Bis[tetraruthenium(IV)]-containing polyoxometalates: [{Ru(IV)4O6(H2O)9}2Sb2W20O68(OH)2]4- and [{Ru(IV)4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]-

The reaction of [Sb(2)W(22)O(74)(OH)(2)](12-) and [Fe(4)(H(2)O)(10)(β-TeW(9)O(33))(2)](4-) with (NH(4))(2)[RuCl(6)] in aqueous solution resulted in the novel ruthenium(IV)-containing polyanions [{Ru(IV)(4)O(6)(H(2)O)(9)}(2)Sb(2)W(20)O(68)(OH)(2)](4-) and [{Ru(IV)(4)O(6)(H(2)O)(9)}(2){Fe(H(2)O)(2)}(2){β-TeW(9)O(33)}(2)H](-), exhibiting two cationic, adamantane-like, tetraruthenium(IV) units {Ru(4)O(6)(H(2)O)(9)}(4+) bound to the respective polyanion in an external, highly accessible fashion.     

Antimonato polyoxovanadates with structure directing transition metal complexes: pseudopolymorphic {Ni(dien)2}3[V15Sb6O42(H2O)]·nH2O compounds and {Ni(dien)2}4[V16Sb4O42(H2O)

Three new poloxovanadates were synthesized under solvothermal conditions and were structurally characterized. The two compounds with composition {Ni(dien)(2)}(3)[V(15)Sb(6)O(42)(H(2)O)]·nH(2)O (n = 12 and 8; dien = bis(2-aminoethyl)amine or diethylenetriamine) are pseudopolymorphs crystallizing in different space groups. The compounds were obtained by applying identical reaction slurries but using different reaction temperatures. Both compounds feature the [V(15)Sb(6)O(42)(H(2)O)](6-) anion which is the antimony analogue to the single molecule magnet [V(15)As(6)O(42)(H(2)O)](6-). Crystal data: 1 tetragonal space group P4, a = 46.9378(3), c = 16.51300(10) ? and V = 36380.7(4) ?(3). 2 rhombohedral space group R3c with a = 23.0517(4), c = 28.6216(5) ? and V = 13171.3(4) ?(3). In 1 several unusual short inter-cluster Sb···O contacts lead to the formation of three different super-clusters with composition V(60)Sb(24)O(168). The 12 unique {Ni(dien)(2)}(2+) complexes adopt all three possible configurations. In 2 the special arrangement of the {Ni(dien)(2)}(2+) complexes around the cluster anion prevents inter-cluster Sb···O contacts. The main structural motif of the third compound {Ni(dien)(2)}(4)[V(16)Sb(4)O(42)(H(2)O)] (3) is the [V(16)Sb(4)O(42)(H(2)O)](8-) cluster anion consisting of two perpendicular eight-membered rings of VO(5) pyramids. Two additional VO(5) polyhedra are located on opposite sides. Crystal data: 3 triclinic space group P1 = 13.5159(4), b = 14.2497(5), c = 14.9419(4) ?, α = 98.322(2), β = 114.080(2), γ = 110.130(2)° and V = 2326.35(12) ?(3).     

Synthesis and Crystal Structure of a Novel Heptanuclear Ruthenium- and Sodium-containing Polyoxomolybdate [ {Na(H2O)3}2{Ru(dmso)3}2(MoO4)3]·3H2O

The title compound, [{Na(H2O)3}2{Ru(dmso)3}2(MoO4)3]·3H2O, has been obstructure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the triclinic system, space group P1 with a = 12.3333(3), b = 12.6289(3), c = 32.0284(14)(A), α =79.873(7), β = 87.549(9), y = 64.500(4)°, V = 4429.5(2) (A)3, Z = 4, Mr = 1358.85, Dc = 2.038g/cm3, F(000) = 2696 and μ = 1.874 mm-1. The compound contains a novel pentanuclear triangle bipyramidal core, [{ Ru(dmso)3 } 2(MoO4)3]2-, which consists of two { Ru(dmso)3 } 2+ fragments and three {μ2-MoO4}2- units. Furthermore, the dmso ligands bridge the pentanuclear [Ru2Mo3] core and two [Na(H2O)3]+ fragments together, forming a neutral heptanuclear ruthenium- and sodiumcontaining polyoxomolybdate.     

