Synthesis and Crystal Structure of[Co3(CO)9(μ3-C)C(O)OCH2]2

The title compound [Co3(CO)9(μ3-C)C(O)OCH2]2 was synthesized by the reaction of [Cl3CC(O)OCH2]2 with Co2(CO)8 at 40～50 ℃. Crystal data: C24H4O22Co6, Mr=997.88, monoclinic, space group P21/n(#14), a=9.330(2), b=15.197(4), c=11.783(4), β=91.16(2)°, V=1670.4(7) 3, Z=2, Dc=1.984 g/cm3, μ(MoKα)=30.01 cm-1, F(000)=972.00, T=293K, final R=0.045, Rw=0.051 for 1936 observed reflections with I＞2σ(I). The structure contains two centrosymmetric dimeric molecules in a unit cell, each of which has two tetrahedral skeletons (CCo3) connected through a C(O)OCH3CH2OC(O) bridge.     

Crystal structure of [Pd3(μ-OH)(μ-CH3COO)5]

The crystals of the [Pd₃(μ-OH)(μ-CH₃COO)₅] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) ų, space group Pna2₁, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd₃(μ-OH)(μ-CH₃COO)₅], in which the OH^? group, together with five CH₃COO^? anions, is a bridge ligand.     

Rhenium complexes with pyrazoles. Synthesis and crystal structure of trans-[Re(O)(OMe)L4]Br2·L·4H2O (L is 3,5-dimethylpyrazole)

The first mononuclear Re^V complex with four pyrazole ligands, viz., [Re(O)(OMe)L₄]Br₂ (L is 3,5-dimethylpyrazole), and its molecular adduct with L, viz., [Re(O)(OMe)L₄]Br₂·L·4H₂O, were synthesized. The complex is resistant to hydrolysis in a neutral aqueous solution. The structure of the adduct was established by X-ray diffraction analysis.     

Synthesis, structure and characterization of binuclear copper(Ⅱ) complexes

At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.     

Synthesis and crystal structure of platinum(II) acetamidates [Pt(2,2′-bipy)(NHCOCH3)2] and [enPt(μ-NHCOCH3)(μ-OH)Pten](NO3)2

The diamines PtbipyCl₂, and PtenCl₂ and their aqua and hydroxy derivatives react with acetonitrile to give the Pt(II) acetamidates [Pt(2,2′-bipy)(NHCOCH₃)₂] · 4.125 H₂O (I) and [enPt(μ-NHCOCH₃(μ-OH)Pten](NO₃)₂ · H₂O (II), which are characterized by X-ray diffraction. The crystals of I are triclinic, a = 7.137(10) Å, b = 12.655(3) Å, c = 21.914(6) Å, α = 81.82(2)°, β = 82.12(2)°, γ = 77.72(2)°, V = 1908.6(7) ų, space group P $\overline 1 $ , Z = 4, R = 0.033 for 3700 reflections. Complex I is a mononuclear acetamidate with terminal (NHCOCH₃)^? ligands. The crystals of II are monoclinic, a = 11.413(2) Å, b = 10.981(2) Å, c = 14.385(3) Å, β = 105.90(3)°, V = 1733.8(6) ų, space group P2₁/n, R = 0.028 for 2797 reflections. Complex II is a dimer with bridging (NHCOCH₃)^? and (OH)^? groups. The Pt-Pt distance is 3.1667(7) Å.     

Identification of the cobalt(II) chloride ‘mixed’ solvate Co4Cl8(H2O)4(MeCN)6: the ionic structure trans-[Co(H2O)2(MeCN)4] trans-[Co(H2O)2(MeCN)2(CoCl4)2]

The structure of the title compound features mononuclear octahedral Co^II cations, trans-[Co(H₂O)₂(MeCN)₄]²⁺, and trinuclear anions, trans-[Co(H₂O)₂(MeCN)₂(CoCl₄)₂]^2–; the latter centrosymmetric units contain a central octahedral Co(H₂O)₂(MeCN)₂ moiety with two tetrahedral [CoCl₄]^2– ligands. These two large ions are held in a network of intra- and inter-molecular hydrogen bonding.     

