Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X-Ray Crystal Structures of [Mn(ph)(Phen)(2)(H(2)O)]. 4H(2)O, [Mn(Phen)(2)(H(2)O)(2)](2)(Isoph)(2)(Phen). 12H(2)O and {[Mn(Isoph)(bipy)](4). 2.75biby}(n)(phH(2) = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10-Phenanthroline; bipy = 2,2-Bipyridine)

Manganese(II) acetate reacts with phthalic acid (phH(2)) to give [Mn(ph)].0.5H(2)O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)].2H(2)O (2) and [Mn(ph)(phen)(2)(H(2)O)].4H(2)O (3). Reaction of isophthalic acid (isophH(2)) with manganese(II) acetate results in the formation of [Mn(isoph)].2H(2)O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn(2) (isoph)(2)(phen)(3))].4H(2)O (5), [(Mn(phen)(2)(H(2)O)(2)](2)(isoph)(2)(phen).12H(2)O (6) and {[Mn(isoph)(bipy)](4).2.75 biby}(n) (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the "metal free" 1,10-phenanthroline and its manganese complexes were found to be active.     

Interaction of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] and [Rh(2)(O(2)CCH(OH)Ph)(2)(phen)(2)(H(2)O)(2)](O(2)C-CH(OH)Ph)(2) With Sulfhydryl Compounds and Ceruloplasmin

The interaction of binuclear rhodium(II) complexes [Rh(2)(OOCCH(3))(4)(H(2)O)(2)], [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] {OOCCH(OH)Ph}(2), [Rh(2)(OOCCH(3))(2)(bpy)(2)(H(2)O)(2)](OOCCH(3))(2) and [Rh(2)Cl(2)(OOCMe)(2)(bpy)(2)](3H(2)O) with ceruloplasmin, cysteine, glutathione and coenzyme A have been investigated using. UV-Vis and CD spectroscopies. The complexes containing phen or bpy at pH = 7.4 and 4.0 are readily reduced with sulfhydryl compounds, while rhodium(II) acetate is relatively stable in these conditions. Complex [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] strongly changes structure of ceruloplasmin leading to the decrease of of alpha-helix content and loss of oxidase activity.     

Preparation and Molecular Structure of {[Ca(CHZ)2(H2O)](NTO)2⋅3.5H2O}n

The title compound {[Ca(CHZ)₂(H₂O)](NTO)₂⋅3.5H₂O}_n was synthesized by using an aqueous solution of calcium 3‐nitro‐1,2,4‐triazol‐5‐onate and carbohydrazide (CHZ, NH₂NHCONHNH₂). Its molecular structure was determined by X‐ray diffraction and its crystals have monoclinic form, with space group C2/c, where a=2.4483(4) nm, b=1.2581(2) nm, c =1.6269(3) nm, β=121.168(12)°, V=4.2879(13) nm³, Z=8, d_c=1.727 g⋅cm⁻³, μ (Mo K_α)=3.9 cm⁻¹, M=557.47, F(000)=2312. The coordination polyhedron is a tricapped trigonal prism in a tetradecahedron with a coordination number of nine. The whole molecule has many long chains formed through the carbohydrazide bridges, and every long chain is unlimited along the c axis. The long chains are linked by hydrogen bonds to form the crystal structure.     

Single crystal structure of a heterometallic one-dimensional polymer: [{Cu(1,10-phen)}2(V2O4)(O3PCH2CH2CH2CH2PO3H)2(H2O)]n

A heterometallic one-dimensional polymer [{Cu(1,10-phen)}₂(V₂O₄)(O₃PCH₂CH₂CH₂CH₂PO₃H)₂(H₂O)]_n 1 (1,10-phen=1,10-phenanthroline) has been synthesized under hydrothermal conditions. The structure of 1 shows a stepped chain with two parallel 1,4-butylenediphosphonate ligands as linking units.     

