Synthesis and Crystal Structure of a Tetranuclear Cu(Ⅰ) Complex with Vinyfidenebis(diphenylphosphine)

The vinylidenebis(diphenylphosphine) (vdpp) reacts with CuBr to give a tetranuclear complex, [Cu4(μ3-Br)2(μ2-Br)2(μ2-vdpp)2(CH3CN)2]·(CH3CN)2 1. The title complex has crystallo-graphically imposed centrosymmetry and presents a Cu4Br4 core with distorted stair-like structure. All copper(Ⅰ) atoms in 1 assume distorted tetrahedral coordination geometry. The distance of 2.7745(11) A between the two copper centers indicates the presence of ligand-supported Cu…Cu interactions. Crystal data for 1: C60H56Br4Cu4N4P4, Mr = 1530.77, triclinic, space group P1, a = 11.6593(9), b = 11.7181(9), c = 13.8711(11) A, α = 110.1020(10), ,β = 102.0050(10), γ = 109.8040(10)°, V = 1557.5(2) A3, Z = 1, Dc = 1.632 g/cm3, F(000) = 760, λ = 0.71073 A, T = 298(2) K, 2θmax = 50.04°,μ = 4.056 mm-1, S = 1.181, R = 0.0507 and wR = 0.1025.     

A Tetranuclear Complex Assembled from N,N＇-Bis（4-（3＇-formyl-5＇-methylsalicyclidene）-iminoethyl）-4-methyl-2,6-bimethyliminophenol

The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.     

A Diphenoxo-bridged Ferromagnetic Copper（Ⅱ） Dimer Based on N-（2-Hydroxybenzyl）salicylaldimine

A new dinuclear copper（Ⅱ） complex, [Cu（L）（py）]2 1 （H2L = N-（2-hydroxybenzyl）- salicylaldimine, py = pyridine）, has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ（MoKα） = 1.422 mm-1, F（000） = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper（H） centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper（Ⅱ） ion and shares the other phenolate group between the two copper（H） ions, affording a Cu2O2 plane. Each copper（Ⅱ） center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data （2-300 K） of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑（Xobsd -Xcalcd）2/∑Xobsd2= 2.76 × 10^-3.     

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of a New Dinuclear Copper Complex [C2H6ON]2[Cu2Cl2（μ-CH3COO）4]

The hydrothermal reaction of copper chloride dihydrate and 5,5-dimethyl-imidazolidine,-2,4-dione with a mole ratio of 1：1 in acetonitrile resulted in the formation of a new acetate-bridged dinuclear copper complex, [C2H6ON]2[Cu2Cl2（μ-CH3COO）4]. Protonated acetamide in eaolie form and acetic acid were yielded by the hydrolysis of acetonitrile under hydrothennal condition. The rifle complex （C12H24Cl2Cu2N2O10） was characterized by X-ray single-crystal diffraction, IR spectrum, elemental and electrochemical analysis. It crystallizes in the monoclinic system, space group P21/c with a = 8.298004）, b = 14.358（2）, c = 12.0010（2） A^°, β= 130.620（3）°, V = 1085.3（2） A^°^3, Dc = 1.696 g/cm^3, 34, = 554.31, Z = 2, F（000） = 564 and μ = 2.254 mm^-1. The crystal structure consists of a tetraacetate-bridging dinulcear copper complex anion [Cu2Cl2（μ-CH3COO）4]^2-, with the chlorine anions in the axial positions, and two protonated acetamide cations [C2H6ON]^＋, which were connected through hydrogen bonds to form a three-dimensional infinite network.     

Synthesis and Crystal Structure ofa Bipy Bridged Binuclear Cu^Ⅱ Complex Containing Aminomethanesulfonic Acid [Cu2（Sams）2（Bipy）（H2O）2]·（H2O）

The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis （TGA） and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533（17）, b = 8.3408（13）, c = 16.714（3） A^°, β = 101.295（4）°, V = 1494.3（4） A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper（Ⅱ） complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C（10）-H（10）…O（3） and C（13）- H（13）…O（3）, an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.     