Synthesis and characterization of heteronuclear germanium(IV) and lanthanum(III) (chromium(III)) complexes with 1,3-diamino-2-propanoltetraacetic acid: Crystal and molecular structure of [Ge(OH)(μ-Hpdta)(μ-OH)La(H2O)4] · H2O

Two heteronuclear germanium(IV) and lanthanum(III) (chromium(III)) complexes with 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) have been synthesized. The compounds have been characterized by elemental analysis and X-ray powder diffraction data. The structure of [Ge(OH)(??-Hpdta)(??-OH)La(H₂O)₄] · H₂O (I) has been determined by X-ray crystallography. The crystals are monoclinic, a = 9.3805(3) ?, b = 10.3023(4) ?, c = 21.6527(6) ?, ?? = 94.829(2)°, V = 2085.10(12) ?³, Z = 4, space group P2₁/n, R1 = 0.0294 based on 5480 reflections with I > 2??(I). Compound I is composed of binuclear [Ge(OH)(??-Hpdta)(??-OH)La(H₂O)₄] molecules and crystal water molecules. In the dimeric molecule, the germanium and lanthanum atoms are linked by the bridging oxygen atom of the hydroxo ligand and the oxygen atom of the deprotonated isopropanol group of Hpdta^5?. The coordination spheres of germanium and lanthanum each contains one nitrogen atom and two carboxyl oxygen atoms of the four acetate arms of the heptadentate Hpdta^5? ligand. The Ge coordination polyhedron is completed to a distorted octahedron by the oxygen atom of the terminal hydroxo group, and the lanthanum coordination polyhedron is completed to a nine-vertex polyhedron by the oxygen atoms of four water molecules. In crystal, the complex molecules and crystal water molecules are combined by a system of hydrogen bonds.     

Synthesis and structure of novel dinitrosyl iron complexes [Fe2(μ-SCH2CH2NHR)2(NO)4]

Two novel dinitrosyl iron complexes with thiolate bridging ligands [Fe₂(μ-SCH₂CH₂NHR)₂(NO)₄] (R = Ac, Boc), derived from the cysteamine complex [Fe₂(μ-SCH₂CH₂NH₃)₂(NO)₄]²⁺ are described. The complex with acylated cysteamine is characterized by X-ray diffraction analysis. The cysteamine complex is a convenient precursor for modification of the bridging ligand.     

Synthesis and Crystal Structure of[Fe_2V (μ_3-O) (μ-O_2CCH_3)_6 (THF)_3]Cl· 3H_2O

lmTR0DUCTI0NTrivanadium(III)ox0-carb0xylat0complexeshaveattractedmuchinterestre-cently"~".Manyc0mp0unds0fthiskindhavebeensynthesizedandtheirstructural,physicalandspectr0sc0picpr0pertieshavebeenstudied.Butnone0fthiskindofcom-plexeswithmixedmeta1shavebeensynthesized.Hereinwereportthecrystalstruc-tureofthefirstmixedmeta1carboxylatocomp0undofvanadium.2EXPERIMENTAL2.1Synthesis0.l6g(lmmol)VCl3,0.32g(2mmol)FeCl3and0.48g(6mm0l)NaCO,CH,wasdisso1vedinaso1uti0n0ft0luerie(20ml),THF(lOml),ac…     

Synthesis of the hydroxide cluster [Al13(μ3-OH)6(μ-OH)18(H2O)24]15+ from an aqueous solution

A scalable synthesis of the "flat" tridecameric inorganic cluster [Al(13)(μ(3)-OH)(6)(μ-OH)(18)(H(2)O)(24)](15+) has been realized by treating an aqueous aluminum nitrate solution with a zinc-metal powder at room temperature. Single crystals and polycrystalline samples are readily obtained in yields exceeding 55% relative to the starting reagent Al(NO(3))(3). Products have been characterized by X-ray diffraction and solid-state (27)Al MAS and MQMAS NMR.     

