Two mixed-valence vanadium(III,IV) phosphonoacetates with 16-ring channels: H2(DABCO)[V(IV)O(H2O)V(III)(OH)(O3PCH2CO2)2].2.5H2O and H2(PIP)[V(IVO)(H2O)V(III)(OH)(O3PCH2CO2)2].2.5H2O

Two isostructural mixed-valence vanadium phosphonoacetates H2(DABCO)[V(IV)O(H2O)V(III)(OH)(O3PCH2CO2)2].2.5H2O (1) and H2(PIP)[V(IV)O(H2O)V(III)(OH)(O3PCH2CO2)2].2.5H2O (2) have been synthesized. They crystallize in the orthorhombic space group Pnna with a = 7.0479(10) A, b = 15.307(2) A, and c = 17.537(3) A for 1 and a = 7.0465(9) A, b = 15.646(2) A, and c = 17.396(2) A for 2. X-ray single-crystal diffraction reveals that 1 and 2 have a three-dimensional open framework featuring 16-ring ellipsoid channels that are filled with doubly protonated 1,4-diazabicyclo[2,2,2]octanium/piperazinium cations and water molecules. According to the classification in metal-organic frameworks, 1 and 2 contain infinite (-O-V-)(infinity) chains that are cross-linked by "metalloligand" [VO(H2O)(O3PCH2CO2)2](4-) into a 3-D net of the sra topology. The temperature dependence of the magnetic susceptibility of 1 shows that the chi(m)T value in the range of 60-320 K is constant of 1.105 cm3 K mol(-1)/V2 unit, and upon further cooling, the chi(m)T value rapidly increases to 1.81 cm3 K mol(-1) at 2 K. The corresponding effective magnetic moment (mu(eff))/V2 unit varies from 2.97 mu(B) at 320 K to 3.80 mu(B) at 2 K. The magnetic data in the range of 2-320 K follow the Curie-Weiss law with C = 1.074 cm3 K mol(-1) and Theta= -1.34 K.     

V2O2F4(H2O)2·H2O: a new V4+ layer structure related to VOF3

V^IV oxyfluorides are of interest as frustrated magnets. The successful synthesis of two‐dimensionally connected vanadium(IV) oxyfluoride structures generally requires the use of ionic liquids as solvents. During solvothermal synthesis experiments aimed at producing two‐ and three‐dimensional vanadium(IV) selenites with triangular lattices, the title compound, diaquatetra‐μ‐fluorido‐dioxidodivanadium(IV) monohydrate, V₂O₂F₄(H₂O)₂·H₂O, was discovered and features a new infinite V⁴⁺‐containing two‐dimensional layer comprised of fluorine‐bridged corner‐ and edge‐sharing VOF₄(H₂O) octahedral building units. The synthesis was carried out under solvothermal conditions. The V⁴⁺ centre exhibits a typical off‐centring, with a short V=O bond and an elongated trans‐V—F bond. Hydrogen‐bonded water molecules occur between the layers. The structure is related to previously reported vanadium oxyfluoride structures, in particular, the same layer topology is seen in VOF₃.     

Ni(bpy)(H2O)(V2O6)和[Ni(bpy)2]2(V6O17)的水热合成与晶体结构

用NiCl2·6H2O,2,2＇-联吡啶（bpy）,NH4VO3,WO3在443K下通过水热反应法得到了两种多钒酸镍配合物Ni（bpy）（H2O）（V2O6）（1）和[Ni（bpy）2]2（V6O17）（2）．单晶X射线衍射结果表明化合物（1）属于正交晶系,空间群为Pcα2（1）,晶胞参数为0=0．91704（18）nm,b=1．0519（2）nm,c=1．4336（3）nm,V=1．3830（5）nm^3,Z=4;化合物（2）属于单斜晶系,空间群为P2（1）／c,晶胞参数为α=1．5467（3）nm,b=1．4740（3）nm,c=1．0457（2）nm,β=91．99（3）°,V=2．3826（8）nm^3,Z=4．化合物（1）由2,2’-联吡啶修饰的二维[Ni（V2O6）（H2O）]∞电中性层构成,而化合物（2）则由2,2＇-联吡啶修饰的、呈正弦波浪状的[Ni：（V6O17）]∞二维电中性层构成．     

Na6(H2O)20(V10O28)·4H2O,a novel polyvanadate(V) with a three‐dimensional framework

The novel title polyvanadate(V), poly[[octa‐μ‐aqua‐dodecaaqua‐μ₄‐octacosaoxidodecavanadato‐hexasodium] tetrahydrate], [Na₆(H₂O)₂₀(V₁₀O₂₈)·4H₂O]_n, contains [V₁₀O₂₈]⁶⁻ anions which lie about inversion centres and have approximate 2/m symmetry and which are linked to [Na₃(H₂O)₁₀]³⁺ cations through two terminal and two μ₂‐bridging O atoms. The structure contains three inequivalent Na⁺ cations, two of which form [Na₂(H₂O)₈]_n chains, which are linked via NaO₆ octahedra involving the third Na⁺ ion, thus forming a three‐dimensional framework.     

