Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) ?, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) ?(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) ?, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) ?(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not significantly couple with the S = 1/2 vanadyl groups. The susceptibility data can be successfully reproduced assuming a distorted ligand field for the Co(2+) ions (1) and an O(h)-symmetric Ni(2+) ligand field (2).     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

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.     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

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。     

Hydrothermal syntheses and crystal structures of two transition metal complexes supported by vanadate {V4O12}: {[ M (dpa)2]2V4O12} ( M = Co,Ni. dpa = 2,2′-dipyridylamine)

Hydrothermal reactions have been exploited in the syntheses of two new metavanadates, {[Co(dpa)₂]₂V₄O₁₂}?·?H₂O (1) and {[Ni(dpa)₂]₂V₄O₁₂}?·?H₂O (2), which were characterized by X-ray diffraction, IR and thermogravimetric analysis. Crystal data: C₄₀H₃₈N₁₂O₁₃Co₂V₄ (1) monoclinic. P2(1), a?=?10.126(2), b?=?17.639(4), c?=?12.930(3) Å,?α?= 90°,?β?= 98.356(4)°,?γ?= 90°, Z?=?2; C₄₀H₃₈N₁₂O₁₃Ni₂V₄ (2) monoclinic. P2(1), a?=?10.1037(9), b?=?17.6680(14), c?=?12.8832(10) Å,?α?= 90°,?β?= 98.423(2)°,?γ?= 90°, Z?=?2. The two complexes are isomorphic and their structures consist of a [V₄O₁₂]^4? cluster bound to two [M(dpa)₂]²⁺ moieties through the terminal oxygen atoms in a trans-conformation; the [V₄O₁₂]^4? cluster adopts a chair-like configuration.     

三元配合物{Ni[S2P(4-MeC6H4O)]2(4-Me Py)2}的合成、晶体结构与光谱性质

以[(4-MeC6H4O)2PS2]2Ni和4-甲基吡啶(4-MePy)反应合成了三元配合物{Ni[S2P(4-MeOC6H4)]2(4-MePy)2},用元素分析、红外光谱、紫外-可见光谱和热重分析对其进行了表征,并用X-射线衍射法测定了晶体结构.该晶体属于单斜晶系,P21/n空间群;晶胞参数为:a=0.95364(...     

Hydrothermal Synthesis and Characterization of [V16O38(Cl)][Cu(enMe)2]3.5·2H2O Containing {V16O38} Cluster

Compound [V16O38(Cl)][Cu(enMe)2]3.5*2H2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction, elemental analysis, IR, EPR and TGA analysis. The X-ray crystallography shows that compound 1 contains a new {V16O38} cluster shell, which is connected by [Cu(enMe)2]2 coordination fragments into a 3-D framework. The compound crystallized in a monoclinic system with space group P2(1)/n, M=2235.82, a=1.26076(3) nm, b=2.55802(6) nm, c=2.14742(4) nm, β=90.7380(10)°, V=6.9250(3) nm3, Z=4, F(000)=4418, Dc=2.145 g*cm-3, μ=3.227 mm-1,(Δ/σ)=0.000, S=1.066.     

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.     

Hydrothermal Synthesis and Crystal Structure of [H4As8V14O42(H2O)]·6H2O

The title compound [H4As8V14O42(H2O)]·6H2O 1 has been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis. It crystallizes in trigonal, space group R3c with a = b = 36.447(6), c = 21.485(5) (A), V = 24717(8) (A)3, Z = 18, Mr = 2114.66, Dc = 2.557g/cm3, F(000) = 17928, μ = 7.149 mm-1, R = 0.0792 and wR = 0.1265. The [H4As8V14O42- (H2O)] cluster consists of fourteen VO5 square pyramids linked by four As2O5 handle-like units.     

