Orthotelluric Acid as Substitute for Crystal‐Water: Syntheses and Crystal Structure of the Co‐crystallate [Te(OH)6 · 2 Adenine · 4 H2O] and the Disodium Ditellurate(VI) Aggregate {[Te2O2(OH)6(ONa)2]2[NaOH · 12.5 H2O]}

Supramolecular aspects on Te(OH)₆ as substitute for crystal‐water in adenine hydrate complexes and the first disodium ditellurate(VI) are reported. The co‐crystallate [Te(OH)₆ · 2 adenine · 4 H₂O] ( 1 ) has been prepared in 41% yield from the 1 : 1 mixing of Te(OH)₆ with the nitrogenous base adenine. The adduct of infinite stacks of adenine molecules, Te(OH)₆ and water not only proves that Te(OH)₆ mimicks the role of water in the related hydrate adenine · 3 H₂O but also shows that the inclusion of Te(OH)₆ raises the number of HO–H and N–HO contacts and therefore increases the distance between the adenine rings to 3.31 Å in 1 in comparison to that in adenine trihydrate (3.22 Å). Additionally, the disodium ditellurate(VI) aggregate {[Te₂(O)₂(OH)₆(ONa)₂]₂ [NaOH · 12.5 H₂O]} ( 2 ) resulted from the reaction of 1 with 2 molar equivalents of aqueous NaOH. Dinuclear 2 represents the first X‐ray diffraction characterized example of a sodium tellurate(VI) constructed from [Te₂O₄(OH)₆]^2– dianions.     

The First Sodium Uranyl Chromate,Na4[(UO2)(CrO4)3]: Synthesis and Crystal Structure Determination

The first sodium uranyl chromate, Na₄[(UO₂)(CrO₄)₃], has been obtained by high‐temperature solid‐state reaction. The structure (triclinic, P1¯, Z = 2, a = 7.1548(3), b = 8.4420(3), c = 11.5102(5)Å, α = 80.203(1)°, β = 79.310(1)°, γ = 70.415(1)° V = 639.24(4)ų ) has been solved by direct methods and refined on the basis of F² for all unique reflections to R1 = 0.024 [calculated on the basis of 4374 unique observed reflections (‖F_o‖ 4σF)]. The structure is based on chains of composition [(UO₂)(CrO₄)₃] that are parallel to [1¯01]. The chains contain UrO₅ pentagonal bipyramids (Ur = Uranyl) that share all equatorial corners with CrO₄ tetrahedra. Cr(1)O₄ and Cr(3)O₄ tetrahedra bridge between two adjacent UrO₅ bipyramids, whereas Cr(2)O₄ tetrahedra share one corner with one UrO₅ bipyramid each. The [(UO₂)(CrO₄)₃] chains are planar and oriented parallel to (313). The Na⁺ cations provide linkage of the chains in the structure.     

Diiodobis(diphenyltelluride)mercury(II), [(Ph2Te)2HgI2]

Diiodobis(diphenyltelluride)mercury(II), [(Ph₂Te)₂HgI₂], is formed during the reaction of [(PhTe)₂Hg] with HgI₂ in refluxing THF. The same product can be obtained from a pressure reaction between PhTeI₃ and elemental mercury. The mercury atom is co‐ordinated in a distorted tetrahedral environment with I‐Hg‐I angles of 117?. Long range I···Te contacts of about 3.8 Å link the [(Ph₂Te)₂HgI₂] units to infinite chains along the b axis of the unit cell.     

Bis(2,4,6‐trimethylphenyl)tellurium(IV) Dicyanide: the First Crystal Structure for a Tellurium Cyanide of the Type R2Te(CN)2

The reaction of Mes₂TeF₂ (Mes = 2,4,6‐trimethylphenyl) with trimethylsilyl cyanide yields the corresponding tellurium(IV) dicyanide Mes₂Te(CN)₂. Isolation of suitable crystals allows the determination of the first crystal structure of a compound of the type R₂Te(CN)₂.     

New Mixed Ligand Organotellurium(IV) Compounds Containing Dithiocarbamates and the More Flexible Imidotetraphenyldithiodiphosphinates. The Crystal Structures of C8H8Te(S2CNEt2)[(SPPh2)2N] · H2O,C8H8Te(S2CNC5H10)[(SPPh2)2N], and C8H8Te(S2CNC4H8S)[(SPPh2)2N]

The synthesis of the following mixed ligand organotellurium(IV) compounds C₈H₈Te(S₂CNEt₂)[(SPPh₂)₂N] · H₂O ( 1 ), C₈H₈Te(S₂CNC₅H₁₀)[(SPPh₂)₂N] ( 2 ), C₈H₈Te(S₂CNC₄H₈O)[(SPPh₂)₂N] ( 3 ) and C₈H₈Te(S₂CNC₄H₈S)[(SPPh₂)₂N] ( 4 ) was achieved. They were characterized by IR, ¹H, ¹³C, ³¹P and ¹²⁵Te NMR, mass spectroscopy, and elemental analyses. The X‐ray crystal structures of 1 , 2 and 4 were determined. The both types of ligands display an asymmetrical chelating coordination mode on interaction with the tellurium atom. When these aniso‐bonded donor atoms are included in the coordination sphere, the tellurium atom exhibit an effective co‐ordination number of seven. The arrangement may be described as 1 : 2 : 2 : 2 coordination with a presumably stereoactive lone‐pair of electrons.     

