Synthesis and crystal structure of a novel tartrate copper(II) two-dimensional coordination polymer: {[Cu2(C4H4O6)2(H2O)2]·4H2O}∞

A new 2D coordination polymer, {[Cu₂(C₄H₄O₆)₂(H₂O)₂]·4H₂O}_∞ has been synthesized by the hydrothermal method and characterized by X-ray single crystal diffraction. Every copper(II) atom adopts a distorted octahedral geometry and coordinates with six oxygen atoms from one water molecule and three tartrate acid ions. The two tartrate acid ions have different coordination modes, one provides four oxygen atoms to coordinate with Cu(II) and another coordinates with all six oxygen atoms. Such a coordination mode generates a two-dimensional coordination polymer. In the solid state, the title compound forms a 3D network structure through hydrogen bonds.     

Synthesis, crystal structure, and interaction with DNA of a novel coordination polymer: {[Cd(Pmal)(Bipy)] · 4H2O} n

A novel coordination polymer {[Cd(Pmal)(Bipy)] · 4H₂O} _n (I), where Bipy = 2,2??-Bipyridine, Pmal = phenethylmalonate, has been synthesized and characterized using IR, ¹H NMR, elemental analysis, and single-crystal X-ray diffractometry. The unit cell parameters for complex I: a = 12.3752(15), b = 6.8283(9), c = 13.4739(17) ?, ?? = 91.108(2)°, V = 1138.4(2) ?³, Z = 2, space group P2₁. The binding of complex I with fish sperm DNA (FS-DNA) was investigated by fluorescence spectroscopy, showing that the complex has the ability of interaction with DNA. Gel-electrophoresis assay demonstrates the ability of complex I to cleave the pBR322 plasmid DNA.     

Preparation,characterization, and properties of a Ag(I) coordination polymer {[Ag(H3bptc)(bpe)] · 2H2O} n

A new coordination polymer, {[Ag(H₃bptc)(bpe)]?·?2H₂O} _n (1) (H₄bptc?=?3,3′,4,4′-benzophenonetetracarboxylic acid, bpe?=?1,2-bis(4-pyridyl)ethene), has been synthesized through a hydrothermal technique and structurally characterized. The crystal structure of 1 exhibits a 2-D hydrogen-bonding sheet between H₃bptc^? and two free water molecules. Fluorescent property, TG analysis, and X-ray powder diffraction for 1 were also measured and discussed.     

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.     

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.     

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.     

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.     

Hydrothermal synthesis and characterization of LaIII and CuII coordination polymers with 5-nitroisophthalic acid (H2Nip), [La2(μ-Nip)(μ-SO4)2(H2O)5] n and {[Cu3(μ-OH)2(μ-Nip)2(μ-H2O)2] · 2H2O} n

3D La^III and 2D Cu^II coordination polymers with 5-nitroisophthalate anions, [La₂(μ-Nip)(μ-SO₄)₂(H₂O)₅] _n (1) and {[Cu₃(μ-OH)₂(μ-Nip)₂(μ-H₂O)₂] ·?2H₂O} _n (2), have been synthesized, characterized and studied by X-ray crystallography. The La atoms have eight–coordinate geometries in distorted square antiprism environments and the Cu atoms have five- and six–coordinate geometries with distorted square pyramidal and octahedral environments. Self-assembly of these compounds in the solid state occurs through coordination and hydrogen bonding.     

Synthesis,crystal structure and magnetic properties of a 1D coordination polymer[Ni(phth)(phen)(H2O)] n · n H2O

A new one-dimensional coordination polymer [Ni(phth)(phen)(H₂O)] _n ?·?nH₂O was synthesized. The structure was determined by X-ray crystallography revealing that each nickel atom is five-coordinate bridged via phthalate ion to form a zigzag chain. The chains are further linked together via hydrogen-bonding interactions to construct a three dimensional supramolecular network. The magnetic properties of the complex show that there are weak antiferromagnetic interactions between Ni(II) centers.     

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.     

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.     

Copper(II)–malonato coordination frameworks with ethanolammonium cations. Synthesis,spectral, thermal and structural characterization of trans-[Cu(mal)2(meaH)2] and {(deaH)2[Cu(μ-mal)2]·H2O}∞ (meaH=monoethanolammonium,deaH=diethanolammonium and mal=malonate)

Two isomorphous malonato–copper(II) complexes, [Cu(mal)₂(meaH)₂] and {(deaH)₂[Cu(μ-mal)₂]·H₂O}_∞ (meaH=monoethanolammonium, deaH=diethanolammonium and mal=malonate), have been prepared and characterized by elemental analyses, IR, UV–vis, magnetic measurements and single crystal X-ray diffraction. The mononuclear complex crystallizes in the monoclinic space group P2₁/n, with a=8.6630(8) Å, b=7.5122(5) Å, c=11.4390(10) Å, β=95.530(7) and Z=2. The polymeric malonato-bridged copper(II) complex crystallizes in the monoclinic space group P2₁/c, with a=26.5169(14) Å, b=8.2544(5) Å, c=9.5243(5) Å, β=96.256(4) and Z=4. The monomeric complex consists of individual units in which copper(II) sits on the inversion center and is octahedrally coordinated by two bidentate mal and two monodendate meaH ligands. The structural units are joined into the framework by the system of hydrogen bonds. The polymeric complex composed of two-dimensional chains containing the mal bridged [Cu(mal)₂]²⁻ ions and each mal ligand simultaneously exhibits chelating bidentate (at one copper atom) and bridging (at the adjacent copper atom) coordination modes. The intrachain Cu1⋯Cu2 separation is 6.302(4) Å. The deaH cations are not coordinated to copper(II) and occupy the voids of the frame work, together with the lattice water molecules. The IR spectra and thermal decompositions of both complexes are described in detail.     

