Crystal Structure and Superoxide Dismutase Activity of [Cu(Imidazole)2(Quinoline)Cl2]·0.5[Cu(Imidazole)4Cl2]

The preparation, spectroscopic properties and crystal structure of (bis-imidazole)quinoline-copper(II) dichloride [Cu(Im)₂(quin)Cl₂] (Im = imidazole, quin = quinoline) and tetraimidazole-copper(II)-dichloride [Cu(Im)₄Cl₂] are reported. Both cocrystallize on the triclinic system, space group P-1, with cell constants a = 8.095(5) Å, b = 12.141(5) Å, c = 13.847(5) Å, α = 108.816(5)°, β = 104.173(5)°, γ = 94.965(5)° and Z = 2. In the [Cu(Im)₂(quin)Cl₂] complex the copper(II) ion is coordinated to two imidazole molecules, to one quinoline and two chlorine ions, with the copper(II) ion in a distorted trigonal bipyramidal coordination geometry. In the [Cu(Im)₄Cl₂] complex, the copper(II) ion has a distorted octahedral coordination geometry. The superoxide dismutase mimetic activity of the complexes was investigated using the indirect xanthine-xanthine oxidase-nitroblue tetrazolium method and compared to that of the native enzyme.     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O

The title complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O (C18H34Cl2CuN2O14S2) (tssb = taurine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3)nm, α = 103.800(4), β = 95.030(4), γ = 104.416(4)°, Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, μ = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are positioned diagonally on a plane.     

The coordination chemistry of mono and bis(di-2-pyridylamine)copper(II) complexes: preparation,characterization and crystal structures of [Cu(L)(NO2)2], [Cu(L)(H2O)2(SO4)], [Cu(L)2(NCS)](SCN)·0.5DMSO and [Cu(L)2(SCN)2]

The crystal structures of two mono(dpyam)copper(II) complexes, [Cu(dpyam)(NO₂)₂] (1) and [Cu(dpyam)(H₂O)₂(SO₄)] (2) and two dithiocyanate compounds containing bis(dpyam)copper(II) units, [Cu(dpyam)₂(NCS)](SCN)·0.5DMSO (3) and [Cu(dpyam)₂(SCN)₂] (4) have been determined by X-ray crystallography. The second orthorhombic form of the monomeric Cu(II) complex 1 was obtained by the reaction of di-2-pyridylamine (dpyam) with CuCl and NaNO₂ in water–methanol solution. Each copper(II) ion in 1 exhibits a tetrahedrally-distorted square base of the CuN₂O₂ chromophore, with off-the-z-axis coordinated nitrito groups weakly bound in approximately axial positions. Complex 2 is an example of a polymeric copper(II) derivative containing the bidentate bridging sulfate ligand in the long-bonded axial positions. Each copper(II) ion in 2 shows an elongated tetragonal octahedral stereochemistry. The CuN₄N′ chromophore of 3 involves a square-based pyramidal structure, slightly distorted towards a trigonal bipyramidal stereochemistry, τ=0.13. One of the SCN⁻ anions is bonded to the copper(II) ion via the N atom in the axial position of the square pyramid. Complex 4 is centrosymmetric and octahedrally elongated, with the SCN⁻ anions coordinating in axial positions via the S atom. The structures of complexes 1–4 and their ESR and electronic reflectance spectra are compared with those of related complexes.     

Synthesis,spectroscopic, and biological activities of two binuclear complexes [Cu(II)(1-phenylamidino-O-methylurea)2(H2O)]2(Cl2)2 and [Cu(II)(1-phenylamidino-O-i-butylurea)tmen]2(Cl2)2·2H2O

EPR spectra of two copper(II) binuclear complexes, [Cu(II)(1-phenylamidino-O-methylurea)₂(H₂O)]₂(Cl₂)₂ (1) and [Cu(II)(1-phenylamidino-O-i-butylurea)tmen]₂(Cl₂)₂?·?2H₂O (2), at room temperature showed fine structure transitions (ΔM _s?=?±1) and a very weak half-field signal corresponding to forbidden transitions (ΔM _s?=?±2). The spectrum of 1 showed disappearance of normal and half-field transitions when cooled to 77?K, suggesting antiferromagnetical coupling dicopper complex which is also supported by the low magnetic moments (µ _eff?=?1.64?B.M.). The isotropic exchange interaction constant J (41?cm^?1) for 2 indicated that interaction between the two spins of the binuclear complex is ferromagnetic, confirmed from the high magnetic moment value (µ _eff?=?2.25?B.M.). The binding of these complexes with calf thymus DNA suggested that these complexes interact with DNA by electrostatic or groove binding, not by intercalation. The two complexes have good antibacterial activity against tested bacteria responsible for urinary tract infection.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

