Unique seven-node rare-earth octacyanomolybdate(IV) three-dimensional molecular frameworks: {[Er(H2O)5(Er(H2O)4)3][Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu(H2O)4)3][Mo(CN)8]3·11H2O}n

The crystal structure analyses of {[Er(H₂O)₅(Er(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (1) and {[Eu(H₂O)₅(Eu(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (2), show that they are not only new neutral three-dimensional rare-earth octacyanomolybdate(IV) molecular frameworks, but that they also belong to an unknown structure type having seven different nodes. To the best of our knowledge this is different to any other known molybdenum(IV) octacyanide complexes published to date. Both compounds crystallize in the triclinic system, space group P-1, and are isostructural and isotypic. The coordination polyhedra of the molybdenum atoms in the three different [Mo(CN)₈]⁴⁻ anions are trigonal prisms, with two additional atoms. A new bridging mode for octacyanometallates is also observed with five of the eight cyanide groups involved in bridging either three or four rare-earth atoms, while the three remaining cyanide groups are terminal and are involved in hydrogen bonding. The four rare-earth atoms in 1 and 2 have different coordination polyhedra in the form of trigonal prisms with two additional atoms. The three-dimensional structures are made up of infinite two-dimensional slabs linked by one of the rare-earth metal atoms. In both compounds, apart from the 17 coordinated water molecules, there are 11 lattice water molecules of crystallization present in the cavities of the three-dimensional frameworks. The 28 water molecules and the terminal CN⁻ groups are involved in an extensive O–H⋯O and O–H⋯N hydrogen bonding network.     

A polyoxoniobate based on dimeric hexanionbate: [Cu(en)2]4{[Nb6O19H2]K(H2O)5}2 · (H2en) · 17H2O

A polyoxoniobate, [Cu(en)₂]₄{[Nb₆O₁₉H₂]K(H₂O)₅}₂ ? (H₂en) ? 17H₂O (en = ethylenediamine) (1), has been synthesized and characterized by elemental analysis, IR, XPS, TGA, and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a = 12.3533(16) Å, b = 12.7188(16) Å, c = 29.626(4) Å, α = 93.235(2)°, β = 96.094(1)°, γ = 106.098(2)°, V = 4429.0(10) ų, Z = 2. The polyoxoanion is composed of a Lindqvist-type [Nb₆O₁₉H₂]^6? dimer bi-bridged via two K⁺. K⁺ is 10-coordinate with 10 oxygens, three from one [Nb₆O₁₉H₂]^6?, one from a terminal oxygen of another [Nb₆O₁₉H₂]^6? moiety, and the other six from water molecule. Adjacent dimeric polyoxoanions are linked to form an infinite 1-D chain via O–H ··· O hydrogen-bonding interactions which exist between the two water trimers and the dimeric polyoxoanions.     

A porous metal-organic framework (MOF) with unusual 2D→3D polycatenation based on honeycomb layers

A novel mixed-ligand 3D metal-organic framework (MOF), {Zn(2)(TMTA)(bipy)(0.5)(H(2)O)(2)·NO(3)·2DMF·H(2)O}(n) (1) (H(3)TMTA = 4,4',4'-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoic acid, bipy = 4,4'-bipyridine, DMF = dimethylformamide), was constructed based on bipy-pillared honeycomb bilayers and showed the unusual 2D→3D polycatenation of bilayers.     

Synthesis and crystal structure of a three-dimensional 3d-4f heterometallic coordination polymer {[Sm2Ni(Pdc)2(SO4)2(H2O)6] · H2O} n

A new 3d-4f coordination polymer {[Sm₂Ni(Pdc)₂(SO₄)₂(H₂O)₆] · H₂O} _n (H₂Pdc = pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions and structurally determined by X-ray diffraction method. The X-ray diffraction analysis reveals the compound crystallizes in the triclinic system, space group $P\bar 1$ , with a = 10.062(4), b = 10.249(4), c = 12.744(5) Å, α = 93.548(4)°, β = 102.601(4)°, γ = 94.022(3)°, V = 1275.4(8) ų, F(000) = 972, M _r = 1077.85, Z = 2, ρ _c = 2.624 g cm^?3, μ = 5.55 mm^?1, final R = 0.0299, wR = 0.0805 for 4716 independent reflections with R _int = 0.0204. According to the structure determination the complex is a three-dimensional (3D) network structure in which infinite lanthanide-carboxylate chains are linked by [Ni(SO₄)₂]^2? metalloligands to form a mixed-metal coordination network.     

