Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

Synthesis,Crystal Structure and DNA-binding Properties of a New Copper(Ⅱ) Schiff Base Complex

A new asymmetric bidentate copper（Ⅱ） complex,CuL 2（HL=2-（（E）-（4-bromophenylimino）methyl）-6-bromo-4-chlorophenol）,has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218（3）,b=9.355（3）,c=13.449（4）,β=108.722（4）°,V=1336.8（6）3,Z=2,Dc=2.008 g/cm 3,μ（MoKα）=7.024 mm-1,F（000）=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections （I〉2σ（I））.The central copper（Ⅱ） is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA（CT-DNA）,presumably via a partial intercalative mode.The intrinsic binding constant of the Cu（Ⅱ） complex with DNA is 7.335×10 3 M-1.

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex with 4,4′,6,6′-Tetrabromo-2,2′- [ethylenedioxybis(nitrilomethylidyne)]diphenol

A new mononuclear Cu（II） complex, [Cu（L）] （H2L = 4,4′,6,6v-tetrabromo-2,2′- [ethylenedioxybis（nitrilomethylidyne）]diphenol）, has been synthesized and structurally characterized. X-ray crystal structure of the complex reveals that the Cu（Ⅱ） ion is four-coordinated by two oxygen atoms and two nitrogen atoms from L2- unit. Crystallographic data： monoclinic, space group P21/n with a = 14.076（2）, b = 6.9801（14）, c = 19.858 （2） A, β= 107.613（2）°, C16n10Br4CuN2O4, Mr = 677.44, V = 1859.6（5） A3, Dc = 2.420 g/cm3,μ = 9.796 mm^-1, F（000） = 1284, Z = 4, the final R = 0.0516 and wR = 0.0938 for 1879 observed reflections with I 〉 2σ（/）. The dihedral angel between the two coordination planes of Cu（1）-N（2）--O（4） and Cu（1 ）-N（ 1 ）-O（3）） is 30.08（6）°.

π-π Stacking, Hydrogen Bonding and Magnetic Coupling Mechanism on a Mono-nuclear Cu^Ⅱ Complex

A new mono-nuclear CuII complex [Cu（DPP）（DP）Br]（ClO4）H2O （DPP = 2-（3,5- dimethyl-1H-pyrazol-1-yl）-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole） has been syn- thesized with 2-（3,5-dimethyl-1H-pyrazol-1-yl）-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765（2）, b = 17.044（3）, c = 10.9044（16）, β= 97.112（2）°, V = 2538.5（6）3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F（000） = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.

Synthesis and Crystal Structure of Binuclear Copper (Ⅱ) Complex Containing (Dimethylaminomethyl)ferrocene

A binuclear complex including ferrocenyl, Cu2{Fe(C5H5)[C5H4CH2N(CH3)2]}2 (CH3COO)4, was synthesized and characterized by X-ray diffraction. The title complex crystallizes in triclinic, space group P with a = 8.2779(8), b = 9.4830(8), c = 12.262(1) ? = 81.079(5), b = 80.620(4), g = 78.960(4), V = 924.4(1) 3, Z = 1, C34H46Cu2Fe2N2O8, Mr = 849.51, Dc = 1.526 g/cm3, l(MoK) = 0.71073 ? ?= 1.954 mm-1, F(000) = 438, R = 0.0297 and wR = 0.0901. Both cyclopentadienyl rings in each dmaf (dmaf = (dimethylaminomethyl)ferrocene, Fe(C5H5)- [C5H4CH2N(CH3)2]) have an eclipsed conformation. The binuclear molecule has a crystallographic centrosymmetry; four acetates and two Cu atoms form a cage structure with the distance between two neighboring Cu atoms of 2.655(1) .

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

Synthesis and Crystal Structure of a Copper(Ⅱ) Compound Constructed by N-(4,6-Dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea

A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385（7）, c = 22.0008（18） A, β = 108.077（2）°, V = 3104.3（5） A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ（MoKa） = 0.920 mm^-1, F（000） = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections （I 〉 2σ（I））. X-ray diffraction shows the existence of weak complementary intramolecular N-H...O （DA） hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu（Ⅱ） ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.

Microwave Synthesis and Crystal Structure of Bis{2-[(2,4-dichloro-phenylimino)methyl]-4,6-diiodo-phenol}-copper(Ⅱ)

Bis{2-[（2,4-dichloro-phenytimino）-methyl]-4,6-diiodo-phenol}-copper（II） （1） has been synthesized and its structure determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 14.7558（17）, b = 20.770（2）, c = 20.3260（19） A, β = 90.6110（10）°, V= 6229.2（11） A3 and Z = 8. The Cu atom is surrounded by two O atoms and two N atoms from two 2-[（2,4-diehloro-phenylimino）-methyl]-4,6-diiodo-phenol molecules to form a tetrahedral coordination environment. The complex is linked into a column by weak intermolecular interactions.

