Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

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 and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.

Synthesis, Crystal Structure and Properties of a New Binuclear Copper(Ⅱ) Complex with 5-Oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic Acid(TNCA)

A new binuclear copper（Ⅱ） complex [Cu2（Hpt）2（TNCA）2（H2O）2]·4 H2O（1） has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid（TNCA） and 3-（pyridin-2-yl）-1,2,4-triazole（Hpt）. It crystallizes in the triclinic space group P-1, with a = 8.8199（18）, b = 14.278（3）, c = 15.269（3） A, α = 76.21（3）o, β = 81.07（3）o, γ = 76.07（3）o, V = 1802.7（6） A3, Dc = 1.636 g/cm3, Z = 2, F（000） = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ2-η^1：η^0-3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of the Cu（1） ion is CuO2N3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu（Ⅱ） ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.

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) .

Characterization and Crystal Structures of Two Copper(Ⅱ) Complexes Constructed by a Flexible Double Betaine Ligand

A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.

Synthesis,Structure and Magnetic Properties of Novel Carboxylato-bridged Pentanuclear Copper(Ⅱ)-Lanthanoid(Ⅲ)Complexes

Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. The X ray crystallography established the structure of the Gd complex, which contains a pair of quadruply acetato bridged CuGd dinuclear subunits, and each of them is linked to the central Cu atom by a single acetato bridge. The coordination sphere of each Gd atom is completed by three aqua ligands [Gd-O=0.242 8(5)-0.244 4(4) nm] to form an 8 coordinated distorted square antiprism. The central Cu atom is coordinated by two oxygen atoms from the two bridging acetato groups and two oxygen atoms from the two monodentate acetato groups in a slightly distorted square planar fashion, while each terminal Cu atom is coordinated by the four acetato oxygen atoms at the basal plane and an aqua ligand at the apical position to form a square pyramid. The variable temperature (4 320 K) magnetic susceptibility data of the Gd complex were measured, and fitted to the Curie Weiss law with C =16.38 K cm 3·mol -1 and θ =-1.55 K, indicating very weak antiferromagnetic interaction.

Synthesis and Crystal Structures of the α and β Forms of Bis(salicylaldoxime)copper(Ⅱ) Complexes

Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.

Syntheses of Binuclear Copper(I) Complexes Containing Benzimidazole

A binuclear copper（I） complex [Cu2（dppm）2（C7H6N2）2]（NO3）2 （C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2） has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167（3）, b = 21.209（4）, c =20.680（4）A°, β = 103.93（3）°, C32H28CuN3O3P2, Mr = 628.05, Z = 8, μ = 0.868 mm^-1, V = 6031 （2） ,A°^3,F（000） = 2592, De= 1.383 g/cm^3, R = 0.0593 and wR = 0.1736. A total of 5297 independent reflections were collected, of which 3503 were observed with 1 〉 2σ（/）. The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole. In the coordination sphere, the bond lengths of Cu-P（1） and Cu-P（2） are 2.2607（17） and 2.2503（16） A°,respectively and the P-Cu-P bond angle is 127.26（6）°.

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5- Benzenetetracarboxylato Trivalent Anion

The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.

Synthesis, Properties and Structureof a Novel Unsymmetrical Bis (phenoxo) BridgedBinuclear Copper (Ⅱ) Complex

A novel bis (phenoxo) bridged binuclear copper ( II) complex with dissimilar coordination environments was synthesized and characterized by spectroscopies and X-ray crystallography. It crystallized in the monoclinic system with space group C2/c, a=2. 241 1(2) nm, b=1. 834 2 (2) nm, c=1.877 9(2) nm, β=122.861(2)°, V=6.484 3(11) nm3, Z=8. Itconsistsof two unsymmetrical Cu (Ⅱ ) centers bridged by two phenolic oxygen atoms to yield a Cu2O2 core with the Cu-Cu separation of 0. 310 2 nm, in which Cul and Cu2 ions exhibit distorted N2O3 and N3O2 square pyramidal geometries, respectively.