一维梯状配合物{[Cu2(4,4''-bpy)3(p-Ab)2(H2O)2]·(NO3)2·4H2O}n的晶体结构

合成了一维分子梯状配合物{[Cu2(4,4'-bpy)3(p-Ab)2(H2O)2]·(NO3) 2·4H2O}n(4,4'-bpy=4,4'-联吡啶,p-Ab-=对氨基苯甲酸根离子),该配合物晶体属单斜晶系,P2(1)/c空间群,晶胞参数:a=1.110 7(5) nm,b=1.550 4(3) nm,c=1.450 9(3) nm,β=104.81(3)°,V=2.415 5(12) nm3,Z=2.铜离子周围有3个氧原子和3个氮原子与之配位,其中2个氧原子由对氨基苯甲酸的螯合氧原子提供,另一个氧原子由配位水提供,3个氮原子分别由三个4,4'-联吡啶提供.这六个原子在铜离子周围形成一个畸变的八面体配位环境.配体对氨基苯甲酸只有一种配位形式--双齿螯合,第二配体4,4'-联吡啶的两个氮原子均参与配位,将配合物组装成一维分子梯结构.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Synthesis and Crystal Structure of a Mixed Cu-Cd Bimetallic Complex {[CuCd(pba)(H2O)3]·2H2O}n

A one-dimensional bimetallic compound {[CuCd(pba)(H2O)3]·2H2O}n in which pba was propylenebis (oxamic acid), was prepared. Crystal structure of the title compound was determined. It belongs to orthorhombic system, molecular formula CuCdC7H16N2O11, Mr=480.17, space group Pnma(#62), a=12.953(2), b=21.626(6), c=5.253(3)(A), V=1471(2)(A)3 and Dx=2.17g/cm3 for Z=4. The structure was solved by direct methods with final R=0.052 and Rw=0.063 for 1055 observed reflections with I>3σ(I). Two nitrogen atoms and two oxygen atoms from the oxamide and a water molecule coordinated to the CuII ion forming a square pyramidal geometry. Four oxygen atoms from the oxamide and two water molecules coordinated to the CdII ion forming an elongated octahedral geometry.     

Synthesis and crystal structure of a three-dimensional 3d-4f heterometallic supramolecular complex {Eu(DMF)4(H2O)2Cr(CN)6·;H2O} n

A lanthanide-transition heterometallic supramolecular complex {Eu(DMF)₄(H₂O)₂Cr(CN)₆·H₂O} _n (1) has been synthesized based on the reaction of K₃[Cr(CN)₆], N,N-dimethylformamide (DMF) and Eu(NO₃)₃·6H₂O. 1 crystallizes in the monoclinic space group P2(1)/c with a=13.130(6)Å, b=12.923(7)Å, c=19.184(9)Å and Z=4. In 1 each Eu(III) is eight-coordinate with six oxygen atoms from four DMF molecules and two H₂O molecules and two nitrogen atoms from two cis-bridging CN ligands to form a distorted dodecahedron. 1 has a three-dimensional network created by the incorporation of coordinative linkage, three inter-molecular and an intrachain hydrogen bond.     

ChemInform Abstract: Unique Seven-Node Rare-Earth Octacyanomolybdate(IV) Three-Dimensional Molecular Frameworks: {[Er(H2O)5(Er (H2O)4)3] [Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu (H2O)4)3] [Mo(CN)8]3·11H2O}n.

Good quality single crystals of the title compound are obtained by reaction of H₄[Mo(CN)₈] with the rare earth carbonates.     