Hydrothermal Synthesis and Crystal Structure of a Copper Complex

The title compound [Cu（IB）2]n·n（H2O） 1 was synthesized via the hydrothermal reaction of CuSO4·5H2O and NaOH with 4-（1H-Imidazol-1-yl）benzoic acid（HIB）,and character-rized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in monoclinic,space group C2/c with a = 14.349（7）,b = 5.977（3）,c = 21.368（9） ,β = 104.956（9）o,V = 1770.5（2）3,Z = 4,C20H16CuN4O5,Mr = 455.92,Dc = 1.710 g/cm3,F（000） = 932 and μ（MoKα） = 1.279 mm-1.The final R = 0.0337 and wR = 0.0888 for 1972 observed reflections with Ⅰ 〉 2σ（Ⅰ） and R = 0.0369 and wR = 0.0926 for all data.X-ray diffraction reveals that the IB ligand links the Cu（Ⅱ） atoms into a double stranded chain.The extensive supramolecular interactions lead to the formation of an infinite 2D structure.

CFD simulation of an industrial hydrocyclone with Eulerian-Eulerian approach: A case study

In the present study, a three-dimensional computational fluid dynamics simulation together with experimental field measurements was applied to optimize the performance of an industrial hydrocyclone at Sarcheshmeh copper complex. In the simulation, the Eulerian–Eulerian approach was used for solid and liquid phases, the latter being water. In this approach, nine continuous phases were considered for the solid particles with different sizes and one continuous phase for water. The continuity and momentum equations with inclusion of buoyancy and drag forces were solved by the finite volume method. The k–e RNG turbulence model was used for modeling of turbulency. There was a good agreement between the simulation results and the experimental data. After validation of the model accuracy, the effect of inlet solid percentage, pulp inlet velocity, rod inserting in the middle of the hydrocyclone and apex diameter on hydrocyclone performance was investigated. The results showed that by decreasing the inlet solid percentage and increasing the pulp inlet velocity, the efficiency of hydrocyclone increased. Decreasing the apex diameter caused an increase in the hydrocyclone efficiency.

A Stable ‘Three-in-one’ Coordination Polymer

The title compound [Cu2（IB）2（HIB）2] 1 was synthesized via the hydrothermal reaction of CuSO4·5H2O and NaOH with 4-（1H-Imidazol-1-yl）benzoic acid （HIB）, and characte- rized by elemental analysis and infrared spectra. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 24.513（8）, b = 18.948（5）, c = 17.248（6）, β = 119.81（2）o, V = 6951（4）3, Z = 8, C40H30Cu2N8O8, Mr = 877.80, Dc = 1.678 g/cm3, F（000） = 3584 and μ（MoKα） = 1.295 mm-1. The final R = 0.0542 and wR = 0.1335 for 5398 observed reflections with I 〉 2σ（I） and R = 0.0845 and wR = 0.1520 for all data. X-ray diffraction analysis reveals that the title complex is a unique ＇three-in-one＇ crystal of coordination network through strong hydrogen bonds and coordination covalent bonds. The thermogravimetric analysis measurement showed that compound 1 has thermal stability as no strictly clean weight loss step occurs below 300 ℃.

Structures and luminescence properties of two copper(I) halide complexes featuring 2-(2-benzimidazolyl)-6-methylpyridine

Two new copper（I） halide complexes bearing 2-（2-benzimidazolyl）-6-methylpyridine （Hbmp） and PPh3 ligands, Cu（Hbmp）（PPh3）X （X = Br （1）; I （2））, have been synthesized and characterized. Single-crystal X-ray structure analysis reveals that the halide ligand has a significant impact on the Cu-Npyridyl bond lengths. Complexes 1 and 2 show the solid-state emissions at ambient temperature, varying with the halide bound to the { Cu（Hbmp）（PPh3） } motif, which are perhaps best attributed to the metal-to-ligand charge-transfer （Cu（I） → Hbmp） transition mixed with some ligand-to-ligand charge-transfer （X and PPh3 → Hbmp） character.

Antibacterial Activities and Nuclease Properties of Two New Ternary Copper（ll） Complexes with 2-（4＇-Thiazolyl）- benzimidazole and 2,2＇-Bipyridine/1,10-phenanthroline

Two new complexes： [Cu（TBZ）（bipy）Cl]Cl[H2O （1） and [Cu（TBZ）（phen）CI]CloH20 （2） [TBZ=2-（4＇-thiazolyl）- benzimidazole, phen = 1,10-phenanthroline and bipy =2,2＇-bipyridine] have been synthesized and characterized by elemental analysis, molar conductivity, IR, and UV-vis methods. Complex 2, structurally characterized by single-crystal X-ray crystallography, crystallizes in the monoclinic space group P21/c in a unit cell of a = 0.85257（12） nm, b=2.5358（4） nm, c=1.15151（13） nm, β=118.721（8）°, V=2.183.2（5） nm^3, Z=4, Dc=1.624 gocm 3, μ= 1.367 mm^-1. The complexes, free ligands and chloride copper（II） salt were each tested for their ability to inhibit the growth of two gram-positive （B. subtilis and S. aureus） and two gram-negative （Salmonella and E. coli） bacteria. The complexes showed good antibacterial activities against the microorganisms. The interaction between the com- plexes and calf thymus DNA in aqueous solution was investigated adopting electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and cyclic voltammetry. Results suggest that the two complexes can bind to DNA by intercalative mode. In addition, the result of agarose gel electrophoresis suggested that the complexes can cleave the plasmid DNA at physiological pH and room temperature. Mechanistic studies with different inhibiting reagents reveal that hydroxyl radicals, and a singlet oxygen-like copper-oxo species are all involved in the DNA scission process mediated by the complexes.

