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.     

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.     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

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.     

Structure of the complex [trans-SnF4(H2O)2· (18-crown-6)· 2H2O]

The molecular and crystal structure of the title complex (I) obtained by addition of tin fluoride in a hydrofluoric acid solution to 18-crown-6 in methanol was investigated by X-ray structure analysis. The crystals are monoclinic, space group P2₁/n, a = 13.497(3), b = 7.806(2), c = 9.892(2) Å, β = 95.57(3)°, Z = 2 for C₁₂H₃₂F₄O₁₀Sn. In the polymer chain, the crown ether molecules alternate with the inorganic complexes [trans-SnF₄(H₂O)₂] and are linked to them by O-H...O type hydrogen bonds involving the intermediate water molecules. The weak C-H...F interactions bind the chains into the layers which are parallel to the xz plane.     

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.     

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.     

[Ni(en)2]6H2[(VO)12O6B18O42]·15H2O的水热合成和晶体结构

在水热的条件下合成了1个多聚钒硼酸盐[Ni(en)2]6H2[(VO)12O6B18O42]15H2O,化学式为C24H128B18N24Ni6O75V12(Mr=3111.62),用单晶X射线衍射方法测定了它的结构,该晶体属三方晶系,R-3空间群,晶胞参数为a=13.942(2)?=96.476(2),V=2653.9(5)?,Z=1,Dc=1.947g/cm3,=21.55cm-1,F(000)=1574,2108个可观察衍射点(I>2(I)),最终结构精修到偏离因子R=0.0594,wR=0.1398,S=1.009。在该化合物的结构中,18员环的B18O42通过18个B(3-O)V键被2个V6O15簇夹在中间,6个[Ni(en)2]基团分别通过2个Ni(3-O)B与B18O42环相连。     

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.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

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.     

CLUSTER CONVERSION OF [MoW2O2(O2CEt)9]− TO [MoW2O4(O2 CEt)8]4- BY CHROMIUM HEXACARBONYL CRYSTAL STRUCTURES OF Na[MoW2O2(O2CMe)9] · H2O, [MoW2O2(O2CEt)6(H2O)3] ZnCl4 · 2H2O AND Na2Cr2[MoW2O4(O2CEt)8]2

Abstract

Reactions of Mo(CO)₆ with Na₂WO₄ · 2H₂O in refluxing carboxylic anhydride produce the triangular bioxo-capped mixed-metal carboxylate clusters Na[MoW₂O₂(O₂CR)₉] (R = Me, 1; Et, 2), the propionate being hydrolyzed in 2M HCl containing ZnCl₂ to form [MoW₂O₂(O₂CEt)⁶(H₂O)₃]ZnCl₄·2H₂O (3). Cluster 2 is converted to the incomplete cuboidal tetraanion [MoW₂O₄(O₂CEt)₈]^4- upon reacting with Cr(CO)₆ in propionic anhydride at 120°, the latter species being trapped by Cr^3± and Na^± ions in the reaction mixture to afford the octanuclear heterometallic chain-like cluster Na₂Cr₂ [MoW₂O₄(O₂CEt)₈]₂ (4). Clusters 1, 3 and 4 have been characterized by X-ray crystallography with the following crystal data, for 1: monoclinic, space group P2₁/c, a = 16.666(8), b = 11.096(3), c = 16.541(7) Å, β = 94.60(4)°, V = 3048.9 ų, Z = 4, R, Rw = 0.070, 0.079; for 3, monoclinic, space group Cm, a = 10.259(3), b = 15.756(3), c = 10.870(3) Å, β = 96.18(3)°, V = 1746.8 ų, Z = 2, R, Rw = 0.028, 0.034; for 4, triclinic, space group P-1, a = 13.013(5), b = 14.005(4), c = 12.357(4) Å, α = 109.71(2), β = 117.77(3), γ = 90.41(3)°, V = 1838.9 ų, Z = 1, R, Rw = 0.037, 0.042.     

化合物[H3DETA]3[H2DETA]2[Pr(SiW11O39)2]·2H2O的水热合成及晶体结构

通过水热合成制得了硅钨杂多酸镨化合物[H3DETA]3[H2DETA]2[Pr(S iW11O39)2].2H2O[DETA:二乙烯三胺].晶体结构解析表明:该化合物属于三斜晶系,P1-空间群,a=1.200 0(2)nm,b=2.026 1(4)nm,c=2.239 2(5)nm,α=111.60(3)°,β=92.92(3)°,γ=103.56(3)°;V=4.863 8(17)nm3,Z=2,ρ=4.152 g/cm3,μ=26.519 mm-1,F(000)=5 374.化合物中Pr3+键合两个[S iW11O39]8-构成一个[Pr(S iW11O39)2]13-多阴离子,Pr3+与两个[S iW11O39]8-阴离子的八个氧原子配位构成一个畸变的四方反棱柱.此外,多阴离子[Pr(S iW11O39)2]13-和有机分子还通过氢键形成一个大的空腔.     

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.     

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex [La(betaine)2(H2O)6Fe(CN)6]·2H2O

The title complex [La(betaine)2(H2O)6Fe(CN)6](2H2O (betaine = (CH3)3NCH2CO2) has been synthesized and characterized by X-ray single-crystal structure analysis. The crystal crystallizes in monoclinic, space group P21/n with a = 15.793(5), b = 8.927(3), c = 22.257(7) (A), β = 110.147(5)°, C16H38FeLaN8O12, Mr = 729.31, Z = 4, V = 2946.0(15) (A)3, Dc = 1.640 g/m3, μ(MoKα) = 1.988 mm-1, F(000) =1476, R = 0.0388 and wR = 0.0827 for 4237 observed reflections (I > 2σ(I)). The La3+ ion is nine-coordinated by one cyano nitrogen atom and eight oxygen atoms of two betaine and six water molecules. Each complex molecule is connected to form a 3D network structure by some O-H…O and O-H…N hydrogen bonds.     