Mixed-valence uranium germanate and silicate: Cs(x)(U(V)O)(U(IV/V)O)2(Ge2O7)2 (x = 3.18) and Cs4(U(V)O)(U(IV/V)O)2(Si2O7)2

A new mixed-valence uranium germanate and the silicate analogue have been synthesized under hydrothermal conditions at 600 °C and 165 MPa. Their crystal structures contain infinite -U(V)-O-U(IV/V)-O-U(IV/V)-O-U(V)- chains that are connected by Ge(2)O(7) or Si(2)O(7) groups to form a 3D framework with six-ring channels where the Cs(+) cations are located. Two of the Cs sites in the germanate are partially occupied. Bond-valence-sum calculation and an U 4f X-ray photoelectron spectroscopy study confirm the valence states of the uranium.     

[Ni(H2O)6]2[Na(H2O)3]2[V10O28]·4H2O,bis(nickel hexahydrate) bis(sodium trihydrate) decavanadate tetrahydrate

Polyoxometallates are capable of including transition metals in their crystal structures as either discrete cations or heteroatoms. The title compound crystallizes with triclinic symmetry and consists of a centrosymmetric [V₁₀O₂₈]^6? anion, a trimeric {[Na(H₂O)₃][Ni(H₂O)₆][Na(H₂O)₃]}⁴⁺ cation, an [Ni(H₂O)₆]²⁺ cation and four water molecules of crystallization. The compound possesses two Ni atoms (each on independent inversion centres), one as a discrete cation and one in a disodium–nickel trimeric cation involved in the one‐dimensional polycation–polyanion hybrid polymer. The polymers are bound together via hydrogen bonds to the water mol­ecules and the nickel(II) hexahydrate cation. Several structures of decavanadate compounds having transition metal atoms, monovalent cations and [V₁₀O₂₈]^6? anions in the ratio 2:2:1 have been reported previously. However, the present compound differs from these in its arrangement of monovalent cations and transition metal atoms.     

Two New Polyoxovanadate‐supported Transition Metal Complexes: [Zn(en)2][Zn(en)2(H2O)2][{Zn(en)(enMe)}As6V15O42(H2O)]·4H2O and [Zn2(enMe)2(en)3][{Zn(enMe)2}As6V15O42(H2O)]·4H2O

Two novel As‐V‐O cluster supported transition metal complexes, [Zn(en)₂][Zn(en)₂(H₂O)₂][{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 1 ) and [Zn₂(enMe)₂(en)₃][{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 2 ), have been hydrothermally synthesized. The single X‐ray diffraction studies reveal that both compounds consist of discrete noncentral polyoxoanions [{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]^4? or [{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]^4? cocrystallized with respective zinc coordination complexes. Interestingly, compounds 1 and 2 exhibit the first two polyoxovanadates containing As₈V₁₅O₄₂‐(H₂O)]^6? cluster decorated by only one transition metal complex. Crystal data: 1 , monoclinic, P2₁/n, a = 14.9037(4) Å, b = 18.1243(5) Å, c = 27.6103(7) Å, β = 105.376(6)°, Z = 4; 2 monoclinic, P2₁/n, a = 14.9786(7) Å, b = 33.0534(16) Å, c = 14.9811(5) Å, Z = 4.     

Vibrational and thermal studies of the complexes (NH4)[VO(O2)2(phen)].2H2O and (NH4)[V(O2)3(phen)].2H2O

The infrared spectra of the oxodiperoxo and triperoxo complexes, (NH4)[VO(O2)2(phen)].2H2O and (NH4)[V(O2)3(phen)].2H2O have been recorded and the observed bands are assigned on the basis of Cs symmetry. Thermogravimetric (TG) and differential thermal analysis (DTA) measurements on these two complexes were also carried out. A detailed mechanism for the mode of thermal decomposition of the two complexes has been given and supported by infrared spectral measurements on the thermal decomposition products. The data obtained agree quite well with the expected structure and indicate that the final thermal decomposition product of these two complexes is V2O5.     

