Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Synthesis,DNA-binding and photocleavage studies of cobalt(III) complexes [Co(bpy)<Subscript>2</Subscript>(dpta)]<Superscript>3+</Superscript> and [Co(bpy)<Subscript>2</Subscript>(amtp)]<Superscript>3+</Superscript>

Two novel cobalt(III) mixed-polypyridyl complexes [Co(bpy)₂(dpta)]³⁺ and [Co(bpy)₂(amtp)]³⁺ (bpy = 2,2′-bipyridine, dpta = dipyrido-[3,2-a;2′,3′-c]-thien-[3,4-c]azine, amtp = 3-amino-1,2,4-triazino[5,6-f]-1,10-phenanthroline) have been synthesized and characterized. The interaction of Co^III complexes with calf thymus DNA was investigated by spectroscopic and viscosity measurements. Results suggest that the two complexes bind to DNA via an intercalative mode. Moreover, Co^III complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The mechanism studies reveal that hydroxyl radical (OH^•) is likely to be the reactive species responsible for the cleavage of plasmid DNA by [Co(bpy)₂(dpta)]³⁺ and superoxide anion radical (O ₂ ^•− ) acts as the key role in the cleavage reaction of plasmid DNA by [Co(bpy)₂(amtp)]³⁺.     

Synthesis,characterization, crystal structure and biological activity of the cobalt(IV) complex of 2,6-diacetylpyridine dioxime: [Co(dapdo)<Subscript>2</Subscript>]

The cobalt(IV) complex of 2,6-diacetylpyridine dioxime (dapdoH₂) was prepared and characterized by X-ray diffraction, elemental analysis and FT-IR. The titled complex was found to crystallize in the orthorhombic space group and was screened for antibacterial and antifungal activities by the disc diffusion and microtitter plate techniques using DMF as solvent. It has been found that the antimicrobial activity of the complex [Co(dapdo)₂] is slightly higher than the free ligand (dapdoH₂).     

Structure of M(OOPh)<Subscript>2</Subscript>[O(H)Me]<Subscript>4</Subscript> (M = Zn(II), Co(II), and Ni(II)) adducts

The structures of adducts M(OOPh)₂[O(H)Me]₄ (M = Zn(II), Co(II), and Ni(II)), synthesized by the reactions between corresponding aqueous metal acetates and benzoic acid under boiling in methanol were studied by X-ray diffraction.     

Crystal structure and EPR spectra of (Bu<Subscript>4</Subscript>N)<Subscript>2</Subscript>[V(dmit)<Subscript>3</Subscript>]

The tris-chelate complex of vanadium(IV) (Bu₄N)₂[V(dmit)₃] is prepared from VCl₃ and (Bu₄N)₂[Zn(dmit)₂] (dmit = isotrithionedithiolate C₃S₅ ^2–) and characterized by single crystal XRD and mass spectrometry. The complex crystallizes in the space group Pna2₁ and has a distorted octahedral environment of vanadium. The complex is paramagnetic and gives a characteristic EPR spectrum in both solution and solid phase. The g factors and hyperfine interaction constants are determined.     

Ionothermal syntheses of two new 2D metal-organic frameworks: (EMIM)<Subscript>2</Subscript>[M(Pydc)<Subscript>2</Subscript>] (M = Co,Zn)

Two new coordination polymers, (EMIM)₂[M(Pydc)₂] (M is Co, Zn; EMIM is 1-ethyl-3-methylimidazolium; H₂Pydc is 2,5-pyridinedicarboxylic acid), have been synthesized through the reaction of cobalt or zinc nitrate with H₂Pydc in the ionic liquid medium. The structures exhibit a two-dimensional 4.4-network with the imidazolium cations, acting as charge compensating agent, located between the layers of the coordination anion polymeric frameworks. The article is published in the original.     

