New assembly of organic components and transition metal complexes based on [VMo6O22]3? and [V2Mo6O26]6? building blocks: syntheses, crystal structures, and magnetic properties

Two new molybdovanadates, (H₃NCH₂CH₂NH₃)₃ [Mo₆VO₂₂(CH₃COO)₃]·5H₂O (1) and (H₃NCH₂CH₂NH₃)₂{(Mo₆V₂O₂₆)[Cu(NH₂CH₂CH₂NH₂)(H₂O)₂]}·4H₂O (2), have been synthesized in aqueous solution and characterized by IR, UV–vis, single-crystal X-ray diffraction, thermal gravimetric, elemental analysis, and magnetic analysis. Compound 1 is a crown-shaped ring consisted of six edge-sharing MoO₆ octahedra linked to a central {VO₄} unit. The MoO₆ octahedra are in pairs connected with the carboxylato ligands from three acetic acid molecules. Compound 1 is the first example of a molybdovanadate coordinated by acetic acid molecules. In addition, multipoint hydrogen-bonding interactions exist in 1, which bridge the crown-shaped [Mo₆VO₂₂ (CH₃COO)₃]⁶⁻ clusters and the protonated ethylenediamine molecules into three-dimensional (3D) networks. The structural feature of compound 2 is the formation of one-dimensional (1D) zip-zag chain in which [Mo₆V₂O₂₆]⁶⁻ clusters are covalently bonded to copper coordination groups through the terminal oxygen of the {VO₄} tetrahedron. The magnetic investigation on compound 2 demonstrates the possible occurrence of antiferromagnetic interactions by intermolecular linkage.     

Synthesis, structure and spectroscopic characterization of a new organic cation diphosphate: [2,6-(C2H5)2C6H3NH3]2H2P2O7?·?2H2O

The chemical preparation, crystal structure and spectroscopic characterization of [2,6-(C₂H₅)₂C₆H₃NH₃]₂H₂P₂O₇ · 2H₂O have been reported. The compound crystallizes in the monoclinic system in space group P2₁/c and cell parameters a = 14.323(2), b = 11.158(3), c = 16.387(2) ? and β = 96.34(3)°; V = 2602.8(9) ?³ and Z = 4. Crystal structure has been determined and refined to R = 0.044, using 3528 independent reflections. The atomic arrangement of the title compound shows anionic layer of formulae [H₂P₂O₇(H₂O)₂] _n ²ⁿ⁻ stacked along the c-axis. The 2,6-diethylanilinium cations establish on both sides of these inorganic layer hydrogen bonds so as to contribute to the intralayer cohesion in the network. The different building species are held together by means of O–H···O and N–H···O intermolecular hydrogen bonds in addition to electrostatic and van der Waals interactions.     

[Mo(C9H6NO)2O2]的合成和晶体结构

合成了标题化合物[Mo(C9H6NO)2(O)2](C9H6NO=8-羟基喹啉),测定了化合物的晶体结构.晶体属单斜晶系,空间群Cc,a=13.372(3),b=9.421(2),c=13.554(3)A,β=109.71(3)°,V=1607.6(8)A3.结构由直接法解出,最后可靠性因子R=0.0473,Rw=0.062.Mo原子为6配位,位于八面体的中心.两个配体氧相互处于邻位,分别与8-羟基喹啉中的N原子处于对位.     

Crystal structure and spectral characteristics of {[(C6H5)NH]2C=NH(C6H5)}[B(C6H5)4]·C2H5OH

A novel compound of {[(C₆H₅)NH]₂C=NH(C₆H₅)}[B(C₆H₅)₄]·C₂H₅OH is prepared and examined by single crystal X-ray diffraction. Crystal data: C₄₅H₄₄BN₃O, M = 653.64, monoclinic, space group P2₁/c, unit cell parameters: a = 24.375(2) Å, b = 17.5829(15) Å, c = 18.090(1) Å, β = 105.277(2)°, V = 7479.0(11) ų, Z = 8, d _calc = 1.161 g/cm³, T = 293 K, R ₁ = 0.064. The structure contains two crystallographically independent cations, two anions, and two solvate ethanol molecules. Three types of interactions occur between them: interionic N-H(N)⋯π and N(H)⋯π⋯H(C), π-delocalized system of Ph rings of the anions, and interaction of ions with ethanol molecules N-H⋯O-H(O)⋯π. The compound is characterized by IR and luminescence spectra. At room temperature, the emission intensity grows with time of exposure to UV irradiation. Original Russian Text Copyright ? 2008 by T. M. Polyanskaya, E. A. Il’inchik, V. V. Volkov, M. K. Drozdova, O. P. Yur’eva, and G. V. Romanenko __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 3, pp. 512–521, May–June, 2008.     

