Synthesis and characterization of μ-oxamido copper(Ⅱ)-iron(Ⅱ) heterobinuclear complexes with an antiferromagnetic exchange interaction

Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. Complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-2     

Synthesis, Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper(Ⅱ) Complex with IM-1'-MeBzIm-κ2 N, O Mode

A new dinuclear copper(Ⅱ) complex with imino nitroxide radicals [Cu2(NO3)2(IM-1'-MeBzlm)2(dca)2] (IM-1'-MeBzlm = 2-{2'-[(1'-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimi-dazoline-1-oxyl, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinie, space group P1, with a =9.440(5), b = 10.124(6), c = 11.603(7)(A°), α= 102.904(7),β = 94.033(6), γ= 104.299(7)°,C34H40Cu2N16O8, Mr= 927.90, V= 1038.2(10) (A°)3, Z = 1, Dc=1.484 g/cm3,μ(MoKα) = 1.093 mm-1,F(000) = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with I > 2σ(I). X-ray analysis reveals that two Cu(Ⅱ) atoms are bridged by two dicyanamides to form a centrosymmetric Cu(Ⅱ)-Cu(Ⅱ) dinuclear entity. Every Cu(Ⅱ) ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1'-MeBzlm ligand coordinates to the metal ion with the κ2 N(1'-MeBzlm), O(IM) mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu(Ⅱ) ion and the IM-1'-MeBzlm are ferromagnetic with J = 12.46 cm-1, where the spin Hamitonian is defined as H= -2JS1S2 within the complex.     

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.     

Synthesis and Crystal Structure of a Novel Binuclear Cu(Ⅱ) Complex with Tetradentate Schiff-base Ligand

A novel binuclear complex ([Cu2(μ2-shed)(hshed)]·(ClO4)·H2O, h2shed = N-salicylidene-N′-(2-hydroxyethyl)ethylenediamine) has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 12.511(10), b =15.750(12), c = 14.281(12) (A), β = 100.564(14)°, C22H31ClN4O9Cu2, Mr = 658.04, V= 2766(4) (A)3, Z =4, Dc = 1.580 g/cm3, μ(MoKα) = 1.689 mm-1, F(000) = 1352, the final R = 0.0528 and wR = 0.1433 for 4880 independent reflections with Rint = 0.0577. The complex is a binuclear copper compound,and two Cu(Ⅱ ) ions in the binuclear cation are in different coordination environments. The Cu(1) ion adopts a distorted square pyramidal geometry (τ = 0.22) with four donor atoms (N2O2) of the ligand in the basal plane, and one hydroxyl oxygen atom with protonated form occupying the apical position.The Cu(2) ion assumes the geometry of a distorted square plane with four donor atoms (N2O2) of the ligand. The Cu…Cu separation is 3.103 (A). In addition, N-H…O and C-H…O intermolecular hydrogen bonding interactions link these binuclear cations into a quasi one-dimensional chain along the a axis.     

Synthesis and Characterization of Nickel(Ⅱ) and Copper(Ⅱ) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)

Two homochiral metallosalen complexes,Ni(salen) (salen=(1R,2R)-(-)-diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene) 1 and Cu(salen) 2,have been synthesized and characterized by IR,microanalysis,TGA,powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P2_12_12 with Z=4. For 1,α= 12.082(2),b = 15.447(3),c = 18.784(4)(A),V= 3505.7(12) (A)~3,M_r = 731.50,D_c = 1.386 g/cm~3,μ= 0.606 mm~(-1),F(000)=1544,the final GOOF=1.043,R=0.0496 and wR=0.1248 for 4791 observed reflections with Ⅰ> 2σ(Ⅰ). For 2,α=12.181(2),b=15.501(3),c=18.877(4)(A),V= 3564.3(12)(A)~3,M_r=736.33,Dc = 1.372 g/cm~3,μ=0.665 mm~(-1),F(000)=1548,the final GOOF= 1.062,R=0.0575 and wR=0.1508 for 4562 observed reflections with Ⅰ> 20(Ⅰ). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.     

Synthesis and Crystal Structure of a Manganese(Ⅱ) Complex with 2-(4'-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Mn2(cbba)4(phen)2 (Hcbba = 2-(4'-chlorine-benzoyl)-benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.154(5), b = 18.166(7), c =31.197(13) (A°), V = 6887(5) (A°)3, C80H48C14Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm3, μ(MoKa) =0.591 mm-1, F(000) = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections (I > 2σ(I)). In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.     

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu(C9H11N3)Cl2]2 (C18H22Cl4Cu2N6), has been synthe- sized and characterized by X-ray structure determination. It crystallizes in the triclinic P1 space group with a = 7.526(3), b = 9.473(4), c = 9.535(3) , α = 117.214(10), β = 108.251(9), γ = 91.560(6)o, V = 562.3(4) 3, Z = 1, Mr = 591.30, F(000) = 298, Dc = 1.746 g/cm3, μ(MoKα) = 2.385 mm-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted trigonal bipyramid of five coordination atoms (two nitrogen and three chlorine atoms). Two copper(II) atoms were bridged by two chlorine anions (Cl(2) and Cl(2a)) to form a Cu(II)-Cu(II) binuclear entity with the distance between two copper(II) atoms of 3.398 .     

Trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes bridged by μ_3-carbonato anion

The trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes [(CuTPA)_3(μ3-CO_3)] (ClO_4)_4(1) and [(ZnTPA)_3(μ_3-CO_3)] (ClO_4)_4 (2) (TPA=tri(pyridylmethyl) amine) have been synthesized. X-ray structure analysis of the two complexes proves that CO_3~(2-) anion has an unusual triply bridging ligand, bridging three CuTPA and ZnTPA units respectively, and assembles new trinuclear complexes. The CO_3_(2-) comes from atmospheric CO_2. The structure of each trinuclear unit consists of three copper or zinc atoms in a five-coordinate triangular bipyramidal environment. The [(CuTPA)_3 (μ_3-CO_3)] (ClO_4)_4 compound shows a very weak antiferromagnetic coupling.     

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C_(13)H_9N_2O)Cl]_2·(CH_3CN)_2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu(C13H9N2O)Cl]2·(CH3CN)2 (C30H24Cl2Cu2N6O2), has been synthesized and characterized by X-ray structure determination. It crystallizes in the tricli- nic system, space group P1, with a = 7.6677(14), b = 9.2375(17), c = 11.227(2) , α = 81.338(3), β = 88.173(4), γ = 66.199(3)o, V = 718.9(2) 3, Z = 1, Mr = 698.53, F(000) = 354, Dc = 1.613 g/cm3, μ(MoKα) = 1.705 mm-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms (one nitrogen atom, two oxygen anions, and one chlorine atom). Two copper(II) atoms are bridged by two oxygen anions (O(1) and O(1a)) of two phenolates to form a Cu(II)–Cu(II) binuclear entity, and the distance between two copper(II) atoms is 3.0144(15) .     

Synthesis and Crystal Structure of Zn(Ⅱ) Complex with Tridentate Ligand N-(2-Hydroxy-1-naphthylidene)-L-serine

A new Zn(Ⅱ) complex, [Zn(L)2(H2O)2], where H2L = N-(2-hydroxy-l-naphthylidene)-L-serine, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 13.669(2), b = 6.4657(9), c =31.463(5) (A), β = 98.010(2)°, V = 2753.6(7) (A)3, Z = 8, Mr = 358.64, Dc = 1.730 g/cm3, F(000) =1472,μ(MoKa) = 1.814 mm-1, the final R = 0.0355 and wR = 0.0706. The Zn(Ⅱ) atom adopts a square-pyramidal geometry coordinated by the tridentate ligand and two water molecules.Intermolecular hydrogen bonds link the complex molecules into a two-dimensional layer.     

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(ClO4)2]2.2H2O was 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(ClO4)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.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Cobalt(Ⅱ) Complex with 2-Pyridinecarboxyic Acid and 4,4'-Bipyridine Ligands

A new metal-organic coordination polymer [Co(2-pya)2(4,4'-bipy)]2n·[(4,4'- bipy)0.5· H2O]2n(2-pya = 2-pyridinecarboxylic acid, 4,4'-bipy = 4,4'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719(2), c = 10.710(2) A, V = 5527.8(14) A3, C54H46N10Co2O10, Mr = 1112.87, Dc = 1.337 g/cm3,μ(MoKα) = 0.665 mm-1, F(000) = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections (I ＞ 2σ(I)). It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4'-bipyridine.     

Synthesis and Magnetism of 2-Hydroxy-1,3-propylene-bis(oxamato)-bridged Co~ⅡCu~ⅡCo~Ⅱ Complexes

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Hydrothermal Synthesis, Crystal Structure and Magnetic Property of a Novel Pentanuclear Copper(Ⅱ) Complex: [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5

The pentanuclear complex, [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5 (H3SIP=5-sulfoi-sophthalic acid), has been synthesized by the hydrothermal reaction of CuCl2 with NaH2SIP at 160 ℃, and characterized by single-crystal X-ray diffraction and IR spectrum. The crystal of the complex crystallizes in a trielinic system, space group P1, with a = 7.0018(5), b = 11.9725(8), c = 19.0424(13) A, α = 78.8540(10), β = 85.1710(10),γ = 83.6080(10)~, V = 1553.24(19) A3, Z = 1, C32H60O51S4Cu5, Mr= 1706.74, Dc= 1.825 g/cm3,μ = 1.937 mm-1, F(000) = 869, the final R = 0.0709 and wR = 0.1503 for 4235 observed reflections with I > 2σ(I). The five Cu2+ ions are connected by two symmetry-related tridentate SIP3- ligands and charge-balanced by two monodentate HSIP2- ligands, giving a discrete pentanuclear structure. The pentanuclear copper molecules are linked by hydrogen bonds to form a three-dimensional supramolecular structure. The temperature-dependent magnetic susceptibility data revealed weak ferromagnetic magnetic interactions between the Cu2+ ions.     