Synthesis,structure, and properties of the [RuNO(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>][Co(CN)<Subscript>6</Subscript>] complex containing a photochromic cation

The salt of cobalt hexacyanide with the photochromic mononitrosyl cation [RuNO(NH₃)₅]³⁺ with the composition [RuNO(NH₃)₅][Co(CN)₆] was synthesized. Single crystals of the salt were grown, and the crystal structure was solved. The photochromic properties were studied by differential scanning calorimetry (DSC). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 545–548, March, 2008.     

Synthesis and Selected Physicochemical Properties of Complex Na<Subscript>2</Subscript>[Zr(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The interaction of Zr(NO₃)₄ and Na₂MoO₄ in an aqueous medium has been studied by the method of residual concentrations at 20°C. The compound Nа₂[Zr(MoO₄)₃] is formed starting at the molar ratio Zr(NO₃)₄/Na₂MoO₄ ≥ 0.66. The compound has been characterized by X-ray diffraction, IR spectroscopy, and thermal analysis.     

Crystal structure of new ammonium fluoroindate(III) (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>[InF<Subscript>5</Subscript>]

A new indium(III) fluoride complex with the ammonium cation (NH₄)₂[InF₅] is synthesized and its crystal structure is studied. The structure of (NH₄)₂[InF₅] is formed of NH₄ ⁺ cations and complex [InF₅]^2– anions. The In atom in the complex anion surrounded by four terminal and two bridging F atoms forms an almost regular octahedral coordination polyhedron (CN 6) with two terminal F atoms in the axial positions and two terminal and two bridging F atoms in the equatorial plane. Through bridging F atoms, the InF6 polyhedra are arranged in polymer trans- vertex-connected corrugated anion chains (InF₅) _n ^2n? directed along the c axis. The N–H?F hydrogen bonds organize the chains in a three-dimensional framework.     

[Co(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>](WO<Subscript>4</Subscript>)Cl: Synthesis,crystal structure,and thermal properties

The crystal structure of [Co(NH₃)₆](WO₄)Cl complex salt is determined by single crystal X-ray. The thermal properties are examined, and the products obtained on heating the salt in different gaseous atmospheres are analyzed by powder X-ray diffraction.     

Binuclear cobalt(II/II) and cobalt(II/III) chelates with O<Subscript>2</Subscript>N<Subscript>2</Subscript> ligands: synthesis,structure and magnetic studies

Abstract  The title complexes and have been synthesized in excellent yields by reacting Co(OAc)₂·4H₂O with H₂L¹ and H₂L², respectively, in acetonitrile solution. Here, [L¹]²⁻ and [L²]²⁻ are the deprotonated forms of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and N,N-bis(2-hydroxybenzyl)-2-picolylamine, respectively. The crystal structures of and were determined by x-ray crystallography. In , each cobalt atom has distorted trigonal bipyramid geometry, while in , each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in . The magnetic characterization for is in agreement with the presence of Co(II) and Co(III) centers. Graphical Abstract  The title complexes and have been synthesized in excellent yields by reacting Co(OAc)₂·4H₂O with dianionic N₂O₂ coordinating ligands. In complex 1, each cobalt atom has distorted trigonal bipyramid geometry, while in complex 2, each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in complex 1. The magnetic characterization for complex 2 is in agreement with the presence of Co(II) and Co(III) centers. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,characterization and very strong luminescence of a new 3 D europium sulfate Eu<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript>

A new 3 D europium sulfate Eu₂(H₂O)₄(SO₄)₃ 1 is synthesized solvothermally and characterized by single crystal X-ray diffraction, IR spectrum, TG, powder XRD, and ultraviolet excitation and emission spectrum. This compound crystallizes in the triclinic system with the space group P-1, a = 6.7520(9) Å, b = 9.1077(12) Å, c = 10.5910(14) Å, α = 94.432(2)°, β = 107.1170(10)°, γ = 99.160(2)°, V = 609.17(14) ų, Z = 2. The open framework of the title compound is an eight-membered ring channel along the crystallographic a-axis, which is built up by EuO₈ polyhedra and SO₄ tetrahedra.     