Nitrilotris(methylenephosphonic) Complexes of Lanthanides [Na(H2O)x]2[LnIIINa6H(H2O)10{N(CH2PO3)3}2] · nH2O (LnIII = Pr,Nd)

Russian Journal of Coordination Chemistry - The sodium salts of lanthanide nitrilotris(mehylenephosphonate) complexes [Na(H2O)x]2[LnIIINa6H(H2O)10{N(CH2PO3)3}2] · nH2O, where LnIII = Pr (I),...     

新型杂多化合物[(CH3CH2)4N]4H3O· {Na[(HMo2O5)3(HPO4)(H2PO4)3]2}·(H2PO4)2·10H2O的水热合成与晶体结构

杂多化合物在催化、医药、材料及光化学等方面具有广泛的应用前景 [1～ 4 ] ,其中钼磷多金属氧酸盐具有优异的氧化催化性能 [5,6 ] .近年来合成的新奇结构的钼磷多金属氧酸盐中已测定结构的有含帽[7,8] 和非帽[9～ 12 ] 系列 .本文利用水热法合成了未见文献报道的结构新颖的夹心型磷钼多金属氧酸盐[( CH3CH2 ) 4N]4 H3O{Na[( HMo2 O5) 3( HPO4 ) ( H2 PO4 ) 3]2 }· ( H2 PO4 ) 2 · 1 0 H2 O,并测定了其晶体结构 .1　实验与晶体结构分析1 .1　仪器与试剂　元素 Na用美国原子吸收分光光度计测定 ;C,H和 N用 Perkin- Elmer 2 4 0…     

Synthesis and crystal structure of a three-dimensional 3d-4f heterometallic supramolecular complex {Eu(DMF)4(H2O)2Cr(CN)6·;H2O} n

A lanthanide-transition heterometallic supramolecular complex {Eu(DMF)₄(H₂O)₂Cr(CN)₆·H₂O} _n (1) has been synthesized based on the reaction of K₃[Cr(CN)₆], N,N-dimethylformamide (DMF) and Eu(NO₃)₃·6H₂O. 1 crystallizes in the monoclinic space group P2(1)/c with a=13.130(6)Å, b=12.923(7)Å, c=19.184(9)Å and Z=4. In 1 each Eu(III) is eight-coordinate with six oxygen atoms from four DMF molecules and two H₂O molecules and two nitrogen atoms from two cis-bridging CN ligands to form a distorted dodecahedron. 1 has a three-dimensional network created by the incorporation of coordinative linkage, three inter-molecular and an intrachain hydrogen bond.     

K3[Fe3.26V0.74(OH)O(PO4)4(H2O)2]·2H2O: a synthetic leucophosphite

A new iron(III)/vanadium(III) phosphate, K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O (1), has been obtained by hydrothermal synthesis and characterized by single crystal X-ray diffraction, Scanning electron microscopy–energy dispersive X-ray spectroscopy, Inductively coupled plasma atomic emission spectroscopy (ICP), thermogravimetric analysis, and FTIR spectroscopy. Single crystal X-ray diffraction reveals a 3D open framework (monoclinic, space group P2₁/n, a?=?9.6391(7)?Å, b?=?9.8063(7)?Å, c?=?9.7268(7)?Å, β?=?100.71(1)°, and V?=?903.38(11)?ų). This structure presents Fe^III and V^III in a 4.4?:?1?M ratio with the metal ions in two different crystallographic sites. Both metallic centers have distorted octahedral environments, linked by PO₄ tetrahedra, forming channels along the a-axis. The asymmetric unit of K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O presents a {M₄(OH)O(PO₄)₄(H₂O)₂}^3? anionic entity, charge balanced by three K⁺, which are located within the channels. It is also possible to distinguish M₄O₂ units whose M^III polyhedra are linked by vertex and edges.     