Synthesis, structural characterisation and thermal decomposition studies of some 2,4′-bipyridyl complexes with cobalt(II), nickel(II) and copper(II)

2,4-Bipyridyl (2,4-bipy orL) complexes with cobalt(II), nickel(II) and copper(II) of the formulae M(2,4-bipy)₂(CH₃COO)₂·2H₂O (M(II) = Co, Ni, Cu), Co(2,4-bipy)₂SO₄·3H₂O or Ni(2,4-bipy)₂SO₄·4H₂O have been prepared and their IR and electronic (VIS) spectra are discussed. The thermal behaviour of the obtained compounds has also been studied. The intermediate products of decomposition at different temperatures have been characterized by chemical analysis and X-ray diffraction.We thank dr. A. Malinowska for performing VIS spectra. This work was supported by the KBN project No. PB 0636/P3/93/04.     

Synthesis and Crystal Structure of a Nitronyl Nitroxide Complex {[Zn(NIT4Py)(fum)(H2O)2]·H2}n

The title compound {[Zn(NIT4Py)(fum)(H2O)2]·H2O}n, where N1T4Py=2-(4'-pyridinyl)-4,4,5,5-tetra-methylimidazoline-l-oxyl-3-oxide and rum=fumarate, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1 with a =6.9533(9), b=9.805(1), c=15.248(2)A, a=94.608(2), β=92.328(2),γ=105.840(2)°,C16H24N3O9Zn, Mr=467.75, V=994.8(2) A3, Z=2, Dc=1.562 g/cm3,μ(MoKa)=1.289 mm-1,F(000)=486, the final R=0.0243 and wR=0.0622 for 3505 independent reflections with Rint=0.0125. The Zn(Ⅱ) adopts a distorted five-coordinate triangle bipyramidal geometry. The basic framework structure of the complex is a 1-D chain. The intrachain hydrogen bonds are helpful to stabilize the 1-D chain structure. Furthermore, the chains are connected by O-H…O hydrogen bonds to give a 2-D double-layer network.     

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.     

Synthesis,Structure,Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[Cd[μ-(4,4'-dps) ]2(H2O)2]·(4-abs )2(H2O)2}n

A new cadmium(Ⅱ) compound,{[Cd[μ-(4,4'-dps) ]2(H2O)2]·(4-abs )2(H2O)2}n1(4,4'-dps=4,4'-dipyridylsulfide,4-abs=deprotonated 4-amino benzenesulfonic acid),has been synthesized and structurally characterized.It belongs to the orthorhombic system,space group Pbcn with a=19.950(3),b=10.6381(13),c=18.055(2) A,V=3831.8(8) A3,Z=4,C32H36CdN6O10S4,Mr=905.31,F(000)=1848,μ=0.850 mm-1,Dc=1.569 Mg/m3,the final R=0.0238 and wR=0.0589 for 3080 observed reflections with I > 2σ(I).Complex 1 is a one-dimensional linear chain coordination polymer and the repeat unit is comprised of doubly charged cadmium complex cation,uncoordinated 4-aminobenzene sulfonate anions and water molecules.The cadmium(Ⅱ) ion adopts a six-coordinate distorted octahedral geometry.Complex 1 is stabilized and linked into a three-dimensional layered structure through intermolecular O-H…O and N-H…O hydrogen bonds together with electrostatic force.The cyclic voltammograms and fluorescence spectrum of 1 were also measured.It shows one irreversible redox process and emits a very strong and sharp fluorescent band at about 341 nm.     

Synthesis, crystal structure, and fluorescence properties of a novel coordination polymer [Zn(L)(4,4′-bipyridine)(H2O)] n · (H2O)4

In this work, a novel and rare coordination polymer, [Zn(L)(Bipy)(H₂O)] _n · (H₂O)₄ (H₂L??sphenylpropylmalonate acid, Bipy??4,4??-bipyridine), has been synthesized and characterized by elemental analysis, FT-IR spectroscopy, and solid fluorimetry studies. In the crystal, the Zn²⁺ ion of the complex is hexacoordinated in a slightly distorted octahedral configuration forming the unit structure, 2D structure, and 3D framework. The supramolecular architecture was constructed by a unit of (H₂O)₄ discrete water cluster. Besides, the coordination polymer displays strong emission spectra due to the metal-to-ligand charge-transfer transition, having potential applications as fluorescent materials.     

Synthesis,Crystal Structure,and Magnetic and Water-induced Reversible Transformation Properties of {[Ni(IBG)(μ-H_2O)(H_2O)_2]·2H_2O}_n

A novel NiⅡ complex {[Ni(IBG)(μ-H2O)(H2O)2]·2H2O}n 1(H2IBG = isophthaloylbisglycine) has been synthesized and characterized by single-crystal X-ray diffraction,elemental analysis,IR spectra,and thermogravimetric analysis.It crystallizes in monoclinic,space group P2/c with a = 15.40(2),b = 6.960(10),c = 7.865(11) ,β = 90.32(3)o,V = 843(2) 3,Z = 2,C12H18NiN2O11,Mr = 424.99,Dc = 1.675 g/cm3,F(000) = 440,μ(MoKα) = 1.214 mm-1,the final R = 0.0514 and wR = 0.1247 for 1078 observed reflections with I 2σ(I).In the structure,each NiⅡcenter is situated in the center of a rather regular octahedron.Moreover,thermal stability has been studied and magnetic measurements show antiferromagnetic interactions for this complex.