Isomerization [trans-B20H18]2– → [iso-B20H18]2– during silver(I) complexation with triphenylphosphine

The trans–iso isomerization of the dimeric borohydride cluster anion [B₂₀H₁₈]^2– in the course of the silver(I) complexation reaction with triphenylphosphine has been described for the first time. The isomeric complexes [Ag₂(Ph₃P)₆[trans-B₂₀H₁₈]] and [Ag₂(Ph₃P)₆[iso-B₂₀H₁₈]] have been isolated and characterized by physicochemical methods. The structures of the compounds have been determined by X-ray crystallography.     

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H2O)6]H3[V10O28] · 2H2O: Synthesis and study

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H₂O)₆]H₃[V₁₀O₂₈] · 2H₂O (I) was obtained and examined by mass spectrometry, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The crystals are monoclinic, space group $P\bar 1$ a = 7.862(3), b = 8.427(5), c = 5.000(2) Å, β = 96.46(4)°, V = 867.0(3) ų, ρ_calcd = 5.83 g/cm³, Z = 1.     

Synthesis and Structural Characterization of a Polyoxomolybdate HNa7[Mo36O112(H2O)16]·47H2O

A new polyoxomolybdate complex HNa7[Mo36O112(H2O)16]·47H2O 1 has been prepared in the beaker solution and characterized by single-crystal X-ray diffraction and elemental analyses. Crystal data: H127Mo36Na7O175, Mr = 6542.79, monoclinic, C2/c, a = 40.891(6), b =17.900(3), c = 25.580(4) (A), β = 125.673(2)°, V = 15210(4)(A)3, Z = 4, Dc = 2.857 g/cm3, F(000) =12464, μ = 3.013 mm-1, R = 0.0633 and wR = 0.1654 (I＞ 2σ(Ⅰ)). With the bridging sodium cations,the [Mo36O112(H2O)16]8- units in compound 1 are linked to form a one-dimensional structure, on the basis of which a three-dimensional architecture is further constructed via other sodium cations and complicated hydrogen bonds.     

Synthesis and electrochemical properties of substituted heteropoly acid with Dawson structure H7[In(H2O)P2W17O61]·23H2O

A new solid high-proton conductor, substituted heteropoly acid with Dawson structure H(7)[In(H(2)O)P(2)W(17)O(61)]·23H(2)O, has been synthesized by the degradation/ion exchange/freezing method. The pH of the synthesis reaction was given. The product was characterized by chemical analysis, IR, UV, XRD and TG-DTA. The determination of conductivity shows that H(7)[In(H(2)O)P(2)W(17)O(61)]·23H(2)O is an excellent solid high-proton conductor with conductivity of 1.34 × 10(-3) S cm(-1) at 18 °C, and 70% relative humidity (RH). Its activation energy is 37.72 kJ mol(-1), which suggests that its mechanism of proton conduction is the Vehicle mechanism.     

Syntheses, Crystal Structures and Characterization of Two Zeotype Crystals of K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62] ·9.5H2O and K4[Cr3O(H2O)3(OOCH)6[H3P2W17Co(H2O)O61]·20H2O

Two novel zeotype crystals, K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62]·9.5H2O(1) and K4 [Cr3O(H2O)3·X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, a=1.5895(2)nm, b=1.5895(2) nm, c=2.1620(4) nm, α=90°, β=90°, γ =120°, V=4.7305(13) nm3, Z=2,R1 =0. 0726, wR2=0. 1542; C6H57O98K4Cr3CoP2W17(2), hexagonal P6(3)/mmc, a=1. 61328 (3) nm, b=1.61328(3) nm, c=2. 06613 (9) nm, α=90°,β=90°, γ=120°, V=4. 6570(2) nm3, Z=2, R1=0. 0377,wR2 =0.1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal 1 and lacunary Wells-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.     

Redox behaviours and electrocatalytic properties of copper within Dawson structure-derived sandwich heteropolyanions [Cu4(H2O)2(X2W15O56)2]16− (X=P or As)

Two Cu²⁺ sandwich-type heteropolyanions with the Dawson moiety [X₂W₁₅O₅₆]¹²⁻ (X=P or As) were synthesized. Their oxidized forms are stable from pH 3 to at least pH 7. Their characterization by cyclic voltammetry revealed the stepwise reduction of Cu²⁺ centers within these heteropolyanions before deposition of Cu⁰ on the glassy carbon electrode surface. The presence of chloride ions in the supporting electrolyte does not induce the extraction of the copper centers from the heteropolyanions. These sandwich-type complexes are shown to have electrocatalytic properties towards the reductions of nitrate, nitrite, dioxygen and hydrogen peroxide. Electrochemical characterization of these complexes is offered for the first time.     

