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.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Synthesis and Crystal Structure of [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O

The title compound, [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O (phen = 1,10-phe-nanthroline and C4H4O4 = fumaric acid), has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P with a = 11.4827(2), b = 11.9086(2), c = 13.77350(10)(A), α = 80.6830(10), β = 66.6480(10), γ = 64.0480(10)o, V = 1554.63(4) (A)3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm3, μ = 0.845 mm-1, F(000) = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections (I > 2σ(I)). The compound contains a six-coordinated copper(II) center, which is surround by four N atoms of two phen ligands (Cu-N distances in the range of 1.997(2)～2.225(2)(A)), one sulfate O atom (Cu-O = 2.0037(17) (A)) and one water O atom (Cu-O(5w) = 2.719(2) (A)) in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

The thermal dehydration and decomposition of Ba[Cu(C2O4)2(H2O)]·5H2O

The thermal behaviour of Ba[Cu(C₂O₄)₂(H₂O)]·5H₂O in N₂ and in O₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311±30 kJ mol^–1 (or 52±5 kJ (mol of H₂O)^–1). The overall enthalpy change for the decomposition of Ba[Cu(C₂O₄)₂] in N₂ was estimated from the combined area of the peaks of the DSC curve as –347 kJ mol^–1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the -time curves could be described by the three dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125±4 kJ mol^–1 and (1.38±0.08)×10¹⁵ min^–1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2.The values ofE _a andA were 206±23 kJ mol^–1 and (2.2±0.5)×10¹⁹ min^–1, respectively, for the fast process, and 259±37 kJ mol^–1 and (6.3±1.8)×10²³ min^–1, respectively, for the slow process.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday     

Synthesis, Crystal Structure, and Photoluminescent and Semiconductive Properties of [La(C6NO2H5)3-(H2O)2]2n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O)

A new heterometallic 4f-5d inorganic-organic metal-isonicotinic acid complex [La(C6NO2H5)3(H2O)2]2n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O) 1 has been synthesized via hydro-thermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell: α= 24.140(7), b = 20.884(7), c = 15.462(2) (A), β = 127.46(1)°,V = 6187(3) (A)3, C36H47Cl13Hg3La2N6O20, Mr = 2224.24, Dc = 2.388 g/cm3, Z = 4, T = 293(2) K, μ(MoKα) = 9.401 mm-1, F(000) = 4160 and R/wR = 0.0376/0.0636 for 4130 observed reflections (I > 2σ(I)) and 5617 unique reflections. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in violet and orange regions. The luminescence spectra show stronger orange emission than violet emission. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap of 3.41 eV.     

Syntheses and Structures of Two New Coordination Polymers:[Cu(C14H9O4)(C14H10O4)(C12H12N2)2] and [Ag(C14H9O4)(C13H14N2)]·0.5 H2O

Under hydrothermal conditions, two new ribbon-like structures, [Cu(C14H9O4)-analysis revealed that these structures were constructed by mixed ligands. The coordination polymer forms the basic architecture while the weak interactions extend the framework into a secondary structure. The whole structures of them are governed by collaboration of the strong and weak interactions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 17.0485(3), b =1 1.0558(3), c = 22.7623(4) A, β = 102.465(1)°, V = 4189.2(2) A3, Z = 4, Mr = 915.44, Dc = 1.451g/mL, F(000) = 1900 andμ(MoKα) = 0.587 cm-1. The final R and wR are 0.0030 and 0.1022,respectively for 3037 observed reflections with I ＞ 2σ(I). Compound 2 crystallizes in monoclinic,space group P21/c with a = 11.5963(4), b = 11.7004(5), c = 17.1254(5) A,β = 95.620(1)°, V =2312.4(1) A3, Z = 4, Mr = 556.35, Dc = 1.598 g/mL, F(000) = 1132 andμ(MoKα) = 0.912 cm-1The final R and wR are 0.0431 and 0.1050, respectively for 2629 observed reflections with I ＞ 2σ(I).     