H10[NiMoV12O40{Ni(H2O)3}4]的水热合成和晶体结构

在水热的条件下合成了1个标题的Mo-Ni-O异核簇合物，化学式为H34NiMo12O52(Mr=2311.10)，用单晶X射线衍射方法测定了它的结构，该晶体属四方晶系，I4l/amd空间群，晶胞参数为a=15.319(2),c=30.645(3)A,V=7191.2(16)A^3,Z=4,Dc=2.135g/cm^3,μ＝3．369mm^-1,F(000)=4376,1036个可观察衍射点（I＞2σ（I）），最终结构偏离因子R＝0．0560，wR=0.1632,S=1.002，该化合物簇阴离子笼中心是Ni^2 ，由12个MoO6八面体和4个NiO6八面体通过共角和共边构成。     

Thermodynamic Model for BiPO4(cr) and Bi(OH)3(am) Solubility in the Aqueous Na+–H+–\mathrm{H}_{2}\mathrm{PO}_{4}^{-}–\mathrm{HPO}_{4}^{2-}–\mathrm{PO}_{4}^{3-}–OH−–Cl−–H2O System

Prior to this study no data for the solubility product of BiPO₄(cr) or the complexation constants of Bi with phosphate were available. The solubility of BiPO₄(cr) was studied at 23±2?°C from both the over- and under-saturation directions as functions of a wide range in time (6–309 days), pH values (0–15), and phosphate concentrations (reaching as high as 1.0 mol?kg^?1). HCl or NaOH were used to obtain a range in pH values. Steady state concentrations and equilibrium were reached in <6 days. The data were interpreted using the SIT model. These extensive data provided a solubility product value for BiPO₄(cr) and an upper limit value for the formation of BiPO₄(aq). Because the aqueous system in this study involved relatively high concentrations of chloride, reliable values for the complexation constants of Bi with chloride were required to accurately interpret the solubility data. Therefore as a part of this investigation, existing Bi–Cl data were critically reviewed and used to obtain values of equilibrium constants for various Bi–Cl complexes at zero ionic strength along with the values for various SIT ion interaction parameters. Predictions based on these thermodynamic quantities agreed closely with our experimental data, the chloride concentrations of which ranged as high as 0.7 mol?kg^?1. The study showed that BiPO₄(cr) is stable at pH values <9.0. At pH values >9.0, Bi(OH)₃(am) is the solubility controlling phase. Reliable values for the Bi(OH)₃(am) solubility reactions involving Bi(OH)₃(aq) and $\mathrm{Bi}(\mathrm{OH})_{4}^{-}$ and the formation constants of these aqueous species are also reported.     

Thermal degradation of a molecular magnetic material: {N(n-C4H9)4[FeIIFeIII(C2O4)3]}∞

Thermal degradation of a mixed-valence oxalate based molecular material {N(n-C₄H₉)₄[Fe^IIFe^III(C₂O₄)₃]}_?? was investigated by thermogravimetric (TG) analysis. Considering the mass loss at each step of TG profile, possible step-wise thermal degradation reaction pathways of the precursor material are proposed which indicate the formation of hematite and magnetite as the solid end product of the degradation reaction. The IR spectroscopy and powder X-ray diffraction (XRD) studies of the thermally degraded samples supplement the proposed reaction pathways.     

A fixation mode of gold(III) in the [Zn2{S2CN(iso-C3H7)2}4]-[AuCl4]−/2 M HCl chemisorption system: Supramolecular structure and thermal behavior of the heteropolynuclear complex ([H3O][Au3{S2CN(iso-C3H7)2}6][ZnCl4]2 · H2O) n