[Cu(phen)2·Cl]·Bsesa的晶体结构

对苯磺酰牛磺酸阴离子一维链构筑的三维配位聚合物[Cu(phen)2·Cl]·Bsesa(phen=o-phenanth-roline,BsesaH=2-Benzenesulfonylamino-ethanesulfonicacid)进行了元素分析、红外光谱、X射线衍射等表征。分析结果表明此配合物属单斜晶系,空间群为P21/c,晶胞参数为:a=0.9719(2)nm,b=2.5521(5)nm,c=1.2505(2)nm,β=93.407(5)°,V=3.096(1)nm3,Z=4,Dc=1.553g/cm3,μ=0.978mm-1,F(000)=1484。配合物中的金属铜离子与2个邻菲咯啉配位,还与一个Cl阴离子配位。苯磺酰牛磺酸阴离子通过N-H…O氢键形成一维螺旋链,配阳离子通过π-π堆积作用形成一维链,邻近的一维链再通过π-π堆积作用形成二维网,在二维网之间平衡插入由苯磺酰牛磺酸阴离子构筑一维螺旋链,邻近的螺旋链之间的距离为0.972(1)nm,螺旋链与二维网之间通过弱而丰富的C-H…O氢键形成三维网结构。     

Characterization of [Re2Cl3(μ-dppm)2(NCCH3)2][Cl] and [Re2Cl3(μ-dppm)2(NCC6H5)2][Cl]·2CH2Cl2 by X-ray Crystallographic and Two-Dimensional NMR Spectroscopic Techniques

The complex Re₂Cl₆(P-n-Bu₃)₂ prepared in situ reacts with CH₃CN to form a blue-green solution. Addition of the chelating phosphine bis(diphenylphosphino)methane (dppm) results in the formation of the complex [Re₂Cl₃(-dppm)₂(NCCH₃)₂][Cl] (1) upon heating. The two acetonitrile molecules adopt a trans geometry on the rhenium center with the axially coordinated chlorine. The analogous trans benzonitrile species [Re₂Cl₃(-dppm)₂(NCC₆H₅)₂][Cl]·2CH₂Cl₂ (2) is synthesized under the same reaction conditions. The coupling constants of the AABB ³¹P{¹H} NMR spectra of the compounds were elucidated from ³¹P–³¹P homonuclear J-resolved NMR experiments. Additional characterization methods include ³¹P{¹H} NMR spectroscopy, UV-vis spectroscopy, and X-ray crystallography.     

Synthesis and crystal structures of supramolecular compounds: [Cu(mpca)2(H2O)] · 3H2O and [Cu2(mpca)2(pyr)4]

A new chelate ligand, 5-methyl-1H-pyrazole-3-carboxylic acid (mpca), has been synthesized. This ligand reacts with cupric sulfate to give two supramolecular compounds [Cu(mpca)₂(H₂O)] · 3H₂O (1) and [Cu₂(mpca)₂(pyr)₄] (Pyr = pyridine) (2), which were characterized by elemental analysis and X-ray crystal diffraction. Helical water chain and strong π–π interaction are important for the stability of the 3-D structure of these supramolecules.     

Copper(I) halide complexes with ethylenediaminium L0(H+)2, N,N,N′,N′-tetraallylethylenediaminium L4(H+)2, and N,N,N,N′,N′-pentaallylethylenediaminium L5(H+). Synthesis and crystal structures of the complexes [L0(H+)2]0.5CuCl2, [L0(H+)2]0.5CuBr1.67Cl0.33, [{L4(H+)2}0.5Cu2Cl3], and [L5(H+)Cu4Br6]