两个金属铜配位聚合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2和Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)混合溶剂热合成及结构与性能研究

在中温混合溶剂热条件下合成了两个金属铜配位聚合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2和Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)(bipy=联吡啶,C8H4O4=1,3-间苯二甲酸),并对其进行了单晶结构解析及相关性能表征.配合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2(1)晶体属三斜晶系,P1空间群,a=1.03314(4)nm,b=1.08350(3)nm,c=1.15826(4)nm,α=83.104(2)°,β=84.609(2)°,γ=66.125(2)°,Z=1.配合物Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)(2)晶体属三斜晶系,P1空间群,a=1.06979(3)nm,b=1.09209(3)nm,c=1.47887(3)nm,α=91.795(2)°,β=93.2460(10)°,γ=118.6170(10)°,Z=2.通过使用不同的有机碱配体(2,2′-联吡啶和4,4′-联吡啶),并调节不同有机碱配体的用量,得到了结构不同的两个目标晶体产物相.产物均可稳定到3...     

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.     

Synthesis,crystal structure of Gd(H2O)(C2O4)2 · NH4 and of La(C2O4)2 · NH4. Characterization of the Ln(H2O)(C2O4)2 · NH4 with Ln=Eu…Yb

Single crystals of two lanthanide complexes, presenting similar formula Ln(H₂O)_x(C₂O₄)₂ · NH₄ with Ln=La, x=0 and Ln=Gd, x=1, have been prepared, in closed system at 200 °C. The gadolinium complex is bi-dimensional. A layer is built by the packing of the basic unit, [Gd(C₂O₄)]₄. The gadolinium atoms are related only by bischelating oxalate ligands, the ammonium ion and the water molecule (bound to the gadolinium atom) are localized into the interlayer space. The lanthanum complex is tri-dimensional. The basic building unit remains approximately the same and the packing of these units form a layer. However, within these units, the lanthanum atoms are related by either an oxalate ligand or an edge. Moreover, an oxalate ligand assumes the connection between the layers. The ammonium ion is localized into two sets of intersecting channels. Pure phase of the gadolinium complex has been prepared at 100 °C and extended to some lanthanide elements, Eu…Yb. As the size of the lanthanide ionic radius is decreasing, it is noticeable that the a unit–cell constant follows an expansion pattern while the others two follow an usual contraction one. The thermal behavior of this family shows that the anhydrous compounds are obtained and that some water molecule is sorbed during the cooling. Thus, the anhydrous compounds present a relatively open-framework with some small micropores.     

Synthesis and properties of tetraalkylammonium chlorides peroxosolvates (CH3)4NCI·H2O2 and (C2H5)4NCl·H2O2

Tetraalkylammonium chlorides peroxosolvates (CH₃)₄NCl·H₂O₂ and (C₂H₅)₄NCl·H₂O₂ were synthesized. The composition of the solvates was proved by chemical analysis; their X-ray patterns, IR spectra, and thermograms were obtained. The solubility of the solvates in water and their stability in aqueous solutions were investigated.     

超分子化合物[Cu(Phen)(C2O4)H2O]·H2O的合成及结构

邻菲罗啉配合物具有良好的光化学、电化学、催化性质和生物活性[1-4],因而引起了人们的极大关注[5-7]。我们利用Phen和K2[Cu(C2O4)2],通过取代反应合成了标题配合物,并对其进行了结构分析,结果表明,中心铜原子处在五配位的变形四方锥环境中,且晶体中结构单元通过分子间氢键形成     

SYNTHESIS AND CRYSTAL STRUCTURE OF A POLYMERIC 1,2,4,5-BENZENETETRACARBOXYLATO COMPLEX OF Cu(II) WITH IMIDAZOLE,Cu2(C10H2O8)(C3H4N2)6(H2O)4 · 4H2O

Abstract

The title complex, Cu₂(C₁₀H₂O₈)(C₃H₄O₂)₆(H₂O)₄ · 4H₂O, consists of polymeric copper(II) complex anions and discrete copper(II) complex cations. Benzenetetracarboxyl anions bridge copper(II) atoms coordinated to water and imidazole groups to form the anionic polymeric chains along the a axis, while discrete copper(II) complex cations involving four imidazole and two water ligands are packed between parallel polymeric anionic chains, an extensive H-bonding network linking complex cations and anions.     