Synthesis and crystal structure of mer-nitroaquatriamminenitrosylruthenium(II) nitrate [RuNO(NH3)3(NO2)(H2O)](NO3)2

The reaction between mer-[RuNO(NH₃)₃(NO₂)(OH)]Cl·0.5H₂O and an excess of 16 M HNO₃ leads to the protonation of the starting complex and crystallization of the complex with a coordinated water molecule and nitrite anion. The crystal structure of the product has been determined. The coordinated water molecule tends to be a weak acid with a measured pK_a of 2.4.     

A novel three-dimensional coordination polymer containing tetranuclear [Co4(μ3-OH)2] building blocks: Synthesis,crystal structure and magnetic behavior of {[Co2(btc)(μ3-OH)(H2O)2] · H2O}n

A cobalt coordination polymer {[Co₂(btc)(μ₃-OH)(H₂O)₂] · H₂O}_n 1 (btc = 1,2,4-benzenetricarboxylate) was synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction method. In 1, the six-coordinated Co(II) ions are held together by two bridging hydroxides to form a tetranuclear [Co₄(μ₃-OH)₂] unit, which are connected further through btc³⁻ ligands in a new μ₇-bridging mode to give a porous three dimensional framework. The study of magnetic properties indicated dominant antiferromagnetic coupling interactions between the adjacent Co(II) sites.     

A novel coordination polymer with double chains structure: hydrothermal syntheses,structures and magnetic properties of [Cu(phen)(H2O)2SO4]n (phen=1,10-phenanthroline)

A coordination polymer [Cu(phen)(H₂O)₂(SO₄)]_n (1) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, thermogravimetric analysis, and single crystal X-ray diffraction. This compound displays a novel double chains structure, in which each one-dimensional chain is constituted by the distorted octahedral complex of copper(II) bridged through bidentate sulfate ligands. Magnetic susceptibility measurement of 1 has been performed down to 2 K. Although paramagnetic behavior is dominantly manifested, compound 1 shows a weak antiferromagnetic interaction on cooling from room temperature to 2 K.     

有机二磺酸钴配合物[Co (H2O)6](1,5-NDS)的合成与晶体结构

合成了一种新的有机二磺酸钴配合物[Co (H2O)6](1,5-NDS)(1,5-NDS2-=1,5-萘二磺酸根),并通过元素分析和单晶X-射线对其进行了表征.该配合物以空间群为P2(1)/C结晶,晶胞参数为a=1.3214(2)nm,b=0.6674(9)nm,c=0.9685(1)nm,β=92.091(2)°,V=0.8541(3)nm3,Z=2,最终R=0.0288,wR=0.0785.在该配合物中,配阳离子中每个钴原子与6个水分子配位形成八面体构型,1,5-萘二磺酸根没有与Co2 形成配位键,而是以平衡离子的形式存在,阴阳离子通过静电吸引和氢键作用构筑了网络结构.     

Hydrothermal synthesis,crystal structure and photoluminescent property of a novel 3-D [La2(C2O4)2(NO3)(OH)(H2O)] · 3H2O

A novel 3D [La₂(C₂O₄)₂(NO₃) (OH)(H₂O)] · 3H₂O 1 has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR, TGA, X-ray powder diffraction, X-ray single crystal diffraction and photoluminescence. The bridging modes of both nitrates and oxalates in compound 1 are uncommon. We have unexpectedly generated an unusual compound by using the simplest ligands, oxalates and nitrates in the presence of nicotinate (HIN).     

Synthesis and crystal structure of trans-nitrosoaquatetraammineruthenium(II) sulphate hydrosulphate, [Ru(NO)(NH3)4(H2O)](SO4)(HSO4)

The reaction between [RuNO(NH₃)₄OH]Cl₂ and an excess of 2 M H₂SO₄ leads to the protonation of the starting complex and crystallisation of the title complex with sulphate and hydrosulphate anions. The crystal structure of the product has been determined. The linear nitroso group and water molecule are coordinated in trans positions.     