Hydrothermal Synthesis and Crystal Structure of a New Manganese(Ⅱ) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2'-Bipyridine Ligands

A new metal-organic complex [Mn_2(PDC)_2(bipy)_2(H_2O)_2] (H_2PDC=2,4-pyridinedicarboxylic acid,bipy=2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic,space group P~(-)1 with α=7.376(3),b=9.990(4),c=11.950(5)(A),α=75.217(5),β=78.052(5),γ=70.655(5)°,V=796.0(5)(A)~3,C_(34)H_(26)Mn_2N_(6O)O_(10),M_r=788.49,D_c= 1.645 g/cm~3,μ(MoKa) = 0.866 mm~(-1),F(000)=235,Z=1,the final R=0.0425 and wR=0.0700 for 1971 observed reflections (Ⅰ > 2σ(Ⅰ)). In the crystal structure,the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands,one aqua ligand,and three nitrogen atoms from 2,2'-bipy and PDC ligands,giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.     

New Ni(Ⅱ)Cu(Ⅱ)Ni(Ⅱ) trinuclear complexes with an S=3/2 high-spin ground state

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10-phenanthroline(NO2-phen) (2), 2,2'-bipyridyl(bpy) (3) and 4,4'-dimethyl-2,2'-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)2.3H2O has been studied in the 4-300 K range, giving the exchange integral J=-109 cm-1. The MT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

Synthesis and Structure of a Two-dimensional Double Chain Iron(Ⅱ)L-Trp Coordination Polymer[Fe(L-trp)2(HL-trp)2]n

The title complex [Fe(L-trp)2(HL-trp)2]n(L-trp=L-tryptohan or 2-amino-3-(1H -indol-3-y1)-propanoic acid)has been formed by a hydrothermal method involving hexaaqua-cobaltous perchlorate and L-tryptophan.The product was characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction.The crysal belongs to the monoclinic system,space group P21/c,with a=19.828(3),b=5.4233(14),c=9.2796(16)(A),β=97.691(2)°,V=988.9(3)(A)3,Z=2,Mr=462.29,Dx=1.553 g/cm3,F(000)=480,μ=0.802 mm-1,the final R=0.0399 and wR=0.0930 for 1738 observed reflections with I＞2o(I).The structural analysis shows that the complex assumes a two-dimensional double chain plane structure.     

Synthesis and Crystal Structure of a Mononuclear Zn(Ⅱ) Complex with Tridentate Schiff Base, Zn(C12H18N2O)(NCS)2

The title complex Zn(HL)(NCS)2 (C14H18N4OS2Zn, Mr = 387.81, HL = N-(3-dimethyl-aminopropyl)-salicylaldimine) has been synthesized by the reaction of ZnSO4·7H2O with the Schiff base N-(3-dimethylaminopropyl)-salicylaldimine derived from the condensation reaction of 3-dimethylamino-1-propylamine with salicyladehyde. It crystallizes in the monoclinic system, space group P21/n with a = 9.8360(8), b = 14.930(1), c = 12.277(1) (A), β= 101.455(2)°, V= 1767.0(3) (A)3,Z = 4, F(000) = 800, Dc = 1.458 g/cm3 and μ(MoKα) = 1.631 mm-1. The structure was refined to R = 0.0463 and wR = 0.1065 for 2681 observed reflections (I ＞ 2σ(Ⅰ)). Crystal analyses revealed that the Zn(Ⅱ) atom is coordinated by two nitrogen atoms of two NCS-, and an oxygen atom as well as a nitrogen atom of amine from the neutral Schiff base ligand of N-(3-dimethyl-aminopropyl)-salicylaldimine to give a distorted tetrahedral geometry.     

Synthesis, Characterization and Cytotoxicity of Ammine/Methylamine Platinum(Ⅱ) Complexes with Carboxylates

Seven novel platinum (Ⅱ) complexes [Pt (Ⅱ) (NH3) (CH3NH2) X2] (Ⅰ -Ⅶ) (X: CH3COO- ,CH2 ClCOO - , CHCl2COO -, C6H5-COO - , p-CH3O-C6H4 -COO - , p-NH2-C6 H4 -COO - , p-NO2 -C6 H4 -COO-) were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis,IR, UV, and 1 H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence: cisplatin ＞Ⅳ＞Ⅴ＞Ⅵ＞Ⅶ＞Ⅰ＞Ⅱ＞Ⅲ. Moreover, the complexes(Ⅰ -Ⅶ) display substantially greater activities against EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.     

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.