Structural Studies and Photoluminescence of a Novel Mercury（Ⅱ） Complex Based on a Tris[4-（1-pyrazolyl）-phenyl]amine

A novel iodine-bridged mercury（Ⅱ） complex [Hg（L）（μ-I）（I）]2 was isolated by a reaction between HgI2 and the organic ligand tris[4-（1-pyrazolyl）phenyl]amine L, and the complex and ligand were both characterized by FT-IR spectroscopy, ^1H NMR and elemental analysis. The complex crystallizes in monoclinic space group P21/c with a = 9.579（5）, b = 27.331 （5）, c = 11.268（5） А, β= 105.624（5）°, Z = 2, Dc = 2.099 g·cm^-3 and μ= 7.620 mm^-1. The title complex C54H42Hg2I4N14 is a diplex bridged dinuclear complex consisting of two Hg（Ⅱ） ions, two ligands, two bridging I-anions, and two terminal I-anions. Universal hydrogen bonds in the complex with the partners of neighboring molecule have generated a supramolecular arrangement. Solid-state emission of the ligand and its complex have been investigated at room temperature.     

Synthesis and Crystal Structure of a Novel Binuclear Copper（Ⅱ） Complex, [Cu（paba）Cl]

A novel binuclear Cu（Ⅱ） complex [Cu（paba）Cl] （pabaH = 2-（2-pyridylmethylimine）benzenesulfonic acid） has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal of the title complex crystallizes in a monoclinic system, space group P21/n, with a = 6.8165（7）, b = 15.3073（16）, c = 12.3795（13） A^°, β= 95.0160（10）°, V= 1286.8（2） A^°^3, Mr = 360.26, Dc= 1.860 g/cm^3,μ = 2.074 mm^-1, F（000） = 724, Z = 4, the final R = 0.0252 and wR = 0.0675 for 2395 observed reflections with I 〉 20（I）. The title complex is centrosymmetric and a pair of chlorides act as μ2-bridges to link two Cu（Ⅱ） ions forming a binuclear complex. Every Cu（Ⅱ） ion is five-coordinated by pyridyl N, imine N and sulfonate O atoms of the tridentate paba ligand as well as two bridging Cl^-, constructing the distorted square-pyramidal geometry. In the structure extensive hydrogen bonds and weak π-π stacking stabilize the solid structures, through which the complex builds its 3-dimensional supramolecular structure.     

硫酰杯[4]芳烃与铜(II)双核配合物的合成与晶体结构

The X-ray crystallographic structure was reported for a dinuclear copper（Ⅱ） complex with a tetraanionic ligand of p-tert-butylsulfonylcalix[4]arene [Cu2L（CH3OH）6]·4CH3OH （H4L=p-tert-butylsuffonylcalix[4]arene）. The complex belongs to triclinic system, P1^-- space group, with a = 1.2303（3） nm, b = 1.2377（3） nm, c = 1.3110（3） nm, a =66.862（4）°, β= 67.206（4）°, γ=61.711（3）°, Z= 1, V= 1.5659（7） nm^3, Dc= 1.371 g/cm^3, F（000） = 682,μ（Mo Kα） = 0.883 mm^-1, R1 =0.0325, wR2=0.0870. In this complex, the calix[4]arene acts as a bis-tridentate chelating ligand with the 1,2-alternate conformation.     

PREPARATION AND CRYSTAL STRUCTURE OF A HETEROBINUC- LEAR COPPER (Ⅱ)-ZINC(Ⅱ) COMPLEX WITH μ-OXAMIDO LIGAND

<正> The complex [Cu(oxap)Zn(phen)2](ClO4)2·H2O·CH3CH2OCH2-CH3(Mr = 980. 61) (oxap = N,N'-bis(2-aminopropyl) oxamido C2O2 (NCH2CH(CH3) NH2)2, phen = 1, 10-phenanthroline) crystallizes in the monoclinic space group P21/n with a=13. 076(4),b=23. 039(7) ,c= 14. 375(3) A,β=98. 11(2)°,V = 4287. 2A3, Z = 4,DX = 1. 541g/cm3,μ=12. 80cm-1 and F(000) = 2020. The final refinement converged with R=0. 067 for 3173 observed independent reflections. The copper(Ⅱ) ion is in an almost planar tetragonal environment while the zinc(Ⅱ) ion is in a distorted octahedron. The Cu....Zn distance is 5. 265A.     