The terminal binding of base mismatched oligonucleotide d(CCGAATGAGG)2 by [Co(phen)2(DPQ)]Cl3

The binding of the complex [Co(phen)₂(DPQ)]Cl₃ to the decanucleotide d(CCGAATGAGG)₂ containing two pairs of sheared G:A mispairs was studied by 2D-NMR. There appear many ¹H NOE cross-peaks from the complex to the oligonucleotide. The results indicate that the complex, with DPQ, intercalates into the oligonucleotide via its terminal base pairs from the minor groove, which further proved our previous conclusion.     

配合物La（C6H5CHOHC00）3（phen）（H2O）的合成

用苯羟基乙酸、邻菲罗啉与稀土的硝酸盐为原料合成了配合物La(C_6H_5CHOHCOO)_3(phen)(H_2O),通过元素分析、红外光谱、核磁共振等测试手段,确定了配合物的组成和结构,并通过热重分析对其热性质进行了表征。结果表明,配合物中邻菲罗啉以双齿螯合方式配位,而苯羟乙酸则以桥联或单齿方式参与配位。     

三元钴配合物[Co（thy）（phen）（H2O）2]的合成、表征及荧光性能研究

用溶液法合成了钴的配合物[Co（thy）（phen）（H2O）2],对它进行了元素分析、红外光谱表征。其中硫代水杨酸和1,10-邻菲啰啉为双齿配位,分别与Co^2＋形成稳定的六,五元螯合环。并进一步研究了配合物和配体硫代水杨酸的荧光性质。     

配位聚合物[Zn(phen)(H_2O)_2SO_4]_n的合成与晶体结构

通过扩散法得到了一个新的配位聚合物[Zn(phen)(H2O)2SO4]n[phen=邻菲啰啉]。通过X-ray单晶衍射对配合物的结构进行了表征。配合物属单斜晶系,Cc空间群,晶胞参数:a=15.1399(10),b=14.1420(10),c=6.6994(5),α=90°,β=103.458(1)°,γ=90°,V=1395.01(17)3,Z=2,μ=0.752 mm-1,R1=0.0214,wR2=0.0602。     

Synthesis,crystal structure and water-induced reversible crystal-to-amorphous transformation property of [Co2(2,4-pydc)2(bpa)(H2O)6](H2O)2

The dinuclear Co^II coordination compound with empirical formula [Co₂(2,4-pydc)₂(bpa)(H₂O)₆](H₂O)₂ (1); bpa = 1,2-bis(2,4-pyridyl)ethane, 2,4-pydc = 2,4-pyridinedicarboxylate anion, has been synthesized and õcharacterized by elemental analysis, single crystal X-ray diffraction, IR and UV–vis spectra, TGA and XRPD. Compound 1 is a symmetry-related dinuclear compound consisting of two six coordinated cobalt atoms, one bpa ligand, two 2,4-pydc ligands and two lattice water molecules. Each Co^II ion is coordinated by one oxygen atom and one nitrogen atom from 2,4-pydc bidentate chelate ligand, one nitrogen atom of bpa bidentate bridging ligand and three water molecules, giving a distorted octahedral geometry with CoN₂O₄ chromophore. The crystal packing of this compound reveals a novel 3D supramolecular network, formed by hydrogen-bonding and C–H⋯π interactions. Investigations of the dynamic structural transformation behavior demonstrate that the title compound exhibits a solvent-induced reversible crystal-to-amorphous transformation with chromotropism when exposed to water vapor. This indicates that the dehydrated amorphous form, Co₂(2,4-pydc)₂(bpa)(H₂O)₂ (1A), may be utilized as an indicator for humidity.     

Developing Carrier Complexes for "Caged NO": RuCl(3)(NO)(H(2)O)(2) Complexes of Dipyridylamine, (dpaH), N,N,N'N'-Tetrakis (2-Pyridyl) Adipamide, (tpada), and (2-Pyridylmethyl) Iminodiacetate, (pida)