Synthesis, thermogravimetric analysis, IR spectrum, and the crystal structure of sodium hexatunstomanganate [Na2(H2O)10][Na(H2O)3]2[MnW6O18(OH)6] · 6H2O

The complex [Na₂(H₂O)₁₀][Na(H₂O)₃]₂[MnW₆O₁₈(OH)₆] · 6H₂O was synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, X-ray diffraction. The crystals are monoclinic, space group P2₁/n, a = 11.698(2), b = 11.670(2), c = 14.652(3) ?, β = 102.52(3)°, V = 1952.7(7) ?³, ρ(calcd.)= 3.45 g/cm³, Z = 2.     

X-ray study of the thermolysis products of (NH4)2[OsCl6]x[PtCl6]1?x

Thermolysis of the complex salts (NH₄)₂[OsCl₆] _x [PtCl₆]_1−x (x = 0.25−0.9) formed nanocrystalline Os _x Pt_1−x phases. Pseudomorphism has been found: the habit of the single crystals of the starting salts is preserved during thermolysis, and the ∼10–20 nm metal particles are agglomerated into octahedral structures sized 5–10 μm.     

Solvothermal indium fluoride chemistry: Syntheses and crystal structures of K5In3F14, β-(NH4)3InF6 and [NH4]3[C6H21N4]2[In4F21]

The solvothermal syntheses and crystal structures of three indium fluorides are presented. K₅In₃F₁₄ (1) and β-(NH₄)₃InF₆ (2) are variants on known inorganic structure types chiolite and cryolite, respectively, with the latter exhibiting a complex and apparently novel structural distortion. [NH₄]₃[C₆H₂₁N₄]₂[In₄F₂₁] (3) represents a new hybrid composition displaying a unique trimeric metal fluoride building unit.     

A new organic-inorganic composite sandwich-type phosphotungstate: Synthesis, crystal structure and properties of [Ni(phen)3]2H6[Ni4(H2O)2(B-α-PW9O34)2] · 4H2O

A new organic-inorganic composite sandwich-type phosphotungstate [Ni(phen)₃]₂H₆[Ni₄(H₂O)₂(B-α-PW₉O₃₄)₂] · 4H₂O (I) (phen = 1,10-phenanthroline) has been synthesized by hydrothermal method and characterized by elemental analysis, IR spectrum, thermogravimetry (TG) analysis, X-ray photoelectron spectroscopy (XPS) and X-ray single crystal diffraction. The structural analysis indicates that each structure unit of the compound III consists of two isolated [Ni(phen)₃]²⁺ cations, six protons, one tetra-Ni^II-substituted sandwich-type [Ni₄(H₂O)₂(B-α-PW₉O₃₄)₂]¹⁰⁻ anion and four crystallization water molecules. In the compound III the cations and the polyanion were linked together through electrostatic interactions and intermolecular forces. XPS measurement indicates that the oxidation state of W and Ni atoms in the compound III are +6 and +2, respectively. TG analysis of the compound III shows two steps of weight loss.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

Functionalised tetraarylstannanes Sn[C6H4-R]4 (R=-CH(CH2O)2, -CHO, -COOH, -CHN-NH-C6H3-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3, -CH[N(C2H4)2O]2)

Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C₆H₄-CH(OCH₂)₂]₄ (2), which was transformed to Sn[C₆H₄-CHO]₄ (3) and its hydrazido and amino derivatives Sn[C₆H₄-CHN-NH-C₆H₃-2,4-(NO₂)₂]₄ (5) and Sn{C₆H₄-CH[N(C₂H₄)₂O]₂}₄ (8). Oxidation of (3) produced Sn[C₆H₄-COOH]₄ (4) while reduction of (3) gave Sn[C₆H₄-CH₂-OH]₄ (6). From the acid 4, an amino acid Sn[C₆H₄-CO-NH-CH₂-CO-OCH₃]₄ (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).     