Synthesis and Crystal Structure of Dinuclear Copper(Ⅱ)Complex Cu_2(μ-PhCOO)_4(amet)_2·2CH_3COCH_3

1INTRODUCT1ONFormode1ingcompoundsofcertaincopper-containingenzymes,theinvestigationofdinuclearcoppercomplexeshasattractedtheattentionofinorganicandbiologicchemistst1i.Actingasoxygentransportproteinsforinvertebrates,oxyhemocyanin(oxyHc)hasadinuclearcoppersitewithaCu-Cuseparationofca.3.6A[2'3i(Fig.1).In1984,Karlinetal-[4ireportedthesynthesisofadinuclearcopper(I)com-plexwithabidentateligand.Thecomplexreactswithdioxygenquasireversibly,whichproducesaperoxodinuclearcopper(I)complex(Nallo=8O3…     

亚乙基硫脲配位聚合物[Cu_3(etu)_3Br_3]_n的合成与晶体结构

CuB r2和亚乙基硫脲反应生成Cu(I)配位聚合物[Cu3(etu)3B r3]n(etu=亚乙基硫脲),单晶X射线衍射测得该晶体为三斜晶系,Pī空间群.晶胞参数:a=0.762 46(6)nm,b=1.198 48(10)nm,c=1.224 52(7)nm,α=68.202(5),°β=74.607(6),°γ=87.652(7)°,V=0.999 61(13)nm3,Z=2,Mr=736.82,Dc=2.448 g.cm-3,μ=9.477 mm-1,F(000)=708,偏差因子R1=0.030 6,wR2=0.071 0.配合物由环状[Cu(etu)B r]3单元聚合而成,形成Cu4S2B r2和Cu2S4B r2聚合体,两聚合体通过μ2-S桥键交替连接,形成平行于晶胞b轴的[Cu3(μ3-etu)(μ2-etu)2(μ2-B r)2B r]n一维链.Cu(I)均为变形四面体配位,亚乙基硫脲以S原子与Cu(I)结合,形成μ2-S和μ3-S两种配位方式.     

Synthesis and Crystal Structure of a One-dimensional Ladder-like Complex [Cu2（L）（dca）2]n （dca = [N（CN）2]^-, L = 1,4-Bis（3-furanyl）-2,3-diaza-1,3-butadiene）

A new Cu（I）-dicyanamide with formula [Cu2（L）（dca）2]n （dca = dicyanamide anion, L = 1,4-bis（3-furanyl）-2,3-diaza-1,3-butadiene） has been synthesized and structurally characterized. The complex crystallizes in the monoclinic system, space group P21/n with a = 9.271（2）, b = 7.7355（16）, c = 11.967（3）A,β = 102.693（3）°, V= 837.3（3）A^3, Z = 4, Mr = 223.68, Dc = 1.775 g/cm^3,μ（MoKa） = 2.567 mm^-1, F（000） = 444, R = 0.0782 and wR = 0.2582 for 951 observed reflections （I 〉 2σ（I））. Single-crystal X-ray analysis reveals that the copper atom is three-coordinated by two nitrogen atoms from two dicyanamide anions and another one from the ligand, and each copper atom is connected by two [N（CN）2] anions to form an infinite double-stranded bridge fashion leading to 1D ladder-like motifs.     

Synthesis and Crystal Structure of Bis[O,O'-di(2-phenylethyl)dithiophosphato](α,α'-bipyridine)copper(Ⅱ)

A ternary adduct Cu[S2P(OCH2CH2Ph)2]2·bipy(bipy=α,α'-bipyridine) was syn-thesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a=10.2320(2),b=11.5249(3),c=18.0916(3),α=98.95(1),β =103.601(1),γ=91.272(2)°,V=2044.49(7)3,Z=2,Dc=1.453 g/cm3,T=153(2) K,C42H44CuN2O4P2S4,Mr=894.51,λ(MoKα)=0.71073,μ=0.86 mm-1,S=0.999,(△/σ)max=0.002,the final R=0.0243 and wR=0.0704.A total of 9221 unique reflections were collected,of which 8573 with Ⅰ 2σ(Ⅰ) were observed.The Cu(Ⅱ) atom is five-coordinated in a rather distorted trigonal bipyramidal geometry(τ value=0.537).The Cu-S distances range from 2.3491(4) to 2.4829(4) ,and the Cu-N distances are 1.9987(12) and 2.0584(11) ,respectively.An interesting feature of this adduct resides in its two-dimensional(2D) open framework constructing through hydrogen bonding and π-π interactions.     

