Two Cobalt(Ⅱ) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-ylethylidene)-ethane-1,2-diamine: Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL2]X·H2O (X = ClO4-,NO3-)

The reactions of Co(CIO4)2.6H2O and Co(NO3)2·6H2O with the di-Schiff base ligand N,N'-bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine (LA) in ethanol have been investigated.The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2](CIO4)2·H2O 1 and [CoL2](NO3)2·H2O 2 as isolatable products (L = N-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine), where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA.Both complexes were characterized by X-ray crystallography.Crystal data for complex 1: monoclinic, space group P21/c, a = 11.9214(10), b = 23.5828(17), c = 14.0387(12)(A), β= 135.219[4]°,C22H30CI2CoN9O9,Mr = 680.37, V = 2780.1(4)(A)3, Z = 4, Dc = 1.625 g/cm3,μ(MoKa) = 0.876 mm-1, F(000) = 1404,the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections (I＞2σ(I)).Crystal data for complex 2: monoclinic, space group P21/c, a = 18.2162(16), b = 10.0610(6), c = 18.593(2)(A),β=130.099(3)°, C22H30CoN10O7, Mr = 605.49, V = 2606.5(4)(A)3, Z = 4, Dc = 1.543 g/cm3,μ(MoKα)= 0.722 mm-1, F(000) = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections (I ＞ 2σ(I)).X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere.In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4- (or NO3-) groups to form a 3D framework.In complex 2, the strong π-π interactions increase the stability of the structure.     

Two Cobalt(II) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine:Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL_2]X·H_2O (X = ClO_4~-, NO_3~-)

The reactions of Co(ClO4)2·6H2O and Co(NO3)2·6H2O with the di-Schiff base ligand N,N'-bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine (LA) in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2](ClO4)2·H2O 1 and [CoL2](NO3)2·H2O 2 as isolatable products (L = N-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine), where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1: monoclinic, space group P21/c, a = 11.9214(10), b = 23.5828(17), c = 14.0387(12) , β = 135.219(4)o, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1(4) 3, Z = 4, Dc = 1.625 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections (I > 2σ(I)). Crystal data for complex 2: monoclinic, space group P21/c, a = 18.2162(16), b = 10.0610(6), c = 18.593(2) , β = 130.099(3)o, C22H30CoN10O7, Mr = 605.49, V = 2606.5(4) 3, Z = 4, Dc = 1.543 g/cm3, μ(MoKα) = 0.722 mm-1, F(000) = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate ligands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4-(or NO3-) groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.     

Syntheses and Crystal Structures of Two New Zinc（ Ⅱ ） Nitroxide Radical Complexes Bridged by Isophthalate

Two novel complexes [Zn（NIT3-py）（ip）]n 1 and [Zn（im3-py）（ip）]n 2 （NIT3-py = 2-（3＇-pyridyl）-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide, im3-py = 2-（3＇-pyridyl）-4,4,5,5-tetramethylimidazoline-1-oxyl, ip = isophthalate） have been synthesized and structurally determined by X-ray diffraction. Crystal data for 1： C32H36N6O8Zn, Mr= 698.04, monoclinic, space group Cc with a = 23.600（3）, b = 10.2073（12）, c = 13.4027（16）A,β = 92.586（2）°, V = 3225.3（7） A^3, Dc= 1.438 g/cm^3, F（000） = 1456,μ（MoKa） = 0.822 mm^-1, Z = 4, the final R = 0.0390 and wR = 0.1032 for 6037 independent reflections with Rint = 0.0214. Crystal data for 2： C32H36N6O6Zn, Mr= 666.04, monoclinic, space group C2/c with a = 24.434（4）, b = 13.543（2）, c = 10.2379（16） A, β = 109.024（2）°, V = 3202.8（9）A3 Dc= 1.381 g/cm^3, F（000） = 1392,μ（MoKa） = 0.820 mm^-1, Z = 4, the final R = 0.0304 and wR = 0.0658 for 2833 independent reflections with Rint = 0.0307. X-ray analysis reveals that both Zn（ Ⅱ ） ions are four-coordinated by two pyridyl-N atoms from nitroxide radicals and two carboxylate oxygen atoms to form distorted tetrahedral geometries. Each isophthalate dianion binds two Zn（ Ⅱ ） ions in a monodentate mode, leading to a I-D chain structure.     