Nine-coordinate rare earth metal complexes with aminopolycarboxylic acids: Mononuclear (NH4)3[TbIII(ttha)]·5H2O and binuclear (NH4)4[Tb 2 III (dtpa)2]·9H2O

The two title coordination compounds, (NH₄)₃[Tb^III(ttha)]·5H₂O (ttha = triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (NH₄)₄[Tb ₂ ^III (ttha)]·9H₂O (dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, TG-DTA and single crystal X-ray diffraction techniques. The (NH₄)₃[Tb^III(ttha)]·5H₂O compound is monoclinic, P2₁/c; a = 10.398(1) Å, b = 12.791(1) Å, c = 23.199(2) Å; β = 90.914(2)°; V = 3084.9(5) ų; Z = 4; D _calc = 1.704 g/cm³; μ(MoK _α ) = 2.376 mm^™; R = 0.023 and wR ² = 0.049 for 5429 observed reflections with I ≥ 2σ(I). The [Tb^III(ttha)]³⁻ complex anion in the crystal has a nine-coordinate mononuclear molecular structure with pseudo-monocapped square-antiprismatic configuration. The (NH₄)₄[Tb ₂ ^III (dtpa)₂]·9H₂O compound is triclinic, P-1; a = 9.739(1) Å, b = 10.010(1) Å, c = 12.968(2) Å; α= 85.890(2)°, β = 77.338(2)°, γ = 77.587(2)°; V = 1204.2(2) ų; Z = 1; D _calc = 1.832 g/cm³; μ(MoK _α ) = 3.015 mm^™; R = 0.024 and wR ² = 0.060 for 4750 observed reflections with I ≥ 2σ(I). The [Tb ₂ ^III (dtpa)₂]₄₋ complex anion has a binuclear structure in the crystal; the two Tb^III centers are equivalent and have a nine-coordinate environment with the same pseudo-tricapped trigonal-prismatic configuration. The thermal analysis revealed that the coordination cores of the (NH₄)₃[Tb^III(ttha)]·5H₂O and (NH₄)₄[Tb ₂ ^III (dtpa)₂]·9H₂O compounds are stable up to 221°C and 252°C, respectively. Original Russian Text Copyright ? 2008 by J. Wang, X. Zh. Liu, X. F. Wang, G. R. Gao, Zh. Q. Xing, X. D. Zhang, and R. Xu The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 81–89, January–February, 2008.     

α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis,characterization, and magnetism of Cu2(phen)4(GeW12O40) and [Ni2(bpy)4(H2O)2(GeW12O40)]⋅2H2O

Two new α-Keggin polyoxometalates, [Cu₂(phen)₄(GeW₁₂O₄₀)] (1) and [Ni₂(bpy)₄(H₂O)₂(GeW₁₂O₄₀)]·2H₂O (2) (phen?=?1,10-phenanthroline, bpy?=?2,2′-bipyridine), have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, single-crystal X-ray diffraction, and magnetic properties. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, and 1 is assembled into two-dimensional (2-D) layers parallel to (1?0?1) based on the adjacent phen π···π stacking interactions (3.788(8)?Å). Variable temperature magnetic measurements show ferromagnetic behavior from 300 to 2?K. Compound 2 crystallizes in the triclinic system, space group P-1, and 2 is assembled into 2-D layers parallel to (1?0?1) based on the adjacent bpy π···π stacking interactions (3.07?Å). Variable temperature magnetic measurements show a weak ferromagnetic behavior from 300 to 26?K followed by antiferromagnetic behavior below 26?K.     

The first transition metal iodato peroxido complex: the synthesis, vibrational spectra and crystal structure from powder diffraction data of K3[V2O2(O2)4(IO3)]·H2O