Synthesis and characterization of a new octamolybdate (NH4)4[Mo8O24(C3H2O2)2] · 4H2O

A new complex with the formula (NH₄)₄[Mo₈O₂₄(C₃H₂O₂)₂] · 4H₂O (1) has been synthesized and characterized by single crystal X-ray diffraction and infrared spectrum. The complex is small yellow crystal and space group P ₁ with a = 9.9869(18) ?, b = 10.030(19) ?, c = 10.366(19) ?, α = 91.68(3)°, β = 98.94(3)°, γ = 119.37(2)°, V = 887(3) ?³, and Z = 1. The complex contains two malonic acid ligands bonded to the γ-Mo_{8 26}⁴⁻ ions which consist of eight MoO₆ edge-sharing octahedral. In this crystal structure, the octamolybdate anion is mutually hydrogen bonded by ammonium ions and water molecules.     

Synthesis and crystal structure of sodium isopolyvanadate [Na2(H2O)8]2H2[V10O28] · 4H2O

The sodium hydrogen oxovanadate [Na₂(H₂O)₈] ₂H₂[V₁₀O₂₈] · 4H₂O was synthesized and studied by TGA, X-ray diffraction, and NMR and IR spectroscopy. The crystals are triclinic, space group P $ \bar 1 $ \bar 1 , a = 8.545(7) ?, b = 10.827(2) ?, c = 11.627(2) ?, α = 105.48(3)°, β = 99.38(3)°, γ = 101.29(3)°, V = 989.9(3) ?³, ρ(calcd) = 2,381 g/cm³, Z= 1.     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

Synthesis, crystal structure, and biological activity of the binuclear complex [Pr2(C10H9N2O4)2(C7H5O3)4(H2O)2] · 2H2O

A novel binuclear praseodymium(III) complex with N-(2-propionyl)salicyloylhydrazone (C₁₀H₁₀N₂O₄, H₃L) and p-hydroxybenzoic acid (C₇H₆O₃, Phba) was prepared in a H₂O-C₂H₅OH mixed solution, and the crystal structure of [Pr₂(H₂L)₂(Phba)₄(H₂O)₂] · 2H₂O (I) was determined by X-ray single crystal diffractometry. Complex I crystallizes in the monoclinic system, space group P2₁/c, a = 1.1050(4), b = 1.9534(7), c = 1.2376(4) ?, β = 94.955(7)°, and Z = 4. In the structure each Pr³⁺ ion lies in a single capped square antiprism geometry coordinated by carboxyl O and acyl O atoms and azomethine N atom of one ligand (H₂L⁻ form), which coordinates via the keto form, four carboxyl O atoms from two Phba, and O atoms of two water molecules. In each molecule, two tridentate ligands were coordinated by the H₂L⁻ form, and each Pr³⁺ ion was chelated by the carboxyl group from Phba. The carboxyl groups of H₂L⁻ and other two Phba were coordinated via μ₂-bridging form and bidentate bridging form, respectively. Complex I and ligands Phba and H₃L were also searched for biological activity against Valsa mali by the growth rate method. The result showed that the inhibitory rate of ligands Phba and H₃L is better than complex I, especially Phba.     

Tetraphenylantimony(V) hexachloroplatinate, tetrachloroaurate, and hexachlorostannate [Ph4Sb] 2+ [PtCl6]2?, [Ph4Sb]+[AuCl4]?, and [Ph4Sb] 2+ [SnCl6]2?: Synthesis and crystal structures

The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony) hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate (III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph₄Sb]⁺ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) ?, respectively. The coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°, respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) ?, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°, the root-mean-square deviation of the atoms from the coordination plane being 0.004 ?. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 5, pp. 373–379.     

三维配位聚合物[C4H12N2]3[PMo12O40]的合成、结构及其电化学性质

The title compound [C4H12N2] 3 [PMo12O40] was synthesized from the hydrothermal reaction and charac-terized by IR, elemental analysis and X-ray signal crystal structural analysis. The crystal of the title complex belongs to trigonal space group R3c with a=1.788 62 nm, c=2.354 3 nm, and V=6.522 62 nm3, Z=6, R1=0.038 4, wR2=0.102 0. The compound consisted of piperazine and PMo12O403-, and the structure is extended to three dimensional framework owing to the hydrogen bond between the O atoms and N atoms. The bulk-modified carbon paste electrode (APM-CPE) using this compound as modifier shows a good electrocatalytic activity toward the oxidation of ascorbic acid(AA). CCDC: 707968.     