Synthesis and Crystal Structure of 1,2-Bis（2-benzimidazolyl）benzene

The title compound C6H4(C7H5N2)2 was prepared by the condensation of o-phenylenediamine with o-phthalic acid and characterized by elemental analysis, IR, UV and ^1H NMR spectra, and its structure was determined by single-crystal X-ray diffraction,showing the compound molecule belongs to (72 point group. A ID chain structure was formed by the intermolecular hydrogen bonds (N(2)H…N(I)).     

Synthesis, Crystal Structure and Characterization of α-（1-Benzimidazolyl） -hypnone Cobalt（Ⅱ） Complex： [CoCl （ C7H5N2CH2COPh）4] Br

The crystal structure of [CoCl ( C7H5N2CH2COPh)4] Br has been determined by means of X-ray crystallography. The molecular structure consists of a discrete [CoCl ( C7H5N2CH2COPh)4] ^ cation and one Br^- anion, in the [CoCl ( C7H5N2CH2COPh)4]^ cation, the coordination geometry of the central Co atom is square-pyramidal with four tertiary N atoms of benzimidazole from four α-( benzimidazol-1-yl) -hypnone ligands in the basal position and one chloride anion in the apical position. In the solid state, [CoCl ( C7H5N2CH2COPh)4]^ and Br^- anion possess intermolecular and intramolecular interactions, which stabilize the crystal structure. The characterization of the title compound were also carried out by using elemeutal analysis, FTIR, UV spectrometries and TG-DSC.     

Synthesis, Crystal Structure, Antibacterial Activity and Interaction with BSA of Copper( Ⅱ ) Complex with Ligand N, N' -Bis ( 4-chlorobenzyl ) propane-1, 2-diamine

合成了N,N'-双(4-氯苄基)-1,2-丙二胺铜(Ⅱ)配合物[ CuCl( C17 H20C12N2)2]·(NH4)·Cl2,通过元素分析和IR光谱对其进行了表征,并通过X射线单晶衍射确定了其晶体结构.晶体结构分析表明,该晶体属于三斜晶系,P1空间群,晶胞参数a=1.35222(16) nm,b=1.37899(17) nm,c=1.39806(19) nm;α=60.954(1)°,β=87.502(2)°,γ=65.970(1)°,V=2.0424(4) nm3,Dc=1.357 g/cm3,Z=2,F(000)=862,R1=0.0925,wR2=0.2668[ Ⅰ＞2σ(Ⅰ)],S=1.001.配合物的金属中心与来自2个配体的4个氮原子和1个末端氯原子配位,形成了轻微扭曲的四方锥几何构型,扭曲指数τ=0.04(1).抗菌实验结果显示,配合物对大肠杆菌、枯草杆菌和金色葡萄球菌均表现出良好的抑菌作用.采用荧光光谱研究了不同温度下配合物与牛血清白蛋白( BSA)的相瓦作用,结果表明,配合物对BSA的荧光猝灭属于静态猝灭.计算了不同温度下配合物与BSA间的结合常数(Ka)、结合位点(n≈1)及相关热力学参数(△H＞0,△S＞0,△G＜0),结果表明,二者主要靠疏水作用力结合.依据F(o)ster的非辐射能量转移理论,求得给体(BSA)与受体(配合物)间的距离r=2.56 nm,说明配合物与BSA之间可能发生了非辐射能量转移.     

Synthesis and One－dimensional Structure of Cobalt（Ⅱ） Complex [－ （NaOC2H5） CoL2]n

The treatment of bis (2-hydroxybenzyl)-amine (HL) with NaOH and Co ( Ⅱ )(NO)2 gives isostructural one-dimensional coordination polymers [-(NaOC2H5)CoL2]n(1). The cobalt ions have an octahedral geometry and are coordinated by two erystallographicaUy independent ligands which are further linked by β-Ophenol bridged Co and Na atoms to give a one-dimentional structure.     

Synthesis,Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n

A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.0293（3）, b = 2.0293（3）, c = 1.3758（2） nm, α =β= γ = 90°, V= 5.6657（13） nm3, Dc= 1.379 g/cm3, Z = 8, μ（MoKa） = 0.815 mm-1, Mr = 588.14, F（000） = 2456, S = 1.047, R = 0.0459 and wR = 0.1053. The crystal structure shows that two neighboring Cu（Ⅱ） ions are linked together by one bridging-chelating 2,4,6-trimethyl-benzoic group, forming a one-dimensional chain structure. Each Cu（Ⅱ） ion is coordinated with two nitrogen atoms from one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethyl-benzoic acid molecules and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. The cyclic voltammetry behavior of the complex was also investigated.     