The interaction of freshly precipitated binuclear zinc dithiocarbamate [Zn₂{S₂CN(iso-C₃H₇)₂}₄] with solutions of AuCl₃ in 2 M HCl is studied. The heterogeneous reaction includes the chemisorption of gold(III) and the partial ion exchange to form a polynuclear ionic gold(III)-zinc complex. The molecular and supramolecular structures of the individual fixation mode of gold(III), coordination compound (H₃O[Au₃{S₂CN(iso-C₃H₇)₂}₆][ZnCl₄]₂ · H₂O) _n (I), are determined by X-ray diffraction analysis. Compound I includes three complex cations [Au{S₂CN(iso-C₃H₇)₂}₂]⁺, two of which (noncentrosymmetric, A) are structurally nonequivalent with respect to the third cation (centrosymmetric, B). The structural self-organization of compound I includes the formation of linear trinuclear fragments [Au₃{S₂CN(iso-C₃H₇)₂}₆]³⁺ by three cations (2A and B) due to nonsymmetric secondary Au…S bonds. The interaction between the [Au₃{S₂CN(iso-C₃H₇)₂}₆]³⁺ fragments results in the formation of zigzag polymer chains ([Au₃{S₂CN(iso-C₃H₇)₂}₆]³⁺) _n . The outer-sphere water molecule and the hydronium ion are involved in the pairwise linkage of the [ZnCl₄]₂-anions due to hydrogen bonds Cl…O. The chemisorption capacity of the zinc dithiocarbamate complex calculated from the reaction of gold(III) fixation is 471.2 mg of gold per 1 g of the sorbent. The conditions for the isolation of chemisorbed gold are determined by the simultaneous thermal analysis of the thermal behavior of compound I. The multistage thermal destruction includes two steps of dehydration of the complex, the thermolysis of the dithiocarbamate moiety and [ZnCl₄]^2? (with the release of metallic gold and zinc chloride and the partial formation of ZnS), and the evaporation of ZnCl₂. The final products of the thermal transformations are metallic gold and ZnS.     

Crystal structure of [Cu4(pytp)2(SO4)2(H2O)10](SO4)2 · 4H2O. A tetranuclear copper(II) complex with a new asymmetric ligand,pytp*, as a bridge

A new asymmetric bridge ligand, pytp, was prepared and characterized systematically by f.t.i.r., u.v.–vis., ¹H-n.m.r. and by FAB-MS spectroscopy. A tetranuclear Cu^II complex [Cu₄(pytp)₂(SO₄)₂(H₂O)₁₀](SO₄)₂·4H₂O (1) was prepared and characterized by elemental analysis and u.v.–vis. spectroscopy. A crystal structure analysis indicates that there are two different coordination spheres in (1) and that two of the copper centers are bridged by two ₂-SO₄ entities, creating a most unusual sulphate bridge.     

Synthesis and Characterization of a Reduced Molybdenum(Ⅴ) Phosphate, (H3dien)2(H2dien)2[NaMo12O24(OH)6-(H2PO4)(HPO4)5(PO4)2]·nH2O(n= 10.92)

A new reduced molybdenum(Ⅴ) phosphate (H3dien)2(H2dien)2[NaMo12O24 (OH)6 (H2PO4)(HPO4)5(PO4)2]·nH2O(n= 10.92,dien = diethylenetriamine) has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR and X-ray diffraction. C16H96.84MO12N12NaO72.92P8 (Mr = 3046.73) crystallizes in the monoclinic system, space group P21/c with a = 13.3575(18), b = 21.907(3), c = 15.654(2) A, β= 110.22(2)°, V= 4298.4(10) (A)3, Dc = 2.354 g/cm3, Z = 2, μ(MoKα) = 1.966 mm-1, F(000) = 2990.4, the final R = 0.0357 and wR = 0.1086 for 8739 observed reflections with Ⅰ> 2σ(Ⅰ). It consists of sandwich-shaped cluster anions [Na{Mo6P4}2]10- held together into a three-dimensional supramolecular framework through intermolecular hydrogen-bonding contacts. A probe reaction of the oxidation of acetaldehyde with H2O2 showed that this compound has high catalytic activity in the reaction.     