EPR study of solid solutions of [Cr(NH3)5Cl]x[Rh(NH3)5Cl]1?x[PdCl4]·nH2O and [Cr(NH3)5Cl]x[Rh(NH3)5Cl]1?x[PtCl4] compounds

In order to determine the features of the structure of double complex salts (DCSs) of [Cr(NH₃)₅Cl]×[MCl₄]·nH₂O, where M = Pd, Pt, n = 0, 1, the DCS solid solutions of palladium and platinum with isostructural DCSs containing the chloropentaammine rhodium cation, [Cr(NH₃)₅Cl] _x [Rh(NH₃)₅Cl]_1−x [MCl₄]·nH₂O, where x = 0.01–0.2, are synthesized and studied by the EPR method. DCSs with the isostructural chloropentaammine rhodium cation are used as a diluter for magneto concentrated systems. It is shown that DCS of platinum and anhydrous DCS of palladium have the identical environment of chromium ions. The EPR spectra of chromium ions for these compounds are described by the following spin Hamiltonian parameters: S = 3/2, g _xx = 1.987, g _yy = 1.987, g _zz = 1.985, D = 1660 Gs, E = 235 Gs. For the palladium complex containing crystalline water, the EPR spectra of chromium ions are described by the parameters: S = 3/2, g _xx = 1.984, g _yy = 1.984, g _zz = 1.984, D = 1060 Gs, E = 350 Gs. A decrease in the crystal field parameters for the aqueous palladium complex is caused by a redistribution of the electron density to the oxygen atom in the second sphere of the chromium ion environment.     

Synthesis and structure of [Ph3MeP]3[Sb3I12]·Me2C=O, [Ph3MeP]3[Sb2I9], [Ph3MeP]2[SbI5], and [Ph3MeP]3[Sb3I12] antimony complexes

Complexes [Ph₃MeP]₃[Sb₃I₁₂]Me₂C=O (I), [Ph₃MeP]₃[Sb₂I₉] (II), and [Ph₃MeP]₂[SbI₅] (III) were obtained via the reaction of triphenylphosphonium iodide with antimony triiodide in acetone in 1:1, 3:2 and 2:1 molar ratios. Reaction of the complex III with antimony triiodide (1:1) affords [Ph₃MeP]₃[Sb₃I₁₂] (IV). The structure of the obtained complexes was confirmed by X-ray analysis.     

Acid nickel oxovanadate [Ni(H2O)6]2[H2V10O28] · 6H2O: Synthesis, IR spectra, thermal analysis, and crystal structure

Acid nickel oxovanadate, [Ni(H₂O)₆]₂[H₂V₁₀O₂₈] · 6H₂O (I) was synthesized and studied by X-ray diffraction analysis, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are triclinic: space group , a = 8.869(2) ?, b = 10.869(2) ?, c = 11.116(2) ?, α = 65.14(3)°, β = 74.11(3)°, γ = 70.47(3)°, V = 907.41 ?³, ρ(calcd.) = 2.56 g/cm³, Z = 1. Original Russian Text ? G.Z. Kaziev, A.V. Oreshkina, S.H. Quinones, D.A. Alekseev, V.E. Zavodnik, T.Yu. Glazunova, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 8, pp. 593–598.     

Synthesis, crystal structure and properties of a new heptamolybdate (NH4)6H2[Cu(C2O4)2(Mo7O24)] · 9H2O

An interesting heptamolybdate (NH₄)₆H₂[Cu(C₂O₄)₂(Mo₇O₂₄)] · 9H₂O (I) was prepared by convenational method in an aqueous solution and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. Crystal data for I: monoclinic, space group P2₁/m with a = 10.1460(5), b = 18.2616(9), c = 10.4994(5) ?, β = 94.3410(10)°, and Z = 2. X-ray structure analysis revealed the complexes to contain a copper center in an octahedral coordination mode bound to two [C₂O₄]²⁻ anios via the oxygen atoms and two oxygen atoms of the new heptamolybdate species. The zigzag chain structure of I is constructed by [Cu(C₂O₄)₂(Mo₇O₂₄)] units via Mo-O-Cu-O-Mo linkers.