The first transition metal iodato peroxido complex, K₃[V₂O₂(O₂)₄(IO₃)]·H₂O (I), was prepared by crystallization from the KVO₃ — KIO₃ — H₂O₂ — H₂O — ethanol (HNO₃) solution. The dinuclear anion is immediately decomposed in aqueous solution; the ⁵¹V NMR spectrum exhibits signals corresponding to [VO(O₂)₂(H₂O)]^?, [V₂O₂(OH)(O₂)₄]^3? and H₂VO₄ ^? species only. The IR and Raman spectra contain all characteristic bands of the VO(O₂)₂ group and the coordinated IO₃ ^? ligand. Based on the positions of bands assigned to the vibrations of the VO(O₂)₂ groups a pentagonal pyramidal arrangement around the vanadium atoms can be supposed. The crystal structure was solved from X-ray synchrotron powder data by direct space method and refined by energy minimization in the solid state employing a hybrid PBE0 functional. This crystal and molecular structure, has confirmed the presence of hexacoordinated vanadium atoms and revealed asymmetric dinuclear structure of the [V₂O₂(O₂)₄(IO₃)]^3? ion. The coordination spheres of vanadium atoms are different — the IO₃ ^? anion is coordinated only to one vanadium center. A thermal analysis of the complex confirmed the presence of water molecules in the crystal structure and revealed a considerable stability of the dehydrated complex.      

Cu–Ni hetero-bimetallic compounds,Part 1: Preparation,structure and properties of [Cu0.05Ni0.95(bpy)2(ox)]·4H2O

New bimetallic compound [Cu_xNi_1?x(bpy)₂(ox)]·4H₂O (x = 0.05, ox = oxalato, bpy = 2,2′-bipyridine) was synthesized and chemically characterized. Its crystal structure is molecular. The octahedron around the metal central atom is deformed due to coordination by one bidentate oxalate anion and two bpy ligands. There are four uncoordinated water molecules in the asymmetric unit. The metal site is occupied by both Cu(II) and Ni(II) atoms in the 5:95 ratio. The complex molecules interact with water molecules through hydrogen bonds and, moreover, π–π interactions between aromatic rings lead to a 1D arrangement of molecules. The susceptibility data measured down to 2 K were analyzed using strong-coupling theory and the best agreement with the experimental data were found for g = 2.1, D/k = 5.6, E/k = 0.35, J/k = 0.2. The dehydration starts at 30 °C. As a final product of its thermal decomposition a solid solution of Cu_xNi_1?xO was detected by X-ray powder diffraction.     

Calixarenes as second-sphere ligands for transition metal ions. Synthesis and crystal structure of [(H2O)5 Ni(NC5H5)]2(Na)[calix[4]arene sulfonate] · 3.5 H2O and [(H2O)4Cu(NC5H5)2]-(H3O)3 [calix[4]arene sulfonate] · 10 H2O

The title compounds crystallize such that bilayers of calixarenes are separated by hydrophilic layers. In each case the transition metal has, in addition to a primary sphere of ligands, a second-sphere coordination by a calixarene. [(H₂O)₅Ni(NC₅H₅)]₂(Na)[calix[4]arene sulfonate]·3.5 H₂O,1, crystallizes in the triclinic space groupP \(\bar 1\) witha = 12.487(4),b = 14.281(2),c = 15.055(5) Å, α = 85.66(2), β = 80.07(2), γ = 80.48(2)°, andD _c = 1.64 g cm^?3 forZ = 2. Refinement based on 2441 observed reflections led to a finalR value of 0.066. There are two different environments for the nickel-containing cations: one is positioned within the hydrophilic layer with the pyridine ligand intercalated into the hydrophobic calixarene bilayer and the other is also positioned within the hydrophilic layer, but the pyridine ligand is inserted into the hydrophobic cavity of the calix[4]arene. [(H₂O)₄Cu(NC₅HS)₂](H₃O)₃[calix[4]arene sulfonate]·10 H₂O,2, crystallizes in the triclinic space groupP \(\bar 1\) witha = 15.438(4),b = 15.727(6),c = 12.121(9) Å, α = 112.74(4), β = 102.02(4), γ = 85.34(4)°, andD _c = 1.57 g cm^?3 forZ = 2. Refinement based on 3925 observed reflections led to a finalR value of 0.107. The structure is similar to that of 1 except that the one copper-containing cation spans the hydrophilic layer and is intercalated into the bilayer of calixarenes on one side and positioned into the calixarene cavity on the other.     

Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution

Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).