Observation of the novel “three-pointed star” cage-like (H2O)5 cluster in a polymeric solid {[Ag2(bpp)2(H2O)2](chd)·9H2O} n

Coordination polymeric solid, {[Ag₂(bpp)₂(H₂O)₂](chd)·9H₂O} _n (1) (bpp = 1,3-bis(4-pyridyl) propane, H₂chd = 1,4-cyclo-hexanedicarboxylic acid), has been obtained by the solution phase ultrasonic synthesis techniques. The structure established through X-ray structural analysis shows that the compound traps an interesting 1D water tape built by the alternating ??three-pointed star?? cage-like pentameric and D _2h tetrameric clusters (C2/c, Z = 4; a = 30.37(2) ?, b = 9.271(5) ?, and c = 18.89(1) ?; ?? = 128.47°; V = 4164(4) ?³). The novelty of the present complex is the rarely crystallographic example of the cage-shaped water pentamer, which is usually ascribed to a less-stable species. A first-principle density functional theory (DFT) calculation demonstrates that the interconnectivity between cage-like pentamers and D _2h tetramers is beneficial for contribution to the structural stabilization of these less-stable water cluster species.     

Synthesis,crystal structure,and magnetism of a dinuclear nickel(II) complex [Ni2(MOBPT)2(N3)4] · 2H2O

A dinuclear nickel(II) complex, [Ni₂(MOBPT)₂(N₃)₄] · 2H₂O (MOBPT = 4-(p-methoxyphenyl)-3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, UV, IR, ESI-MS, and single crystal X-ray crystallography. The complex crystallizes in triclinic system, space group P 1 with a = 9.877(2) Å, b = 10.396(2) Å, c = 11.975(3) Å, α = 71.638(3)°, β = 74.968(3)°, γ = 64.747(3)°, V = 1044.2(4) ų, Z = 1, R = 0.0371 for 5774 observed reflections. The crystal structure determination shows that the dinuclear Ni₂N₈ unit is almost planar with each Ni²⁺ coordinated by four nitrogens from two MOBPT ligands and two axial azides in a distorted octahedral geometry. Magnetic measurements reveal weak antiferromagnetic exchange in the complex.     

A new α-keggin unit coordinated to two cobalt complex moieties {PMoVI 11MovO40[Co(TATP)2(H2O)]2}·4H2O

A new α-Keggin unit supported transition metal complex, {PMo^VI ₁₁Mo^VO₄₀ [Co(TATP)₂(H₂0)]₂}?·?4H₂O (1) (TATP?=?1,4,8,9-tetranitrogen-trisphene), has been hydrothermally synthesized and characterized by single crystal X-ray diffraction. X-Ray analysis showed that the two [Co(TATP)₂(H₂O)] units are covalently bonded to the α-Keggin unit [PMo^VI ₁₁Mo^V04o]^4? via the terminal oxygen atoms. 1 represents the α-Keggin type polyoxoanion coordinated with two transition metal complex moieties, which further acts as a neutral molecular unit to construct an interesting 3D supramolecualr framework.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Cluster cyanide-bridged heterometallic coordination polymers: synthesis and crystal structures of compounds [{Cu2(dien)2(CN)}2{Mo4Te4(CN)12}]·14.5H2O and (H3O)3K[{Mn(H2O)2}2{Mn(H2O)2(NO3)}4{W4Te4(CN)12}2]·8H2O

The reactions of anionic molybdenum and tungsten cyanide cuboidal clusters with Cu^II and Mn^II salts afforded two new cyanide-bridged heterometallic coordination polymers with the composition [{Cu₂(dien)₂(CN)}₂{Mo₄Te₄(CN)₁₂}]?14.5H₂O (1) and (H₃O)₃K[{Mn(H₂O)₂}₂{Mn(H₂O)₂(NO₃)}₄{W₄Te₄(CN)₁₂}₂]·8H₂O (2). The structures of these compounds were established by X-ray diffraction analysis. Compound 1 has a layered structure, in which the cuboidal cluster fragments {Mo₄Te₄(CN)₁₂}^6? are linked to the copper atoms of the dinuclear fragments {(H₂O)(dien)Cu(μ-CN)Cu(dien)(H₂O)} through the bridging CN groups. Coordination polymer 2 has a framework structure, in which the cluster fragments {W₄Te₄(CN)₁₂}^6? are linked to the manganese(II) aqua complexes of two types, viz., the dinuclear fragment {Mn(μ₂-H₂O)₂Mn} and the tetranuclear cyclic fragment {(H₂O)₂Mn(μ₂-NO₃)}₄, through the bridging CN groups.