Delivery agents which can carry the {Ru(NO)}(6) chromophore ("caged NO") are desired for vasodilation and for photodynamic therapy of tumors. Toward these goals, complexes derived from [RuCl(3)(NO)(H(2)O)(2)]= (1) have been prepared using dipyridylamine (dpaH) as mono and bis adducts, [Ru(NO)Cl(3)(dpaH)] = (2) and [Ru(NO)Cl(dpaH)(2)]Cl(2) = (3). The dpaH ligands coordinate cis to the Ru(NO) axis.The mono derivative is a model for a potential DNA groove-spanning binuclear complex {[RuNO)Cl(3)](2)(tpada)} = (4) which has two DNA-coordinating Ru(II) centers, photo-labile {Ru(NO)}(6) sites, and a groove-spanning tether moiety.The binuclear assembly is prepared from the tethered dipyridylamine ligand N,N,N',N'-tetrakis(2-pyridylmethyl)adipamide (tpada) which has recently been shown to provide a binuclear carrier complex suited to transporting Ru(II) and Pd(II) agents. A related complex, [Ru(NO)Cl(pida)] = (5) with the {Ru(NO)}(6) moiety bound to (2-pyridylmethyl) iminodiacetate (pida(2-)) is also characterized as a potential "caged NO" carrier. Structural information concerning the placement of the pyridyl donor groups relative to the {Ru(NO)}(6) unit has been obtained from (1)H and (13)C NMR and infrared methods, noting that a pyridyl donor trans to NO+ causes "trans strengthening" of this ligand for [Ru(NO)Cl(pida)], whereas placement of pyridyl groups cis to NO+ causes a weakening of the N-O bond and a lower NO stretching frequency in the dpa-based complexes.     

两种基于DMBA原位分解的配位聚合物{[Y(C_2O_4)_(1.5)(H_2O)_2]·H_2O}_n和{[Y(C_2O_4)_(1.5)(H_2O)_3]·2H_2O}_n的合成及结构研究

以DMBA(1,3-二甲基巴比妥酸)为底物,通过其原位分解产物H2C2O4(草酸)的自组装,分别制备了两种新颖的由压力调控的二维层状配位聚合物{[Y(C2O4)1.5(H2O)2]·H2O}n(1)和{[Y(C2O4)1.5(H2O)3]·2H2O}n(2)。在水热合成条件下,考察了不同阳离子、阴离子及溶剂对终产物分离的影响。结果显示,配合物(1)的构筑需在Y(Ⅲ)离子及去离子水同时存在的条件下完成。在此基础上,对反应机理进行了初步探究,发现氧化反应、亲核加成反应及消除反应等多种有机转化过程或可诱导原位开环产物的形成。     

Formation of a 1D water chain into the channel of a unique 3D hydrogen-bound coordination polymer {[Cd(μ-Cl)(4-pya)(H2O)]2 · 4H2O}∞ (4-pya = trans-4-pyridylacrylate)

A novel Cd(II)/4-pya coordination polymer {[Cd(μ-Cl)(4-pya)(H₂O)]₂ · 4H₂O}_∞ (1) (4-pya = trans-4-pyridylacrylate) was synthesized and structurally characterized. Single-crystal X-ray diffraction revealed that 1 consists of a 2D (4, 4) network constructed from the 4-pya bridging ligand and the dimeric [Cd(μ-Cl)]₂ cores, in which each six-coordinated Cd(II) ion adopts an octahedral coordination geometry. Each 2D layer is further stacked along the a axis through hydrogen bonding interactions to afford a 3D hydrogen-bound network. An infinite water chain is generated via hydrogen bonds into each resulting 1D channel. The luminescent properties of 1 in the solid state were investigated.     

Hydrothermal synthesis and structural characterization of a new two-dimensional vanadium oxide complex: [Co(2,2-bipy)(H2O)(VO3)2]

The hydrothermal reaction of NH₄VO₃, Co(NO₃)₂ · 6H₂O, 2,2^′-bipyridine, H₃BO₃ and H₂O at 170 °C yields the new complex [Co(2,2-bipy)(H₂O)(VO₃)₂]. The structure consists of layers, each a two-dimensional network built up of corner-sharing VO₄ tetrahedral chains interconnected through [Co(2,2-bipy)(H₂O)]²⁺ groups, and there exists a weak antiferromagnetic exchange interaction between the cobalt ions in the layers.