Alkylation of ethylenediamine with allyl bromide in the presence of NaHCO₃ in benzene-ethanol and acetone-ethanol gave N,N,N′,N′-tetraallylethylenediamine L⁴ and N,N,N,N′,N′-pentaallylethylenediaminium bromide (L₅(H⁺)Br₂), respectively. The ac electrochemical synthesis at copper wire electrodes in solutions of copper(II) halide and an appropriate ligand yielded single crystals of Cu(I) complexes with ethylenediaminium ([L⁰(H⁺)₂]_0.5CuCl₂ (I) and [L⁰(H⁺)₂]_0.5CuBr_1.67Cl_0.33 (II)) and its N-allyl derivatives N,N,N′,N′-tetraallylethylenediaminium ([{L⁴(H⁺)₂}_0.5Cu₂Cl₃] (III)) and N,N,N,N′,N′-pentaallylethylenediaminium ([L⁵(H⁺)Cu₄Br₆] (IV)). The crystal structures of complexes I–IV were determined by X-ray diffraction. The isostructural crystals of complexes I and II are triclinic, space group P $ \bar 1 $ , Z = 2. For I: a = 5.936(3), b = 6.387(3), c = 7.126(4) Å, α = 67.82(4)°, β = 72.98(4)°, γ = 67.55(4)°, V = 227.7(2) ų. For II a = 6.110(3), b = 6.657(3), c = 7.309(3) Å, α = 68.40(3)°, β = 72.38(3)°, γ = 67.23(3)°, V = 250.4(2) ų. In structures I and II, the organic cations are between infinite anionic chains (Cu ₂ ^? ) _n . The crystals of π-complex III are triclinic, space group P $ \bar 1 $ , a = 6.851(4), b = 8.729(4), c = 9.960(4) Å, α = 98.25(3)°, β = 102.29(3)°, γ = 107.30(3)°, V = 541.8(5) ų, Z = 2. In structure III, all the four allyl groups are π-coordinated by the metal atoms of four discrete anions Cu₄Cl ₆ ^2? . The crystals of π-complex IV are monoclinic, space group C2/c, a = 15.228(5), b = 17.095(6), c = 20.182(6) Å, β = 92.43(4)°, V = 5249(3) ų, Z = 8. Only two of five allyl groups at the same N atom are coordinated by copper(I) atoms. Structure IV contains a complex inorganic fragment of the formula (Cu₄Br ₆ ^2? ) _n .     

3-(diallylamino)propanenitrile ((C3H5)2NC2H4CN, L) π-complexes with copper(I) ionic salts. Syntheses and crystal structures of compounds [Cu(H+L)ClO4]ClO4 · H2O, [Cu(H+L)BF4]BF4 · H2O, and [Cu(H+L)(H2O)]SiF6 · H2O

Qualitative single crystals of ??-complexes Cu(H⁺L)(ClO₄)]ClO₄ · H₂O (I), Cu(H⁺L)(BF₄)]BF₄ · H₂O (II), and [Cu(H⁺L)(H₂O)]SiF₆ · H₂O (III) are synthesized from solutions of 3-(diallylamino)propanenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5?C5 and from the copper(II) salts (Cu(ClO₄)₂ · 6H₂O, Cu(BF₄)₂ · 6H₂O, and CuSiF₆ · 4H₂O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostructural, space group P2₁/n, Z = 4. For compound III, space group P2₁/c, Z = 8. Unit cell parameters: for I a =7.8153(3), b = 16.7824(7), c = 12.4426(5) ?, ?? = 93.410(2)°, V = 1629.1(1) ?³; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) ?, ?? = 94.354(2)°, V = 1583.2(1); and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) ?, ?? = 91.820(6)°, V = 2843.9(7) ?³. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H⁺L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO ₄ ^? or BF ₄ ^? anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF ₆ ^2? anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F??H (2.05?C2.51 ?).     

[Cu(bpp)2(bpdc)(H2O)2]×2H2O and [Cu(bpp)2](tdc)×7.5H2O的合成、晶体结构和热稳定性

在室温下, 由Cu(NO3)2 、1,3 -二（4 -吡啶基）丙烷(bpp)、4,4 ’ -联苯二甲酸(H2bpdc)和2,5-噻吩二甲酸(H2tdc)制备出两种新型铜( II)配位聚合物[Cu(bpp)2(bpdc)(H2O)2]n·2nH2O, 1 和[Cu(bpp)2]n·n(tdc) 7.5nH2O, 2。两个配位聚合物均为一维线型结构,铜原子均采取变形的八面体结构,在轴线方向上的两个水分子与铜原子存在较弱的配位作用。在配合物1中,两个bpdc羧酸根离子与铜原子配位,而2中的tdc羧酸离子没有与铜原子键合,只是作为反离子平衡电荷。在两个产物中, 配体bpp具有不同的构象。热重分析表明配合物1与2分别在110°C和160°C以下是稳定的。     

[Cu4Cl4(C10H16S4)2]的合成和晶体结构

早有文献[1]报导，二硫代乙酸丙酮C5H8S2(记为SacSac）能以下列三种形式存在于金属配合物中：（I）（SacSac）2M，如M=Ni，Co等，其中SacSac呈负一价，通过两个S原子和金属直接螫合；（11）（SacSaChMCI。；如M二Mn，CdSn等，（S。Sac）呈正一价，且以阳离子状态存在干晶体和溶     

Synthesis and Crystal Structure of 1-D Chain Copper(Ⅱ) Complex:[Cu(L)Cl2]n(L = 2,5-Di-2-pyridyl-1,3,4-oxodiazole)

