)(DMF)｝n的合成与结构[8…     

配位聚合物{[Co(4,4''''-bpy)(H2O)4](Fum)·4H2O}n的合成和晶体结构

0引言近年来,利用晶体工程方法设计、裁剪和组装具有一维、二维和三维有序超分子结构的配位聚合物引起了人们极大的兴趣,并成为材料科学和化学学科中最活跃的研究领域之一[1~3]。在超分子结构设计方面,利用过渡金属借助配体配位作用引导的自组装已成为一个热点。其中多联吡啶类     

A new ZnII two-dimensional coordination polymer, {[Zn(μ-4,4′-bipy)(1,4-ndc)(H2O)2] · (H2O)} n (4,4′-bipy= 4,4′-bipyridine and 1,4-ndc=1,4-naphthalenedicarboxylate)

A 2D Zn^II(μ-4,4′-bipy) coordination polymer with 1,4-naphthalenedicarboxylate, {[Zn(μ-4,4′-bipy)(1,4-ndc)(H₂O)₂] · (H₂O)} _n , has been synthesized, characterized and studied by X-ray crystallography. The structural studies show the Zn atoms have six-coordinate geometry with a distorted octahedral environment. The 2D structure is grown by hydrogen bonds into a hybrid three-dimensional network.     

氢键构筑的新颖微孔配位聚合物[Co2(Hisor)2·(4,4''-bpy)2(H2O)2]·4,4''-bpy的合成与结构

近年来,微孔配位聚合物的研究越来越引起人们的重视.与传统的微孔材料硅酸盐、硅铝酸盐、磷铝酸盐等相比,微孔配位聚合物具有独特的优势:一方面,可以将金属离子所特有的磁学、光学、电学和氧化-还原等特性引入所设计合成的配位聚合物中;     

Structure of Coordination Polymer,[Zn (bipy) (H2O) 3SO4] · 2H2O (bipy = 4,4'-bipyridine)

The crystal of the title compound (C10H18N2O9SZn Mr= 407. 69) belongs to the hexagonal system, space group P65 with cell parameters: a= 11. 411(2), c=20. 908(4) A, V=2357.7(7)A 3, Z=6, Dc=1. 723g/cm3, F(000)=1260,μ(MoKα) =1. 743mm-1. The final R and wR factors are 0. 072 and 0. 178 respectively for 1335 observed reflections. In the structure, zinc ions are bridged by 4,4'-bipyridine to form infinite chains. The sheets containing parallel chains stack along a 65 screw axis to give a helical staircase motif. The helical structure is mainly controlled by the hydrogen bonds.     

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.     

(4,4′-bipy H)_3[PW_12O_(40)](4,4′-bipy)·7H_2O的水热合成、晶体结构与热性质

用中温水热技术合成了(4,4′-bipyH)3[PW12O40](4,4′-bipy).7 H2O,用元素分析、X射线单晶衍射、IR、UV-vis和TG-DTA对其进行了表征.结果表明,化合物的晶体属单斜晶系,P2(1)/c空间群.标题化合物是由3个质子化的4,4′-bipy分子、一个Keggin结构的钨磷杂多阴离子[PW12O40]3-和一个4,4′-bipy分子及7个结晶水分子所组成.钨磷杂多阴离子与质子化的联吡啶及结晶水分子之间通过氢键作用,连接成无限二维层状结构,形成超分子化合物.     

Building hydrogen-bonded networks from metal complexes containing the heterotopic (N or O) ligand 4,4′-bipyridine-N-monoxide

The heterotopic ligand 4,4′-bipyridine-N-monoxide (BIPYMO) has a rigid, linear structure and contains both a pyridine N-donor and a pyridine-N-oxide O-donor which are capable of coordinating to a metal centre or alternatively acting as a hydrogen bond acceptor. The hydrogen bonding capacity of BIPYMO is first demonstrated by the formation of hydrogen-bonded networks with water and some simple dicarboxylic acids (fumaric = FUM, terephthalic = TPA). It is then shown that BIPYMO can coordinate through the pyridine N-donor to Pd(II) and through the pyridine-N-oxide O-donor to Fe(II), Co(II) and Mn(II). In each case, the peripheral, uncoordinated N- or O-atoms act as a hydrogen bond acceptors and interact with a metal-bound and hydrogen bond donor (H₂O, fumarate = FUM, malonate = MAL, isophthalate = IPA) to form a solid-state, network through a combination of metal–ligand coordination and hydrogen bonding. Single-crystal X-ray structures of {(BIPYMO)(H₂O)₂}_n, {(BIPYMO)(FUM)}_n, {(BIPYMO)(TPA)}_n, {[Pd(BIPYMO)₂(MAL)₂](H₂O)}_n, {[Pd(BIPYMO)₂(IPA)₂](H₂O)₂}_n and {[M(BIPYMO)₂(FUM)₂(H₂O)₂]}_n (M = Mn, Fe, Co), show how the individual building blocks are organised via hydrogen bonding through uncoordinated pyridine N-atoms or pyridine-N-oxide O-atoms to form supramolecular networks.     