配位聚合物{[Co(H2O)6][Co(H2O)4(pmts)]·4H2O}n的合成及晶体结构

以均苯四甲酸(pmts)和CoCl2·6H2O为原料,在碱件水溶液中通过水热法合成了配位聚合物{[Co(H2O)6][Co(H2O)4(pmts)]·4H2O}n,并对其进行了红外、紫外-可见吸收光谱和单品X-射线衍射结构测定.结果表明,Co2+分别与桥配体pmts的1,4位羧基氧及端配体水分子中的氧以轻度畸变的八血体...     

Crystal Structure of a Threedimensional Coordination Polymer {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]·4H2O}n

A novel three-dimensional coordination polymer, {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]·4H2O}n, has been synthesized with oxydiacetate as bridge ligand and structurally determined by X-ray crystallography. The crystal belongs to monoclinic, space group C2/c with a = 17.805(2), b = 9.3923(12), c = 17.255(2)(A), β = 107.838(5)°, V = 2746.8(6) (A)3, Mr = 660.58, C12H28Ca3O23, Dc = 1.597 g/cm3, μ = 0.695 mm-1, Z = 4, F(000) = 1376, GOOF = 1.027, R = 0.0303 and wR = 0.0660. In the complex there are two coordination modes for Ca(Ⅱ) ions, one coordinated by three μ5-OOCCH2OCH2COO2- bridge ligands together with two H2O molecules, and the other by five μ5-OOCCH2OCH2COO2- bridge ligands. In both coordination modes each Ca(Ⅱ) ion assumes a distorted dipentapyramidal CaO7 geometry; whereas each oxydiacetate is coordinated with five Ca(Ⅱ) ions and acts as a pentdentates bridge ligand.     

Synthesis and Crystal Structure of [{Cd(hmbdc)(H2O)3}·2H2O]n

A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ ＞ 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.     

Synthesis and Molecular and Crystal Structure of K4.5{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}I1.5·3H2O and Cs3{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}·2H2O

Crystal structures of two new compounds containing trigonal tellurium-bridged cluster fragments [Mo₃(₃-Te)(₂-Te₂)₃]⁴⁺ were investigated. Crystal data for K_4.5{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}I_1.5·3H₂O: space group , Z = 4, a = 13.280(1), c = 23.800(3) , V = 3635.0(6) ³, d _calc = 3.432 g/cm³, R ₁ = 0.0335, wR2 = 0.0912 for 1378 I _hkl > 2 _I from 3545 measured I _hkl ; for Cs₃{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}·2H₂O: space group P2 ₁ /n, Z = 2, a= 9.650(2) , b = 22.297(5), c = 27.446(7) , = 94.10(2)°, V = 5890(2) ³, d _calc = 4.273 g/cm ³, R ₁ = 0.0384, wR ₂ = 0.0744 for 957 I _hkl > 2 _I from 3758 measured I _hkl (Enraf-Nonius CAD-4 diffractometer, MoK , graphite monochromator). In both compounds, ionic pairs {[Mo₃Te₇(CN)₆]I}^3– with Te_ax...I^– distances of 3.358-3.676 are formed. In the potassium salt, the {[Mo₃Te₇(CN)₆]I}^3– anion pairs are linked by the additional Te_eqI^– short contacts of 3.460 into two-dimensional corrugated layers perpendicular to the c axis of the unit cell. The structure of the cesium salt is ionic with interstitial H₂O molecules and double-layer closest packing of anions.     

Extracting organic contaminants from water using the metal-organic framework CrIII(OH)·{O2C-C6H4-CO2}

The water-stable metal-organic framework MIL-53(Cr) is able to adsorb phenol and p-cresol from contaminated water as well as the monomeric sugar D-(-)-fructose. Based on the isotherm for phenol uptake from the liquid phase, it is proposed that the framework breathes to maximize the uptake.     