Synthèse et étude structurale du polyanion [AsIII 4Mo6W14O72(H2O)2]12– isomorphe de [AsIII 4W20O72(H2O)2]12–

Synthesis and X-ray study of the polyanion [As^III ₄Mo₆W₁₄O₇₂(H₂O)₂]^12– isomorphous of [As^III ₄W₂₀O₇₂(H₂O)₂]^12–. The addition of an excess of MoO₄^2– to a solution of [As^III₂W₈O₃₀(OH)]^7– led at pH=4 to a new polyanion [As^III ₄Mo₆W₁₄O₇₂(H₂O)₂]^12– isostructural of [As^III ₄W₂₀O₇₂(H₂O)₂]^12–. The structure of this compound was determined by X-ray diffraction: a=11.183(4) Å, b=13.432(3) Å, c=19.626(5) Å, α=77.87(2), β=73.57(3), γ=67.44(3)°, V=2 594(1) ų, P1̄. Reliability factors are R=7.89 and R_w=9.97. The starting compound underwent an isomerisation β→α and one tungsten was formally substituted by one molybdenum atom; two other molybdenum atoms were incorporated. The polyanion is formed of two units αB–As^IIIMo₂W₇O₃₃ connected by a double chain As^IIIOMo₂O₂(H₂O). Arsenic and molybdenum are both bound to two octahedrons WO₆ of one unit As^IIIOMoO₂W₇O₃₃, both molybdenum atoms of which are contiguous. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASpolymolybdotungstate / arsenomolybdotungstate / crystal structure / (hexamolybdenumtetradecatungsten)ate / synthesis of a new mixed polytungstate     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

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.     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

Magnetic relaxation in basic iron(III) carboxylate [Fe3O(O2CPh)6(H2O)3]ClO4·py

The magnetic properties of the antiferromagnetic basic iron(III) carboxylate [Fe(3)O(O(2)CPh)(6)(H(2)O)(3)]ClO(4)·py are studied by magnetic susceptometry and electron paramagnetic resonance spectrocopy. Ac susceptometry under moderate external magnetic fields reveals magnetic relaxation at liquid helium temperatures.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

Syntheses and Crystal Structures of Two Ion Pair Complexes, [Ru(bpy)3]2[Fe(CN)6]I · 7H2O and [Ru(bpy)3]- [Fe(CN)5NO]CH3OH · H2O

Two ion pair complexes, [Ru(bpy)₃]₂[Fe(CN)₆]I [sdot] 7H₃O (1) and [Ru(bpy)₃][Fe(CN)₅NO](CH₃OH) [sdot] H₂O (2) (bpy = 2,2-bipyridine) have been synthesized and structurally characterized. X-Ray crystallographic structures of 1 and 2 both show Fe(III) and Ru(II) in distorted octahedral environments. In both complexes, H-bonding interactions between an uncoordinated water molecule and the nitrogen atom of a cyano group exist.     

Synthesis and Crystal Structure of [H-amp]4[Mo8O26(DMF)2]·2H2O (amp = 2-Amino-6-methyl-pyridine)

The reaction of MoO2(acac)2 with 2-amino-6-methyl-pyridine (amp) in the mixed solvent of DMF (N,N-dimethylformamide) and water affords the title complex [H-amp]4- [Mo8O26(DMF)2]·2H2O which was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis with the following crystallographic data: C30H54Mo8N10O30, Mr = 1802.35, monoclinic, P21/n, a = 8.631(1), b = 24.260(3), c = 13.351(2)A,β= 104.688(3)°, V = 2704.2(7) A3, Z = 2, Dc = 2.213 g/cm3, μ =1.890 mm－1 and F(000) = 1760. The final R = 0.0281 and Wr = 0.0620 for 4935 observed reflections with I > 2σ(I). X-ray structure analysis has confirmed the existence of γ-[Mo8O26]4－ anion in the molecule. Eight MoO6 distorted octahedra share edges with short terminal Mo-O bonds from 1.691(3) to 1.749(2)A, medium bonds from 1.868(2) to 1.965(2) A And long bonds from 2.059(2) to 2.450(2) A. In the terminal site there exist two DMF ligands bound to the Mo atom through O atoms with the Mo-ODMF bond length of 2.166(3) A, affording a bond strength of 0.433. A three-dimensional network structure was formed through hydrogen bonds.     