Molar heat capacity and thermodynamic properties of Lu(C5H9NO4)(C3H4N2)6(ClO4)3·5HClO4·10H2O

A complex of Lutetium perchloric acid coordinated with l-glutaminic acid (C₅H₉NO₄) and imidazole (C₃H₄N₂), Lu(C₅H₉NO₄)(C₃H₄N₂)₆(ClO₄)₃·5HClO₄·10H₂O was synthesized and characterized. Thermodynamic properties of the complex were studied with an adiabatic calorimeter (AC) from 80 to 390 K and differential scanning calorimetry (DSC) from 100 to 300 K. Two thermal abnormalities were discovered at 220.34 and 248.47 K, which were deduced to be phase transitions. One was interpreted as a freezing-in phenomenon of the reorientational motion of ClO₄ ^? ions and the other was attributed to the orientational order/disorder process of ClO₄ ^? ions. The low-temperature molar heat capacities were measured by AC and the thermodynamic functions [H _T  ? H _298.15] and [S _T  ? S _298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior of the complex was studied by thermogravimetric analysis and DSC.     

Synthesis and Structural Characterization of a Novel Coordination Polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O

At room temperature, a new three-dimensional organic-inorganic coordination polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O was synthesized by the reaction of Cd(CH3COO)2(2H2O, imidazole and fumaric acid. It was characterized by EA, IR, TG-DTA and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 8.980(3), b = 15.803(5), c = 13.415(4) (A), α = γ = 90.00°, β = 98.450(5)°, F(000) = 936, Mr = 466.73, Z = 4, V = 1883.0(10) (A)3, Dc = 1.646 g/cm3, μ(MoKα) = 1.201 mm-1, S = 1.041, the final R = 0.0237 and wR = 0.0469. The crystal structure shows that the cadmium has a distorted octahedral environment with three carboxyl oxygen donors and three imidazole nitrogen donors. Each cadmium atom is linked by a fumatate as bridging ligand to afford a one-dimensional framework, and then an infinite threedimensional supramolecular network is formed through hydrogen bonding interactions.     

Ab initio electron correlated studies on the intracluster reaction of NO+ (H2O)(n) → H3O+ (H2O)(n-2) (HONO) (n = 4 and 5)

Hydrated nitrosonium ion clusters NO(+)(H(2)O)(n) (n = 4 and 5) were investigated by using MP2/aug-cc-pVTZ level of theory to clarify isomeric reaction pathways for formation of HONO and fully hydrated hydride ions. We found some new isomers and transition state structures in each hydration number, whose lowest activation energies of the intracluster reactions were found to be 4.1 and 3.4 kcal mol(-1) for n = 4 and n = 5, respectively. These thermodynamic properties and full quantum mechanical molecular dynamics simulation suggest that product isomers with HONO and fully hydrated hydride ions can be obtained at n = 4 and n = 5 in terms of excess hydration binding energies which can overcome these activation barriers.     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

Synthesis, Properties and Crystal Structure of a Novel Coordinated Polymer: {(H2en)(H3O)[(BiPb(C2O4)4(H2O)2)]·2(H2O)}n

A novel oxalate compound {(H2en)(H3O)[BiPb(C2O4)4(H2O)2]·2(H2O)}n 1 (en = ethylenediamine) containing lead and bismuth has been synthesized by hydrothermal methods, and structurally characterized by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P21/c with a = 11.6160(1), b = 12.7426(1), c = 15.5683(5) (A), β = 108.442(4)°, BiPbC10N2O21H21, Mr = 921.46, V = 2186.0(4) (A)3, Z = 4, Dc = 2.800 g/cm3, F(000) = 1712 and μ(MoKα) = 15.837 mm-1. The final R = 0.0502 and wR = 0.1261 for 3391 observed reflections with I > 2(σI). The title com- pound consists of 2-D polyanions and protonized organic amine cations, and they are combined to each other by static attractive force and H-bonds to form the so-called organic-inorganic hybrid material.