一维聚合物{[Co(N3)2(dps)2]·0.5H2O}n的合成,结构和磁性质

A coordination polymer {[Co(N3)2(dps)2]·0.5H2O}n (1) (dps=dipyridin-4-ylsulfane) with one dimensional chains has been synthesized and the structure and magnetic properties were characterized. Complex 1 crystallizes belongs to monoclinic system and has space group P21/c. The CoⅡ ion is six-coordinated and located at a compressed octahedral environment due to the Jahn-Teller effect. The ligand of dps bridges between Co Ⅱ ions producing the infinite chains of Co ? ? ? Co along a direction and, interestingly, four pyridy1 groups of dps ligands form a propeller-shaped coordination geometry around CoⅡ ion with the same spiral within the chain. These 1D chains are further linked through the hydrogen bonds to generate a 3D supermolecular network. Magnetic studies indicated that complex 1 shows very weak antiferromagnetic coupling between CoⅡ ions in low temperature.     

Synthesis and crystal structure of a coordination polymer {[Cu2(L)2(Phen)2] · 8H2O} n

A novel metal coordination polymer, {[Cu₂(L)₂(Phen)₂] · 8H₂O} _n (I), has been synthesized by the reaction of Cu(NO₃)₂ with 2,2′-bipyridyl-4,4′-dicarboxylic acid (L) and 1,10-phenanthroline (Phen) at room temperature. The polymer was characterized by IR, elemental analyses and X-ray diffraction. Single-crystal structural analysis reveals that the center Cu²⁺ ions have two coordinated types. The Cu(1) atom has the five-coordinate mode, and Cu(2) forms an is octahedron of the six-coordinate mode. Two Cu²⁺ ions are connected by the O atom of carboxylate group bridges. Complex I contains eight molecules of water clusters and constructed a 1D tape structure.     

Energetic materials composed of coordination polymers: {[Zn(μ-atrz)3](ClO4)2·2H2O}n and {[Cu(μ-atrz)3](NO3)2·2H2O}n

An improved synthetic pathway for trans-4,4′-azo-1,2,4-triazole (atrz) was discovered. Pure atrz was obtained directly without any other separation step in an environment friendly process. Treatment of atrz with zinc perchlorate and cupric nitrate led to the isolation of {[Zn(μ-atrz)₃](ClO₄)₂·2H₂O}_n and {[Cu(μ-atrz)₃](NO₃)₂·2H₂O}_n, which were well characterized. Their structures were determined by X-ray crystallographic analysis. The calculation results of the formation of {[Zn(μ-atrz)₃](ClO₄)₂ 2H₂O}_n and {[Cu(μ-atrz)₃](NO₃)₂ 2H₂O}_n indicates that the perfect crystal structures in spite of much resistance. A fundamental understanding of the structure and thermal properties involves factors, such as conjugated system, crystal structure, and inorganic metallic compounds that affect their thermal behavior. The high energy of the coordination compounds consists of chemical, electronic, and potential energy. The potential for the improvement of the coordination polymer opens up a new world for research of energetic materials.     

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.     

新型一维链状配位聚合物{[Cu2(dhbd)(bipy)2]·10H2O}n的研究

采用水热法合成了标题配位聚合物{[Cu2(dhbd)(bipy)2]·10H2O}n(H4dhbd=2,3-二羟基丁二酸,bipy=2,2'-联吡啶),通过元素分析、红外光谱、热分析、X射线单晶衍射等技术对其进行了表征.配合物属单斜晶系,空间群C2/c,a=2.1965(4)nm,b=1.0671(2)nm,c=1.3662(3)nm,β=93.50(3)°,Z=4,R=0.0388.晶体的基本构建基元包含10个结晶H2O分子和由两个Cu(Ⅱ)原子、一个采用双二齿螯合配位的2,3-二羟基丁二酸根、两个2,2'-联吡啶形成具有C2旋转轴的U形双核单元,相邻的两个方向相反的U形双核单元通过双羧基O桥联形成沿c轴延伸的一维链;链间籍C-H…O和O-H…O氢键扩展为三维结构.配合物中呈现了一种2,3-二羟基丁二酸与过渡金属配位的新方式.