A polyoxoniobate based on dimeric hexanionbate: [Cu(en)2]4{[Nb6O19H2]K(H2O)5}2 · (H2en) · 17H2O

A polyoxoniobate, [Cu(en)₂]₄{[Nb₆O₁₉H₂]K(H₂O)₅}₂ ? (H₂en) ? 17H₂O (en = ethylenediamine) (1), has been synthesized and characterized by elemental analysis, IR, XPS, TGA, and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a = 12.3533(16) Å, b = 12.7188(16) Å, c = 29.626(4) Å, α = 93.235(2)°, β = 96.094(1)°, γ = 106.098(2)°, V = 4429.0(10) ų, Z = 2. The polyoxoanion is composed of a Lindqvist-type [Nb₆O₁₉H₂]^6? dimer bi-bridged via two K⁺. K⁺ is 10-coordinate with 10 oxygens, three from one [Nb₆O₁₉H₂]^6?, one from a terminal oxygen of another [Nb₆O₁₉H₂]^6? moiety, and the other six from water molecule. Adjacent dimeric polyoxoanions are linked to form an infinite 1-D chain via O–H ··· O hydrogen-bonding interactions which exist between the two water trimers and the dimeric polyoxoanions.     

On the thermal decomposition of [Fe2NiO(CH3COO)6(H2O)3]·2H2O

The heteronuclear-oxoacetate with the composition [Fe₂NiO(CH₂COO)₆(H₂O)₃]·2H₂O decomposed on heating, forming nickel ferrite NiFe₂O₄ and (depending on the decomposition conditions) in part other solid phases. H₂O, CH₃COOH, acetone and CO₂ were also formed in the decomposition. A reaction scheme is given for the decomposition. The products were porous powders with grain diameters between 3 and 10m. On increase of the temperature of decomposition from 300 to 800 C, the BET surface area and the surface area of the pores decreased, but only a small alteration in grain size was observed. As a result of thermal treatment in the temperature region abone 800C, larger aggregates of grains were formed in sintering processes.

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Zusammenfassung Heteronukleare-Oxoazetate der Zusammensetzung [Fe₂NiO(CH₃COO)₆(H₂O)₃]·2H₂O werden durch Erhitzen zersetzt, wobei Nickelferrite NiFe₂O₄ und — in AbhÄngigkeit von den Bedingungen der Zersetzung — mit einem Teil anderer fester Phasen gebildet wird. In der Zersetzungsreaktion werden auch H₂O, CH₃COOH, Azeton und CO₂ gebildet. Es wird ein Reaktionsschema für die Zersetzung angegeben. Die Produkte sind poröse Pulver mit einem Korndurchmesser zwischen 3 und 10 m. Wird die Zersetzungstemperatur von 300 auf 800C erhöht, nimmt die BET-OberflÄche und die PorenoberflÄche ab, wobei sich die Korngrö\e aber nur wenig verÄndert. Im Ergebnis der WÄrmebehandlung im Temperaturbereich oberhalb 800C werden durch Sinterprozesse grö\ere Partikelaggregate gebildet.

     

K3[GdⅢ(nta)2(H2O)]·6H2O和(NH4)·[GdⅢ(Cydta)(H2O)2]·5H2O的合成及晶体结构

GdⅢ的配合物常被用作MRI造影剂[1,2]. GdⅢ的离子半径和电子结构分别为0.107 8 nm和高自旋f 7, 理论预测应与氨基多羧酸类配体形成稳定的九配位配合物[3～5]. 为证实理论预测并在此基础上寻找合适的可用于定向修饰的配体以及为提高GdⅢ配合物的脂溶性使其具有更好的细胞渗透性, 选择四齿配体nta和含有脂环烃的六齿配体Cydta分别合成了GdⅢ的配合物, 并测定了它们的分子结构. 结果显示, GdⅢ与nta形成九配位配合物, GdⅢ与Cydta形成八配位配合物.     

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.     

Hydrothermal Synthesis and Crystal Structure of One Rare Earth Substituted Keggin-Type Germanotungstate [Cu(en)2]2[Cu(en)2(H2O)]2H3{[Cu(en)2]2[Na2(H2O)1.75][K(H2O)3][Dy2(H2O)2 (GeW11O39)3]} · 6H2O

A novel germanotungstate derivative based on the dysprosium cation and monovacant Keggin anion, [Cu(en)₂]₂[Cu(en)₂(H₂O)]₂H₃{[Cu(en)₂]₂[Na₂(H₂O)_1.75][K(H₂O)₃][Dy₂(H₂O)₂(GeW₁₁O₃₉)₃]} · 6H₂O(en = ethylenediamine) 1, has been synthesized by hydrothermal method and characterized by elemental analysis, IR-UV spectroscopy, thermal analysis and single-crystal X-ray diffraction. In the compound, one kind of clusters with the Dy³⁺/[GeW₁₁O₃₉]^8? ratio of 2:3 was observed. Especially, the 2:3 type displays the novel cluster based on the rare earth and monolacunary Keggin polyoxometalate.