α,ω—双（2—苯并咪唑）二硫化合物的简便合成

咪唑具有特异的质子授-受性能、共轭酸-碱性能及识别络合性能,享有“生命配体”之美誉。在自然界中,咪唑作为许多酶的活性中心功能基,参与了许多重要的生物化学反应,对生命活动起着十分重要的作用[1,2]。许多药物、农药、酶抑制剂及精细化学品等也含有咪唑结构组分[3-5]。选用咪唑、双咪唑成功构筑了多种人工受体、人工酶及仿生功能体系[6-9]。探索、拓展咪唑、双咪唑化合物的合成反应及应用是很有意义的。近年,我们报道了含脂肪烃、芳香烃、醚键为桥基的几类双咪唑或双苯并咪唑的合成[10-13],以及手性含硫大环配体的合成[14]。本文报道一类…     

Synthesis,Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn （NAA ）2（ 4,4′-bipy ） （H2O）4]n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

Synthesis and Crystal Structure of a Co（ Ⅱ ） Complex with Taurine-5-methyl-2-hydroxyisophthalaldehyde Schiff Bases [Co（C13H16N2O7S2）（H2O）3]2·H2O

The title complex [CoL（H20）3]2·H2O （C26H46N4O21S4CO2）, where L = taurine-5- methyl-2-hydroxyisophthalaldehydes, has been synthesized and characterized by IR and X-ray diffraction analysis. The crystal of the complex belongs to the triclinic system, space group P1, with a = 11.197（4）, b = 13.309（5）, c = 14.486（5） ]A, a = 78.827（13）,β = 70.547（11）, γ = 81.058（13）°, Mr = 996.77, S = 1.08, V= 1987.2（13） A3, Z = 2, Dc = 1.666 g/cm3, F（000） = 1032,μ = 1.131 mm^-1, R = 0.0633 and wR = 0.1293. According to the structural analysis, the Co（ Ⅱ ） ion adopts a slightly distorted six-coordinated octahedral geometry. One N atom of the Schiff base of each molecule was hydrogenated to form hydrogen bond with O atom. Two coterminous molecules packed in one crystal water molecule are linked by intermolecular hydrogen bonds, thus generating an infinite chain constructed by hydrogen bonds.     

Syntheses and Crystal Structures of Two Coordination Compounds CuLCl（H2O） and Ni（L）2 （HL = 2-Carboxy-1,10-phenanthroline）

Two complexes CuLCl（H2O） 1 and Ni（L）2 2 （HL = 2-carboxy-1,10-phenanthroline） have been synthesized and characterized by single-crystal X-ray crystallography. The structure of 1 has a monoclinic space group P21/n with a = 7.985（2）, b = 16.067（3）, c = 9.694（2） A, β = 98.189（30）°, V= 1231.0（4） A^3, Z = 4, Dc = 1.836 g/cm^3,μ =1.998 mm^-1, F（000） = 684, the final R = 0.0301 and wR = 0.0810. The structure of 2 （C26H14N4NiO10） adopts an orthorhombic system, space group Pbea with a = 9.410（2）, b = 23.2410（5）, c = 23.8680（5） A, V = 5219.9（18） A^3, Z = 8, Mr = 601.12, Dc = 1,530 g/cm^3,μ = 0.809 mm^-1, F（000） = 2448, the final R = 0.0448 and wR = 0.1427. The Cu center of complex 1 exhibits a square pyramidal coordination environment with one oxygen and two nitrogen atoms from deprotonated 2-carboxy-1,10-phenanthroline, one oxygen atom from water and one chloride ion. The Ni center of complex 2 assumes a distorted octahedral coordination geometry consisting of two oxygen atoms and four nitrogen atoms of two deprotonated 2-carboxy-1,10-phenanthroline molecules. Supramolecular assembly has been found via noncovalent bonds, such as hydrogen bonds and π-π stacking interactions.     