Synthesis, Antibacterial Activities and Nuclease Properties of Ternary Copper（II） Complex Containing 2-（2＇-Pyridyl）benzothiazole and Glycinate

A new ternary complex [Cu（PBT）（Gly）（H2O）]ClO4 （PBT=2-（2＇-pyridyl）benzothiazole, and Gly=glycinate） has been synthesized and characterized by elemental analysis, molar conductivity, and IR methods. The complex, structurally characterized by single-crystal X-ray crystallography, shows a slightly distorted square-pyramidal coordination geometry in which two nitrogen atoms of PBT and the carboxylate oxygen atom O and the amino nitrogen atom N of Gly bind at the basal plane, a water molecule is coordinated at the apical position. The complex, Cu（ClO4）2 and flee PBT were each tested for their ability to inhibit the growth of two Gram（--） （Escherichia coil, Salmonella） and two Gram（＋） （Bacillus subtilis, Staphylococcus aureus） microorganisms. The complex showed good antibacterial activities against the microorganisms compared with free PBT and Cu（C104）2. The interaction between the complex and calf thymus DNA in aqueous solution was investigated using electronic spectroscopy, fluorescence spectroscopy, circular dichroic spectroscopy, and viscosity measurements. Results suggest that the complex could bind to DNA by an intercalative mode. In addition, the result of agarose gel electrophoresis showed that the complex can cleave the plasmid DNA by hydroxyl radicals and singlet oxygen-like species under the condition of physiological pH and room temperature.

甘油铜络合物溶液化学镀铜的研究

采用单因素优选实验法研究了影响化学镀铜速率和甘油铜镀液稳定性的各因素,确定了适宜的甘油铜化学镀液配方和工艺条件.结果表明,优选出的的镀液稳定性相对较高、沉铜速度快、镀层外观较好.

Synthesis, Characterization and Crystal Structure of (2,2′-Bipyridine)(μ-maleato)copper(II) Dihydrate

The title polymeric complex [Cu(C_4H_2O_4)(C_(10)H_8N_2)]_n·2nH_2O wasprepared and its crystal structure was determined by X-ray diffraction methods. The crystal belongsto space group P2_1/c with cell dimensions of a = 1.0104(1), b = 1.9952(2), c = 0.7357(2) nm, β=98.38(2)° and Z = 4. The complex forms zig-zag chains along crystallographic axis c via Cu―O(car-boxyl) bond in the apical direction. Each repeated unit consists of a square pyramidal Cu( Ⅱ)centre with one maleate dianion and one 2, 2′-bipyridine forming a basal plane. Adjacent chainslink to each other by H-bonding between carboxyl groups and crystalline water. The distance of0.3482 run between parallel bipyridine rings shows a π- π stacking interaction. The title complexwas also characterized by IR, UV and ESR spectra.

Efficient Synthesis of Triarylamines Catalyzed by Copper(I)Diazabutadiene Complexes

Cuprous chloride was coordinated by diazabutadiene(DAB-R)ligands to form Cu(I)-(DAB-R)complexes,most of which have a 1∶1 ratio of Cu to DAB-R as reported.In the case of a special DAB-iPP,N,N'-bis(2,6-diiso-propylphenyl)-1,4-diaza-1,3-butadiene,an unexpected composition of complex was found with the formula Cu(I)Cl(DAB)_(2).When employed as catalyst for triarylamine synthesis from the coupling of aryl halides with pri-mary and secondary arylamines,the new Cu(I)-(DAB-iPP)complex displayed high efficiency.

Synthesis, Structures and Room Temperature Phosphorescence of 2-(2-Methoxynaphthyl)-1H-imidazo[4,5-f][1,10]-(1)phenanthroline-Cu(I) Complexes

A new ligand,2-(2-methoxynaphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline(mnipH),was synthesized by the condensation of 2-methoxy-1-naphthaldehyde and 5,6-diamino-1,10-phenanthroline.Then three ionic copper(I)complexes were obtained through the reactions of[Cu(MeCN)4]ClO4,mnipH and the chelating diphosphine ligands with a molar ratio of 1:1:1.The photoluminescence and the corresponding luminescent mechanism of all copper(I)complexes in the solid state were investigated at room temperature.