Synthesis and structure of two molybdovanadates containing coordinatively bound oxalato ligands: (NH4)6[Mo6V2O24(C2O4)2]·6H2O and (NH4)4[H2Mo2V2O12(C2O4)2]·2H2O

The compounds (NH₄)₆[Mo₆V₂O₂₄(C₂O₄)₂]·6H₂O (I) and (NH₄)₄[H₂Mo₂V₂O₁₂(C₂O₄)₂]·2H₂O (II) have been prepared from molybdenum(VI) oxide and ammonium vanadate in aqueous solution through the addition of ammonium oxalate, and their structures determined by X-ray structure analysis. Whereas the molybdovanadate anion [Mo₆V₂O₂₄(C₂O₄)₂]⁶⁻ found in (I) consists of six MoO₆ and two VO₆ edge-sharing octahedra of the γ-[Mo₈O₂₆]⁴⁻ type structure, the tetranuclear anion [H₂Mo₂V₂O₁₂(C₂O₄)₂]⁴⁻ of (II) adopts the structure with a M₄O₁₆ core. Both complexes contain bidentate oxalato ligands bonded to the vanadium ions. In both crystal structures the molybdovanadate anions are mutually hydrogen bonded by ammonium ions and water molecules.     

K4H2[SiW5Mo6Mn(H2O)O39]·22H2O的晶体结构

合成了一个锰硅钼钨四元取代含氧簇合物,用单晶X射线衍射方法测定了结构,该晶体属于四方晶系,空间群P4/mnc,a=14.119(3),c=12.496(4),V=2490.9(12)3,Mr=2862.70,z=2,Dc=3.817g*cm-3,μ=15.922mm-1,R=0.0462,wR=0.1232.锰硅钼钨阴离子中,中心SiO4四面体在C4轴的两个位置上是无序的.     

Synthesis and physicochemical study of diazabicycloundecene hexamolybdochromate [C9H16N2]H3[CrMo6O18(OH)6] · 2H2O

Quinazoline hexamolybdochromate [C₉H₁₆N₂]H₃[CrMo₆O₁₈(OH)₆] · 2H₂O has been synthesized and studied by mass spectroscopy, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The compound crystallizes in triclinic system with the unit cell parameters a = 15.06 Å, b = 13.08 Å, c = 8.17 Å, α = 59.85°, β = 123.15°, γ = 107.01°, V = 1165.62 ų, ρ_pycn = 3.58 g/cm³, and Z = 2.     

Syntheses and structures of nine-coordinate NH4[HoIII(Edta)(H2O)3] · 1.5H2O, (NH4)4[Ho 2 III (Dtpa)2] · 9H2O, and (NH4)3[HoIII(Ttha)] · 5H2O complexes

The three title complexes, NH₄[Ho^III(Edta)(H₂O)₃] · 1.5H₂O (I) (H₄Edta = ethylenedianine-N,N,N′,N′-tetraacetic acid), (NH₄)₄[Ho ₂ ^III (Dtpa)₂] · 9H₂O (II) (H₅Dtpa = diethylenetriamine-N,N,N′,N″,N″-entaacetic acid), and (NH₄)₃[Ho^III(Ttha)] · 5H₂O (III) (H₆ Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, and single-crystal X-ray diffraction technique. Complex I has a nine-coordinate mononuclear structure with distorted monocapped square antiprismatic conformation and its crystal structure belongs to orthorhombic system and Fdd2 space group. The crystal data are as follows: a = 19.343(9), b = 35.125(17), c = 12.364(6) Å, V = 8400(7) ų, Z = 16, M = 552.26, ρ_calcd = 1.747 g cm^?3 μ = 3.828 mm^?1, and F(000) = 4368. Complex II has a binuclear nine-coordinate pseudomonocapped square antiprismatic conformation and its crystal structure belongs to triclinic system and space P1 group. The crystal data are as follows: a = 9.7637(16), b = 9.9722(16), c = 12.945(2) Å, α= 85.853(2)°, β = 77. 140(2)°, γ = 77.140(2)°, V = 1198.4(3) ų, Z = 1, M = 1340.80, ρ_calcd = 1.858 g cm^?3, μ = 3.380 mm^?1, and F(000) = 674. As for complex III, it also has nine-coordinate mononuclear structure with distorted tricapped trigonal prism and its crystal structure belongs to monoclinic system andP2₁/c space group. The crystal data are as follows: a = 10.349(3), b = 12.760(4), c = 23.142(7) Å, β = 91.020(6)°, V = 3055.6(16) ų, Z = 2, M = 797.55, ρ_calcd = 1.734 g cm^?3, μ = 2.674 mm^?1, and F(000) = 1624. The results showed that although the ligands are different from one another in the shape and the numbers of coordination atoms, they all have nine-coordinate structures. However, one of them has binuclear structure and the other two have mononuclear structures because of the difference of the ligands.