Dielectric characteristics of O2(H2O)i and (O2)2(H2O)i clusters. Computer-aided experiment

Absorption of oxygen molecules by water clusters with sizes of 10 ≤ i ≤ 50 is studied by the molecular dynamics method using the modified TIP4P model. It is revealed that the total dipole moment of the clusters nonmonotonically increases with their sizes. Absorption of O₂ molecules tends to raise the static permittivity of the ultradispersed medium formed by the clusters. The real and imaginary parts of the permittivity of water clusters with absorbed O₂ molecules are aperiodic functions of frequency. The permittivity components turn out to be nonmonotonic functions of cluster sizes. The IR absorption and reflectance spectra are calculated for clusters of pure water and aggregates with absorbed O₂ molecules. After the addition of oxygen molecules, the absorption coefficient of the clusters decreases, while the reflection coefficient increases. It is concluded that the capture of oxygen molecules by atmospheric moisture may reduce the greenhouse effect. Original Russian Text ? A.E. Galashev, V.N. Chukanov, O.A. Galasheva, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 155–160.     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Crystal structure of tetraphenylarsonium aquatetracyanonitridorhenate(V), (AsPh4)2 [ReN(H2O)(CN)4]·5H2O

The crystal structure of (AsPh₄)₂[ReN(H₂O)(CN)₄]·5H₂O has been determined from three-dimensional X-ray diffraction data. The yellow crystals are monoclinic, space group P2₁/n with cell dimensionsa=15.482(1),b=19.950(2),c=16.999(1)? and β=101.69(6)^o,Z=4,D _expt=1.48(1)g cm⁻³ andD _calc=1.52g cm⁻³. The anisotropic refinement of 7858 observed reflections converged toR=0.055. The [ReN(H₂O)(CN)₄]²⁻ ion has a distorted octahedral geometry. Bond distances: Re≡N=1.639(8), Re−OH₂=2.496(7) and Re−C_(av)=2.11(1) ?. The rhenium atom is displaced by 0.35 ? out of the plane formed by the four carbon atoms of the cyano ligands towards the terminal nitrido ligand. TMC 2479     

Two new hybrid organic/inorganic copper(II)-oxovanadate(V) diphosphonates: [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O and [Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8. Synthesis, structure, and magnetic properties

Two new hybrid organic/inorganic copper oxovanadium diphosphonates [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O (1) and [(Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8 (2) have been obtained by hydrothermal synthesis. The compounds are monoclinic, and they crystallize in the space group P2(1)/n with cell parameters of a = 11.788(2) A, b = 17.887(3) A, c = 14.158(2) A, and beta = 93.99(0) degrees and in the space group C2/c with cell parameters of a = 11.025(1) A, b = 18.664(2) A, c = 15.054(2) A, and beta = 90.06(0) degrees, respectively. Both compounds present two-dimensional frameworks built up from infinite chains of corner-sharing vanadium tetrahedra and diphosphonate groups connected by copper tetramers for (1) and copper dimers for (2). The remarkable feature of (2) is the encapsulation of propane molecules, stabilized by strong hydrogen bonding between the layers. The magnetic properties of the compounds have been investigated showing antiferromagnetic coupling with Tmax = 64 K for (1) and Curie-like paramagnetic behavior for (2).     

Anion-directed crystallization of coordination polymers: syntheses and characterization of Cu(4)(2-pzc)(4)(H(2)O)(8)(Mo(8)O(26)).2H(2)O and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2-pzc = 2-pyrazinecarboxylate)

Two new copper 2-pyrazinecarboxylate (2-pzc) coordination polymers incorporating [Mo(8)O(26)](4-) and [V(10)O(28)H(4)](2-) anions were synthesized and structurally characterized: Cu(4)(2-pzc)(4))(H(2)O)(8)(Mo(8)O(26)).2H(2)O (1) and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2). Crystal data: 1, monoclinic, space group P2(1)/n, a = 11.1547(5) A, b = 13.4149(6) A, c = 15.9633(7) A, beta = 90.816(1) degrees; 2, triclinic, space group P1, a = 10.5896(10) A, b = 10.7921(10) A, c = 13.5168(13) A, alpha = 104.689(2) degrees, beta = 99.103(2) degrees, gamma = 113.419(2) degrees. Compound 1 contains [Cu(2-pzc)(H(2)O)(2)] chains charge-balanced by [Mo(8)O(26)](4-) anions. In compound 2, layers of [Cu(3)(2-pzc)(4)(H(2)O)(2)] form cavities that are filled with [V(10)O(28)H(4)](2-) anions. The magnetic properties of both compounds are described.     

Polynuclear vanadium complexes from thermal decomposition of [V3O(O2CPh)6(H2O)3]Cl

Solid-state decomposition of [V3O(O2CPh)6(H2O)3]Cl at 300 degrees C followed by alcoholysis of the product gives the new vanadium complexes [V6O6(PhCO2)6(CH3O)6(CH3OH)3] (1), [V6O6(PhCO2)6(C2H5O)6(C2H5OH)3] (2), [V6O6(PhCO2)6(C3H7O)6(C3H7OH)3] (3), [V6O6(PhCO2)6(C4H9O)6(C4H9OH)3] (4) and [V4O4(OCH3)6(O2CPh)2(HOCH3)2] (5). Complexes 2, 3 and 5 have been crystallographically characterised. DC magnetic susceptibility studies on complex shows antiferromagnetic coupling leading to a S = 0 spin ground state.