Synthesis and Crystal Structure of a Three-dimensional Mn（Ⅱ） Coordination Polymer with 3-（Pyrazin-2-yloxy）-pyridine and Azide Anion as Mixed Bridge Ligand

A three-dimensional coordination polymer [Mn2（μ1.3-N3）4（μ-PP）2]n （PP = 3-（pyrazin-2-yloxy）-pyridine） has been synthesized with 3-（pyrazin-2-yloxy）-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data： triclinic system, space group P1, with a = 6.794（4）, b = 9.885（6）, c = 9.947（6） A, α = 64.170（6）, β= 84.190（8）, γ= 85.319（8）°, V = 597.7（6）A^3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm^3, F（000） = 314 and μ = 1.117 mm^-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn（Ⅱ） ions connect into a two-dimensional sheet on the ab plane, then 3-（pyrazin-2-yloxy）-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along     

Preparation,Crystal Structure and Theoretical Calculation of N-（Pyrimidin-2-yl）-N＇-methoxycarbonyl-thiourea

The compound, N-（pyrimidin-2-yl）-N＇-methoxycarbonyl-thiourea, has been synthesized. The single crystal structure has been determined by an X-ray diffractometer. The crystal belongs to triclinic with space group P-1 and a=0.72152（4） nm, b=0.8056（4） nm, c=0.90772（5） nm, α= 105.141（4）°, β=94.588（4）°, γ= 115.415（4）°, F（000）= 220, the unit cell volume V=0.45704（4） nm^3, the molecule number in one unit cell Z=2, the absorption coefficient μ=0.333 mm^-1, the calculated density Dc= 1.542 g/cm^3. The theoretical investigation of the title compound was carried out with B3LYP/6-311G, HF/6-311G and MP2/6-311G methods, and the atomic charges and natural bond orbital analysis were also discussed.     

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,Characterization and Crystal Structure of a Three-dimensional Coordination Polymer {[Cd（1,5-nds）（Him）2（H2O）]·2H2O}n

A novel cadmium（Ⅱ） coordination polymer {[Cd（1,5-nds）（Him）2（H2O）]·2H2O}n （1,5-nds = naphthalene-1,5-disulfonate and Him = imidazole） was synthesized based on the reaction of cadmium oxide and 1,5-naphthalenedisulfonic acid firstly, and then mixed with imidazole in methanol medium. Its structure was characterized by elemental analysis, IR and TGA, respectively. The crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1, with a = 8.5420（10）, b = 10.2570（10）, c = 13.361（2） A, α = 100.704 （2）, β = 100.195（2）, γ = 108.873（3）°, C16H20Cd N4O9S2, Mr= 588.91, V = 1.0524（2） nm^3, Dc = 1.858 g/cm^3, Z = 2, F（000） = 592, β^ = 1.294 mm-1, R = 0.0397 and wR = 0.1007 for 3180 observed reflections （Ⅰ〉 2σ（Ⅰ））. Structural analysis shows that the cadmiun atom is coordinated with four oxygen atoms from three 1,5-nds and one water molecule together with two nitrogen atoms from two imidazoles, giving a distorted octahedral coordination geometry. The molecules are linked to form a two-dimensional coordination polymer based on bridging ligands of naphthalene- 1,5-disulfonate anions, the sheets of which are then interacted via hydrogen bonds, leading to a three-dimensional network structure.     

Synthesis,Crystal Structure and Electrochemical Properties of a Cobalt Compound Based on N-（4-pyridylmethyl）imidazole Ligand①

One compound with N-(4-pyridylmethyl)imidazole liand, [Co(pyim)2(N3)2]n 1(pyim = N-(4-pyridylmethyl)imidazole), was synthesized and structurally characterized. Compound 1 crystallizes in triclinic, space group P21/c with a = 8.090(3), b = 16.109(3), c = 8.590(3), B= 117.800(12)o, V = 990.3(5) A3, Z = 2, Mr = 461.37, Dc = 1.547 g/cm3, F(000) = 474, μ = 0.901 mm-1, the final R = 0.0381 and wR = 0.0950 for 1581 observed reflections with I 2A(I). In this compound, the unique Co(Ⅱ) resides at a crystallographic inversion center and exhibits an octahedral coordination geometry. The adjacent Co(Ⅱ) ions are connected by the pyim ligands to form a 2D layer structure. The layers are stacked in an ABAB mode and reinforced by the weak interlayer C–H···N hydrogen bonds and π-π stacking to give a 3D architecture. The thermal property and electrochemical property of compound 1 have also been studied.