The title complex, [Cu(L)Cl2]n (L = 2,5-di-2-pyridyl-1,3,4-oxodiazole) 1, has mixture solvent of CH3CN and CH2Cl2 (L is generated from the metal-assisted hydrolysis reaction of bptz) and structurally characterized. It crystallizes in space group C2/c of monoclinic system with cell parameters: a = 9.812(2), b = 12.679(3), c = 1 1.111(2) A, β = 103.92(3)°, V = 1341.6(5)A3, Z = 4, Dc = 1.776 g/cm3, Mr= 358.66, F(000) = 716, μ = 2.024 mm-1 and S = 1.004. The final R = 0.0346 and wR = 0.0938 for 1011 observed reflections with I ＞ 2σ(I). The Cu( Ⅱ ) ion is six-coordinated by four N atoms of two L ligands and two Cl- ions in a distorted octahedral geometry. The ligand L acts as a bis-bidentate ligand to bridge the Cu( Ⅱ ) ions, resulting in an infinite chain structure.     

Synthesis and Crystal Structure of a [Cu(HTren)Cl2]ClO4·H2O Complex (Tren = Tris(2-aminoethyl)amine)

The title complex [Cu(HTren)Cl2]ClO4·H2O (Tren = tris(2-aminoethyl)amine) was crystal (CuC6H21Cl3N4O5) is of triclinic, space group P-1, with a = 8.2689(2), b = 8.4503(3), c=11.6801(4)(A), a = 96.9350(10), β= 108.2440(10), γ = 90.7550(10)°, V= 768.32(4)(A)3, Z= 2, Mr=399.16, Dc= 1.725 g/cm3,μ= 1.962 mm-1, F(000) = 410, T= 293(2) K, the final R = 0.0479 and wR = 0.1339 for 2659 observed reflections with I ＞ 2σ(I). X-ray single-crystal structure analysis reveals that the copper(Ⅱ) atom adopts a slightly distorted square-pyramidal geometry. The distances between Cu and N atoms (N(1), N(2), N(3)) range from 1.975(4) to 2.116(3)(A). The bond lengths of Cu-Cl(1) and Cu-Cl(2) are 2.309(10) and 2.591(10) (A), respectively. The whole crystal presents a three-dimensional network structure by hydrogen bonds.     

Tansition metal complexes with 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL): Synthesis and crystal structure of [Co(L)2(H2O)4] · 6H2O and [Cu(L)2(H2O)2] · 4H2O

Transition metal complexes of 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL), namely [Co(L)₂(H₂O)₄] · 6H₂O (I) and [Cu(L)₂(H₂O)₂] · 4H₂O (II), have been synthesized by a hydrothermal procedure and characterized by X-ray crystallography, CIF files CCDC nos. 1007524 (I), 1007525 (II). Both I and II are mononuclear molecules. In I, the Co²⁺ ion is in octahedral coordiantion environment and surrounded by four O atoms from water molecules and two carboxylate O atoms of two deprotonated ligand (L^?) occupied six culmination. While in II, the Cu²⁺ ion is located in a square-planar geometry, bounded to two aqua O atoms and two carboxylate O atoms from L^?.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Two new Cu(II) m-hydroxybenzoato complexes with chloro- and carboxylato-bridged dinuclear [Cu(µ2−Cl)(µ2−COO)Cu] cores

In aqueous methanolic solution, reactions of CuCl₂, m-hydroxybenzoic acid (HL), and NaOH with 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) at room temperature afforded {[Cu(bpy)L](µ₂?Cl)(µ₂?L)[Cu(bpy)L]}?1.2H₂O (1) and {[Cu(phen)Cl](µ₂?Cl)(µ₂?L)[Cu(phen)L]} (2) with chloro- and carboxylato-bridged dinuclear [Cu(µ₂?Cl)(µ₂?COO)Cu] cores. The Cu₂ dimers in 1 are pairwise aggregated to form H-bonded tetranuclear motifs, which are extended by H₂O into 1-D H-bonded chains and further assembled into 2-D supramolecular networks. The Cu₂ dimers in 2 are also linked into 1-D H-bonded chains and further assembled into 2-D supramolecular layers. Magnetic measurements indicate that significant antiferromagnetic interactions (J = ?15.9, ?12.2 cm^?1) between Cu²⁺ ions are dominant in these dinuclear [Cu(µ₂?Cl)(µ₂?COO)Cu] cores. To the best of our knowledge, 2, crystallizing in the acentric polar orthorhombic space group Pna2₁, represents the first example of metal m-hydroxybenzoato complexes with ferroelectric properties with a remnant polarization (Pr) of ca. 0.04?µC cm^?2, coercive field (Ec) of ca. 2.52 kV cm^?1, and saturation of the spontaneous polarization (Ps) at ca. 0.195?µC cm^?2.     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.