Synthesis,crystal structure,and biological properties of the complex [Co(DmgH)<Subscript>2</Subscript>(Seu)<Subscript>1.4</Subscript>(Se-Seu)<Subscript>0.5</Subscript>(Se<Subscript>2</Subscript>)<Subscript>0.1</Subscript>][BF<Subscript>4</Subscript>]

A new Co(III) dioxime complex with selenocarbamide was obtained by the reaction of Co(BF₄)₂ ? 6H₂O, DmgH₂, and Seu (DmgH2 = dimethylglyoxime, Seu = selenocarbamide). According to X-ray diffraction (CIF file CCDC no. 1485732), the product was an ionic coordination compound with unusual composition, [Co(DmgH)₂(Seu)_1.4(Se-Seu)_0.5(Se₂)_0.1][BF₄] (I). Apart from two monodeprotonated DmgH￣ molecules, the central atom coordinates neutral Seu, Se-Seu, and Se₂ molecules. Thus, the crystal contains the complex cations [Co(DmgH)₂(Seu)₂]⁺, [Co(DmgH)₂(Seu)(Se-Seu)]⁺, and [Co(DmgH)₂(Seu)(Se₂)]⁺. Each [BF₄]￣ anion is linked to the cations not only by electrostatic forces but also by intermolecular N–H···F hydrogen bonds (H-bonds). The complex cations are combined by intermolecular N–H···O H-bonds. The new coordination compound was found to possess biological activity. Treatment of the garlic (Allium sativum L.) foliage with an aqueous solution of I optimizes the content of selenium in the leaves and cloves and enhances the growth and plant productivity. The organs of treated plants are characterized by enhanced antioxidant protection owing to increasing activity of antioxidant enzymes and contents of proline and assimilation pigments, and decreasing lipid peroxidation.     

Crystal structure of fluorosulfate complex compounds of indium(III) M<Subscript>2</Subscript>[InF<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)H<Subscript>2</Subscript>O] (M = K,NH<Subscript>4</Subscript>)

The crystal structures of isostructural mixed-ligand fluorosulfate complex compounds of indium(III) M₂[InF₃(SO₄)H₂O] (M = K, NH₄), formed of K⁺ cations, NH₄ ⁺ respectively, and complex [InF₃(SO₄)H₂O]^2– anions are determined. In the complex anion, the indium atom surrounded by three F atoms, the oxygen atom of the coordinated H₂O molecule, and two oxygen atoms of the bridging sulfate group forms a slightly distorted octahedron (CN 6). Via alternating bridging SO₄ groups, the polyhedra of In(III) atoms are arranged in polymer chains. The O–H???F hydrogen bonds organize the chains in a three-dimensional network. The K⁺ and NH₄ ⁺ cations are located in the structure framework and additionally strengthen it.     

Synthesis and characterization of a new nanomagnetic coordination composite from Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> and Cu(II) complex: as an efficient catalyst in oxidation of benzyl alcohol

New nanomagnetic coordination compound, Cu(salal)@DA@ Fe₃O₄, was synthesized by bonding between the Cu(II) complex and Fe₃O₄ nanoparticles. The Cu complex has two aldehyde groups. The surface of Fe₃O₄ nanoparticles was modified by the dopamine molecules and the amine group of dopamine is free. Therefore, the Cu complex is covalently anchored to Fe₃O₄ nanoparticle by the formation of imine bonds between the aldehyde and amine groups. On the other hand, a Cu-Schiff base complex is immobilized on nano-Fe₃O₄ by dopamine as a bridge. Consequently, the homogeneous Cu complex is easily converted to the heterogeneous-magnetic compound in this project. The Cu complex, Fe₃O₄ and new nanocomposite were characterized by general techniques such as FTIR, TGA, XRD, FESEM, MAP and EDS. The average crystallite size of Fe₃O₄ and Cu(salal)@DA@ Fe₃O₄ were calculated by Scherrer’s formula and they are 18.52 and 24.69 nm, respectively. These results indicated the average crystallite size of Fe₃O₄ nanomaterials is slightly increased by surface modification by Cu complex. The FESEM images show a tiny spherical mushroom morphology for both nanocompounds, and the EDS analysis confirms the presence of Fe, Cu, C and O in the nanomagnetic coordination composite. The catalytic properties of these compounds were studied and compared to oxidation of benzyl alcohol by 30% H₂O₂ at room temperature. The results show that the catalytic properties Cu complex and Fe₃O₄ were enhanced by cooperation of both compounds in a nanocoordination composite.     