Hydrothermal synthesis and structural characterization of a new one-dimensional ladder-shaped metal-organic framework Zn(HTci)(4,4′-bipy)0.5 · H2O (H3Tci = tri(2-carboxyethyl)isocyanurate, 4,4′-bipy = 4,4′-bipyridine)

A new metal-organic coordination polymer, namely, Zn(HTci)(4,4′-Bipy)_0.5 · H₂O (I) (H₃Tci = tri(2-carboxyethyl)isocyanurate, 4,4′-Bipy = 4,4′-bipyridine), has been synthesized under hydrothermal conditions by the reaction of zinc nitrate, H₃Tci, and 4,4′-Bipy with the presence of H₂O and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the triclinic system, $P\bar 1$ space group. The unit cell parameters for I: a = 5.248(1), b = 12.537(2), c = 14.597(2) Å, α = 91.91(1)°, β = 91.22(2)°, γ = 95.75(1)°, V = 954.8(3) ų, Z = 2.     

Two new Pb(II) coordination polymers, [Pb2(μ-4,4′-bipy) (μ-2-sb)2(DMF)] n and {[Pb2(μ-4,4′-bipy) (μ-2-sb)2(H2O)2] · H2O} n (4,4′-bipy = 4,4′-bipyridine and 2-H2sb = 2-sufobenzoic acid)

Two new 2D Pb₂(μ-4,4′-bipy)(μ-2-sb)₂ coordination polymers, [Pb₂(μ-4,4′-bipy)(μ-2-sb)₂(DMF)] _n (1) and {[Pb₂(μ-4,4′-bipy)(μ-2-sb)₂(H₂O)₂] · H₂O} _n (2), have been synthesized, characterized and studied by X-ray crystallography. The structural studies show the Pb atoms to have seven- and eight-coordinate holodirected geometries.     

配合物[Mn(4,4′-bipy)_2(H_2O)_4](HtsgluO)_2·2H_2O的合成及性质研究

<正>金属-有机框架材料(MOFs)是一类具有高度结晶性的配位聚合物,具有很好的稳定性、大的空穴体积和尺寸均一可调的孔洞。近年来,由于其在储氢、分离以及固相催化方面的潜在应用而引起人们的广泛兴趣[1-4]。MOFs的合成条件温和,可以通过选择合适金属离子和有机配体使之更符合特定性能的要求,即金属离子和有机配体的选择是关键。一     

Synthesis and crystal structures of 3D supramolecular compounds: [ M (4,4′-bipy)2(H2O)4] · (4,4′-bipy)2 · (3,5-daba)2 · 8H2O ( M =Zn,Mn)

Two new supramolecular compounds [M(4,4′-bipy)₂ (H₂O)₄] ·?(4,4′-bipy)₂ ·?(3,5-daba)₂ ·?8H₂O (M=Zn(1) or Mn(2), 4,4′-bipy =?4,4′-bipyridine, 3,5-daba =?3,5-diaminobenzoic acid anion) were synthesized and characterized by elemental analysis and X-ray crystal diffraction. In [M(4,4′-bipy)₂(H₂O)₄]²⁺, the M(II) is coordinated by two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four waters to form an octahedral configuration. There exist uncoordinated 4,4′-bipy molecules, 3,5-diaminobenzolate counterions and water guests in the compounds. The 3D structures of the title supramolecular compounds are constructed by rich hydrogen bonds among [M(4,4′-bipy)₂(H₂O)₄]²⁺, uncoordinated 4,4′-bipy molecules, water molecules and 3,5-daba, containing a diverting hexa-member water ring.     

Co(μ2-bpy)V2O6(bpy=4,4′-联吡啶)的水热合成和晶体结构

采用CoCl2·6H2O、4,4′-联吡啶和NH4VO3,以H2O作溶剂(摩尔比1:2:2:1950)在170℃下水热反应合成无机-有机杂化化合物Co(μ2-bpy)V2O6(bpy=4,4′-联吡啶),经单晶X射线衍射测定其晶体结构.此晶体属三斜晶系,空间群为Pi,晶胞常数a=0.81599(7)nm,b=0.85826(7)nm,c=1.02031(8)nm,α=87.111(2)°,β=75.305(2)°,y=74.784(2)°,Z=2.Co(μ2-bpy)V2O6是无机的双金属氧化物层,[Co2V4O12]n通过有机的桥式配体μ2-bpy以N-Co配位键桥联而成.晶体的三维共价结构含有多种开放式孔道,其中最大孔道的尺寸为0.5nm×0.7nm.漫反射光谱研究表明,此晶体具有约2.0 eV的光学能隙,属于半导体,在420℃以下是热稳定的.     

Co(μ2-bpy)V2O6 (bpy =4,4′-联吡啶)的水热合成和晶体结构

采用CoCl2•6H2O、4,4′-联吡啶和NH4VO3,以H2O作溶剂（摩尔比1∶2∶2∶1950）在170 ℃下水热反应合成无机-有机杂化化合物Co(μ2-bpy)V2O6 (bpy=4,4′-联吡啶), 经单晶X射线衍射测定其晶体结构.此晶体属三斜晶系,空间群为Pī,晶胞常数a=0.81599(7) nm,b=0.85826(7) nm, c=1.02031(8) nm,α=87.111(2)°, β=75.305(2)°,γ=74.784(2)°, Z=2. Co(μ2-bpy)V2O6是无机的双金属氧化物层,[Co2V4O12]n通过有机的桥式配体μ2-bpy以N－Co配位键桥联而成.晶体的三维共价结构含有多种开放式孔道,其中最大孔道的尺寸为0.5 nm×0.7 nm.漫反射光谱研究表明,此晶体具有约2.0 eV的光学能隙,属于半导体,在420 ℃以下是热稳定的.