Synthesis,characterization and crystal structure determination of mononuclear and dinuclear copper(II) carboxylates: [Cu(Hdpa)2(en)] and [{Cu2(μ-na)4(CH3OH)2}·2CH3OH]

Two new copper complexes [Cu(Hdpa)₂(en)] (1) and [{Cu₂(μ-na)₄(CH₃OH)₂}·2CH₃OH] (2) (where en is ethylene diamine, Hdpa is 2′-carboxy-[1,10-biphenyl]-2-carboxylate anion and na is 1-naphtalenecarboxylate) have been synthesized and their crystal structures were determined by X-ray crystallography. Complex 1 was prepared from the reaction of Cu(NO₃)₂·3H₂O with ethylene diamine and 2,2′-biphenyldicarboxylic acid in a mixture of water and methanol and complex 2 was prepared from the reaction of CuSO₄·5H₂O with 1-naphtalenecarboxylic acid in methanol. The two complexes were characterized by IR, UV–vis, luminescence and elemental analysis. Moreover, complex 2 was characterized by EPR spectroscopy and thermogravimetric analysis. Complex 1 is a monomer and complex 2 is a dimer with a paddle-wheel structure; both structures are without precedent in the literature.     

[Co(NioxH)2(PPh3)2]SiF5and [Co(NioxH)2(Thio)2]2SiF6· 3H2O Complexes: Synthesis and Structure

Compounds that form in the CoSiF₆· 6H₂O–NioxH₂–A–water–alcohol system, where A is thiourea (Thio) or triphenylphosphine (PPh₃) and NioxH₂is 1,2-cyclohexanedione dioxime, were synthesized and characterized by X-ray diffraction analysis. Crystal structures of the [Co(NioxH)₂(PPh₃)₂]SiF₅and [Co(NioxH)₂(Thio)₂]₂SiF₆· 3H₂O complexes were established. In octahedral Co(III) complexes, two radicals of 1,2-cyclohexanedione dioxime are bound by a hydrogen bond and are located in the equatorial plane. The intramolecular (– and H bonds) and intermolecular (C–H···F and H bonds) interactions in the crystal are discussed.     

Synthesis and Structure of a Novel Mg6 Cluster Molecule Mg6(μ3-OH)2(μ3-Br)2(μ-Br)8(THF)8

A novel Mg₆ cluster molecule with the formula of Mg₆( ₃-OH)₂( ₃-Br)₂(-Br)₈(THF)₈ (1) has been isolated in 38% yield from a reaction of the Grignard reagent, 2-naphthyl-Mg-Br with BBr₃ in THF. The structure of 1, determined by a single-crystal X-ray diffraction analysis, contains two Mg₃ triangles linked together by two bridging bromide ligands. Within each Mg₃ triangle, one hydroxide and one bromide ligand function as triply bridging ligands capping both sides of the Mg₃ triangle. The coordination geometry around each Mg(II) ion is approximately octahedral. NMR studies revealed that compound 1 is highly fluxional in solution.     

Thulium(III) trifluoroacetates Tm(CF3COO)3 · 3H2O and Tm2(CF3COO)6 · 2CF3COOH · 3H2O: Synthesis and crystal structure

Thulium trifluoroacetate compounds have been synthesized, Tm(CF₃COO)₃ · 3H₂O (I) and Tm₂(CF₃COO)₆ · 2CF₃COOH · 3H₂O (II). The structure of I has been refined by the Rietveld method on the basis of the structural data for Cd(CF₃COO)₃ · 3H₂O. The structure of II has been solved in a single-crystal X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic: for I a = 9.062(2) Å, b = 18.678(3) Å, c = 9.687(2) Å, β = 113.93(1)°, Z = 2, space group P2₁/c, R ₁ = 0.062; for II a = 8.560(4) Å, b = 19.866(5) Å, c = 20.813(7) Å, β = 101.69(4)°, Z = 8, space group C2/c, R ₁ = 0.0392. In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted monocapped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm-O bond lengths are in the range 2.28(1)–2.85(2) Å. The thulium atoms are bound into chains through carboxylate groups. These chains are linked into layers through hydrogen bonds.     

Synthesis and structure of osmium complexes [Ph3PR]2[OsCl6]·4DMSO

Russian Journal of General Chemistry - Reaction of sodium hexachloroosmate(IV) dihydrate with (2-oxopropyl)- and (2-carboxyethyl)-triphenylphosphonium chlorides in dimethyl sulfoxide afforded...     