Synthesis, Crystal Structure and Cubic Order NLO Property of Square Compound [PPh4]2[Ni（CN）4Cu（PPh3）2]2·2CH3OH

A new tetranuclear cyanide-bridged complex [PPh4]2[NiⅡ(CN)4CuⅠ(PPh3)2]2·2CH3OH ([PPh4]+ = tetraphenylphosphine cation, PPh3 = triphenylphosphine) 1 has been synthesized and characterized by IR spectroscopy, elemental analysis, electronic absorption spectra and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group Pí with a = 10.910(5), b = 15.777(7), c = 18.275(8), α = 68.752(12), β = 79.776(13), γ = 81.400(14)°, NiCuC65H50N4OP3, Mr = 1122.25, V = 2873(2)3 , Z = 2, Dc = 1.293 g/cm3, F(000) = 1156, μ = 0.826 mm-1, the final R = 0.0755 and wR = 0.2155 for 7324 observed reflections (I > 2σ(I)). The title compound exhibits a discrete square tetranuclear structure and a cubic order NLO property.     

A nonacoordinated bridging selenide in a tricapped trigonal prismatic geometry identified in undecanuclear copper clusters: syntheses, structures, and DFT calculations

Undecanuclear copper clusters, [Cu(11)(micro(9)-Se)(micro(3)-Br)(3)[Se(2)P(OR)(2)](6)] (R = Et, Pr, (i)Pr) (1a-c), were isolated along with closed-shell ion-centered cubes, [Cu(8)(micro(8)-Br)[Se(2)P(OR)(2)](6)] (PF(6)) (2a-c) and [Cu(8)(micro(8)-Se)[Se(2)P(OR)(2)](6)] (3a-c), from the reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NBr in a molar ratio of 2:3:2 in CH(2)Br(2). The molecular formulations of these clusters were confirmed by elemental analysis, positive FAB mass spectrometry, and multinuclear NMR ((1)H, (31)P, and (77)Se). (77)Se NMR spectra of Cu(11) clusters (1a-c) are of special interest as two inequivalent selenium nuclei of the diselenophosphate (dsep) ligand exhibit different scalar coupling patterns with the adjacent phosphorus nuclei. X-ray analysis of 1c reveals a Cu(11)Se core stabilized by three bromide and six dsep ligands. The central core adopts the geometry of a 3,3,4,4,4-pentacapped trigonal prism with a selenium atom in the center. The coordination geometry for the nonacoordinate selenium atom is tricapped trigonal prismatic. The X-ray structure 2a or 2c consists of a cationic cluster in which eight copper ions are linked by six diselenophosphate ligands with a central micro(8)-Br ion. The shape of the molecule is a bromide-centered distorted Cu(8) cube. Each diselenophosphate ligand occupies square faces of the cube and adopts a tetrametallic tetraconnective coordination pattern. Each copper atom of the cube is coordinated by three selenium atoms with a strong interaction with the central bromide ion. Molecular orbital calculations at the B3LYP level of the density functional theory have been carried out to study the Cu-micro(9)-Se interactions for clusters [Cu(11)(micro(9)-Se)(micro(3)-X)(3)[Se(2)P(OR)(2)](6)] (X = Br, I). Calculations show that the formal bond order of each Cu-micro(9)-Se bond is slightly smaller than half of those calculated for the terminal Cu-micro(2)-Se bonds.     

Preparation,Characterization and Crystal Structure Determination of a Nickel Complex [Ni(ftsc)_2NO_3]NO_3(Hftsc=Furan-2-carbaldehyde Thiosemicarbazone)

A new Ni(II) complex, [Ni(ftsc)2NO3]NO3 (Hftsc=furan-2-carbaldehyde thiosemicarba-zone), has been synthesized and characterized by IR, UV spectra and single-crystal X-ray diffraction analysis. It crystallizes in a monoclinic system, space group P21/n, with a=10.5203(13), b=9.2094(11), c=20.829(3), β=91.518(2)°, V=2 017.3(5)3, Z=4, F(000)=1064, Dc=1.716 g/cm3, and wR= 0.0800. The complex contains a six-coordinated nickel(II) center which is bound to two imine nitrogen atoms and two thiolato sulfur atoms of two ligands as well as two oxygen atoms from a nitrate anion to assume a distorted octahedral coordination geometry. In addition, intermolecular N-H···O and C-H···O hydrogen bonds between adjacent molecules link the molecules together to form a three-dimensional structure.