Synthesis,crystal and molecular structure and magnetic properties of an extended two-dimensional fumarato-bridged polymeric cobalt(II) complex [Co(μ-fumarato)(γ-methylpyridine)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>∞</Subscript>

An extended hydrogen-bonded two-dimensional fumarato-bridged complex [Co(μ-fumarato)(γ-methylpyridine)₂(H₂O)₂]_∞ has been synthesized and its crystal structure determined by single crystal X-ray analysis. The X-ray analysis reveals that the cobalt atom is positioned in distorted octahedral surroundings. An extended twodimensional structure was formed through interchain hydrogen bonding. Magnetic measurements showed the presence of weak antiferromagnetic exchange interactions between the cobalt(II) ions within the chain, based on the spin Hamilitonian H = −2J ∑ S_i S_{i+ 1} (J = − 0.22 cm⁻¹).     

Complexation of Zn<Subscript>2</Subscript>[Fe(CN)<Subscript>6</Subscript>] with M<Superscript>2+</Superscript> (M = Mn,Co, Ni,Cu, Cd) in Zn<Subscript>2</Subscript>[Fe(CN)<Subscript>6</Subscript>] gelatin-immobilized matrices

Electrophilic substitution reactions Zn²⁺ M²⁺ (M = Mn, Co, Ni, Cu, Cd) in thin gelatin layers with immobilized zinc(II) hexacyanoferrate brought in contact with the aqueous solutions of d-element chlorides are studied. In all cases (except for Mn(II)), Zn atoms are partially replaced by all metals in question with the formation of the corresponding binuclear ZnM hexacyanoferrates(II). No complete replacement of Zn(II) to mononuclear hexacyanoferrate(II) of substituting metal occurs in neither of the cases.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 110–116. Original Russian Text Copyright © 2005 by Tatarintseva, Mikhailov, Naumkina, Lygina.     

Photoinduced cleavage and DNA-binding of the Ruthenium(II) polypyridyl complex [Ru(phen)<Subscript>2</Subscript>(ipbd)](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

A novel ruthenium(II) polypyridyl complex [Ru(phen)₂{ipbd)](ClO₄)₂ (ipbd = 3-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)-1-benzodioxane, phen = 1,10-phenanthroline} has been synthesized and characterized by elemental analysis, ES-MS and ¹H-NMR spectra. The interaction of the complex with calf thymus DNA (CT-DNA) was investigated by absorption titration, fluorescence spectra, thermal denaturation, viscosity measurements, circular dichroism and photoinduced cleavage. The results suggest that the complex intercalates into the CT-DNA base pairs. Upon irradiation, this novel Ru(II) complex can cleave the plasmid pBR 322 DNA from the supercoiled form I to the open circular form II.     

Synthesis and study of (hexacaprolactam)trionium dodecamolybdophosphate (C<Subscript>6</Subscript>H<Subscript>11</Subscript>NO)<Subscript>6</Subscript>H<Subscript>3</Subscript>[PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>]

(Hexacaprolactam)trionium dodecamolybdophosphate (C₆H₁₁NO)₆H₃[PMo₁₂O₄₀] has been prepared and studied by means of chemical and X-ray diffraction analysis as well as NMR and IR spectroscopy.