Synthesis and molecular structures of the Co3(μ-OOCPh)4(μ,η2-OOCPh)2[OC(Ph)OHNEt3]2 and Co(Hdmpz)2(OOCPh)2 complexes (Hdmpz = 3,5-dimethylpyrazole)

The product of the thermal reaction between cobalt acetate hydrate and benzoic acid reacts with a triethylamine excess to form the trinuclear complex Co₃(μ-OOCPh)₄(μ,η²-OOCPh)₂[OC(Ph)OHNEt₃]₂, and its reaction with 3,5-dimethylpyrazole yields the mononuclear complex Co(Hdmpz)₂(OOCPh)₂. The compound structures are discussed on the basis of X-ray crystallographic data.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

Synthesis and Crystal Structure of [MoOS3Cu3I(dmpzm)2]·2(MeCN)0.5 (dmpzm = Bis(3,5-dimethylpyrazolyl)methane)

Reaction of a preformed cluster [Et4N]4[Mo2O2S6Cu6I6] with bis(3,5-dimethylpyra- zolyl)methane (dmpzm) in acetonitrile afforded the title compound [MoOS3Cu3I(dmpzm)2]·2(MeCN)0.5 1. The single-crystal X-ray diffraction study shows that 1 (C24H35Cu3IMoN9OS3, Mr = 975.25) crystallizes in triclinic, space group (P1-)with a = 11.442(2), b = 11.644(2), c = 16.211(3) (A), α = 99.26(3), β = 102.22(3), γ = 118.51(3)o, V = 1766.5(10) (A)3, Z = 2, Dc = 1.834 g/cm3, T = 193(2) K, F(000) = 960, μ = 32.12 cm-1, λ = 0.71073 (A), R = 0.0355 and wR = 0.0915 for 5686 observed reflections with I > 2σ(I). In the molecular structure of 1, the [MoOS3]2- anion acts as a tridentate ligand to bind one CuI group and two [Cu(dmpzm)]+ units to form a nido-like [MoOS3Cu3] core with an approximate C2v symmetry. The Mo…Cu contacts are in the range of 2.6460(12)～2.6798(11) (A).     

Tetranuclear azido-bridged copper(II) complex [Cu4(μ-salpn)2(μ1,1-N3)2(N3)2(H2O)2]: Synthesis,characterization and crystal structure

The reaction of salpnH₂ Schiff-base ligand (salpnH₂ = N,N′-bis(salicylidene)-1,3-propylenediamine) with Cu(NO₃)₂·3H₂O and a large excess of NaN₃ (1:2:8 molar ration), lead to the formation of [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1), which has been successfully obtained and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. The strong absorption band at about 2000–2100 cm^?1 and at 1597 cm^?1 regions of the IR spectrum of 1 clearly proves the presence of the both end-on (EO) bridging and terminal azido ions and CN (azomethine) groups, respectively. Single-crystal X-ray analyses revealed that the copper atoms are bridged alternately by end-to-on (EO) azido and phenoxo-salpn ligands in the prepared tetranuclear copper(II) complex [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1).     

Preparation and x-ray structure analysis of [Rh2Cl2(μ-CO)(μ-vdpp)2] [vdpp=H2C=C(PPh2)2]

Summary The complex [Rh₂Cl₂(-CO)(-vdpp)₂] (1) (vdpp=H₂C=C(PPh₂)₂) was prepared by reaction of [Rh₂(CO)₄-(-Cl)₂] with vdpp. When (1) is allowed to stand overnight under an atmosphere of CO without stirringtrans-[Rh₂Cl₂(CO)₂(-vdpp)₂] is formed as a red precipitate in low yields. On rapid addition of CO the tricarbonyl complex [Rh₂(CO)₂(-CO)(-Cl)(-vdpp)₂]-Cl is formed instead. The chemical behaviour of the vdpp-substituted complex (1) is very similar to that of the corresponding dppm-substituted complex [Rh₂(Cl₂-(-CO)(-dppm)₂] (dppm=H₂C(PPh₂)₂). this similarity also extends to the molecular structures of both compounds. Unit cell parameters of (1): space group Pben (Z=8),a=2344.7(5),b=1506.9(7),c=3021.6(9)pm. Rh-Rh 267.4(1) pm.