Synthesis and Crystal Structure of Binuclear Complex of Copper(Ⅱ)Chloroacetate with Acetamine

The title complex, Cu 2(O 2CCH 2Cl) 4 OC(NH 2)CH 3 2, crystallizes in space group P2 1/a with a=7.616(4), b=18.665(5), c=7.949(5) , β=106.29(5)°. V=1084(1) 3, Z=2, M r=619.19, D c =1.896 g/cm 3; μ =25.05 cm -1 and F(000)=620.00, R =0.045 and R w =0.054 for 1807 observable reflections. X ray crystal structure analysis revealed that two Cu atoms are bridged by four chloroacetate groups, and the acetamine ligands are bonded by O(carboxide) to the terminal Cu atoms of each dimeric unit. The coordination geometry of Cu atom is a distorted octahedral configuration. The distance between the two Cu atoms is 2.648(1) .

Synthesis and Properties of u-Oxamido Heterobinuclear Cu(Ⅱ)-Co(Ⅱ) Complexes

Three heterobinuclear complexes were synthesized, namely [Cu (oxpn) Co (L)2] (ClO4)2·xH2O(L= 2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen) , and 5-nitro-1, 10-phenanthroline (NO2-phen)), where oxpn represents N, N'-bis(3-aminopropyl) oxam-ido. Based on 1R, elemental analysis, conductivity measurement and electronic spectra, these complexes were characterized by an extended oxamido-bridged structure with Cu(Ⅱ) in a planar environment and Co(Ⅱ) in a octahedral environment. The symmetry of the cation is very close to C2v.The complexes were also characterized with variable temperature (4~300K) magnetic susceptibility, and the data were fit for the susceptibility equation derived from spin Hamilton, H= -2JS1.S2-DSx12 by least square strategy. The exchange integral, J, was found to be -22.36 cm-1 (for bpy);-15.45 cm-1 (for phen); -19. 10cm-1(for NO2-phen), indicating that there is a weak antiferromagnetic spin-exchange interaction between the metal ions.

DNA Cleavage by Copper (Ⅱ) Complexes Without added Coreactants

The cleavage activity of complexes between copper (Ⅱ) and four different amino acidor amino acid methyl ester on DNA was tested at physioloical pH and temperature., It was found that Cu (Ⅱ)-L-His and Cu (Ⅱ)-L-His methyl ester complexes could cleane DNA. The extent ofDNA cleavage is largely dependent on the metal ion-to-ligand ratio. The cleavage of doublestranded DNA mediated by Cu (Ⅱ)-L-His complexes occurs via a hydrolytie mechanism.

Synthesis and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.

Synthesis and Magnetic Properties of Copper (Ⅱ) Complexes with Pyridine N-Oxide-2-ylmethy-lidenedithiocarbazate as Ligands

A series of copper (Ⅱ) complexes with pyridine N- oxide- 2- ylmethylidened-ithiocarbazates as ligands were synthesized and characterized by IR spectra, electronic spectra and magnetic moments measurement at room temperature. Variable temperature magnetic susceptibilites (3-300K) of four complexs were measured and fitted with the Bleaney-Bowers dimer equation by considering the magnetic interaction between molecules. The fitting results show the existence of intramolecular ferromagnetic interactions and intermolecu-lar anti-ferromagnetic interactions in these copper( Ⅱ) complexes.

Crystal Structures of Dinuclear Copper(Ⅱ) Complexesof bis (1,4,7-triazacyclononane) Ligands Containing Rigid Bridging Groups

Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.

STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.

PREPARATION, CHARACTERIZATION AND ELECTROCHEMISTRY OF BINUCLEAR COPPER(I) COMPLEXES Cu_2(dppm)Cl_2 AND Cu_2(dppe)Cl_2

Two binuclear copper(I) complexes with novel structures and novel bonding,Cu_2(Ph_2PCH_2PPh_2)Cl_2 (Ph_2PCH_2PPh_2=dppm) and Cu_2(Ph_2P-CH_2CH_2PPh_2)Cl_2 (Ph_2PCH_2CH_2PPh_2=dppe), were prepared and characterized through elemental analyses, ICP, IR(4000-200 cm^(-1), CsI disc.), ^(31)P-NMR spectra. Their electronic conductivities, oxidation and reduction potentials were measured. Preliminary studies show that both of the two complexes have chlorobridging and phosphorus-bridging structures.