[Te8]2[Ta4O4Cl16]: A Two‐dimensional Tellurium Polycation obtained via Ionic Liquid‐Based Synthesis

By reaction of elemental tellurium, tellurium(IV) chloride, tantalum(V) chloride and tantalum(V) oxychloride in the ionic liquid [BMIM]Cl ([BMIM]Cl:1‐Butyl‐3‐methylimidazolium chloride),[Te₈]₂[Ta₄O₄Cl₁₆] is obtained in the form of lucent black crystals. The title compound consists of infinite [Te–Te–(Te₆)]_n²⁺ chains (Te–Te: 264.9(1)–284.3(1) pm) and isolated [Ta₄O₄Cl₁₆]^4– anions. The [Te–Te–(Te₆)]_n²⁺ chains are interconnected to form a two‐dimensional tellurium network (Te–Te: 335.9 pm). Due to this interaction the [Te–Te–(Te₆)]_n²⁺ chains in [Te₈]₂[Ta₄O₄Cl₁₆] show an arrangement that differs significantly from known polycationic [Te₈]_n²⁺ chains. The two‐dimensional tellurium network is finally separated by tetrameric, corner‐sharing oxidochloridotantalate anions [(TaO_2/2Cl_4/1)₄]^4– that are firstly observed. The composition of [Te₈]₂[Ta₄O₄Cl₁₆] is confirmed by EDX analysis; its optical band gap is estimated to 1.1–1.2 eV via UV/Vis spectroscopy.     

Synthesis and Crystal Structure of [(n5-C5Me5)2Fe2S4](PF6)2

Abstract

The title compound was synthesized by electrochemical oxidation of (η⁵-C₅Me₅)₂Fe₂S₄ and its X-ray crystal structure was determined. A μ₂-S₂ ligand is converted to μ₂-η²-s₂ ligand by the oxidation.     

Synthesis and Crystal Structure of Cs(VO2)3(TeO3)2, a New Layered Cesium Vanadium(V) Tellurite

Synthetic Cs(VO₂)₃(TeO₃)₂ is built up from infinite sheets of distorted octahedral V^VO₆ groups, sharing vertices. These octahedral layers are “capped” by Te atoms (as parts of pyramidal [Te^IVO₃]^2– groups) on both faces of each V/O sheet, with inter‐layer, 12‐coordinate, Cs⁺ cations providing charge compensation. Cs(VO₂)₃(TeO₃)₂ is isostructural with M(VO₂)₃(SeO₃)₂ (M = NH₄, K). Crystal data: Cs(VO₂)₃(TeO₃)₂, M_r = 732.93, hexagonal, space group P6₃ (No. 173), a = 7.2351(9) Å, c = 11.584(2) Å, V = 525.1(2) ų, Z = 2, R(F) = 0.030, wR(F ²) = 0.063.     

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…     

First Mixed Alkaline Uranyl Molybdates: Synthesis and Crystal Structures of CsNa3[(UO2)4O4(Mo2O8)] and Cs2Na8[(UO2)8O8(Mo5O20)]

Two new mixed alkaline uranyl molybdates CsNa₃[(UO₂)₄O₄Mo₂O₈] ( 1 ) and Cs₂Na₈[(UO₂)₈O₈(Mo₅O₂₀)] ( 2 ) have been obtained by high‐temperature solid state reactions. Their crystal structures have been solved by direct methods: Compound 1 : triclinic, P , a = 6.46(1), b = 6.90(1), c = 11.381(2) Å, α = 84.3(1), β = 91.91(1), γ = 80.23(1)°, V = 488.6(2) ų, R₁ = 0.06 for 2865 unique reflections with |F_o| ≥ 4σ_F; Compound 2 : orthorhombic, Ibam, a = 6.8460(2), b = 23.3855(7), c = 12.3373(3) Å, V = 1975.2(1) ų, R₁ = 0.049 for 2120 unique reflections with |F_o| ≥ 4σ_F. The structure of 1 contains complex sheets of UrO₅ pentagonal bipyramids and molybdenum polyhedra. The sheets have [(UO₂)₂O₂(MoO₅)] composition. Natrium and cesium atoms are located in the interlayer space. Cesium atoms are situated between the molybdenum clusters, whereas natrium atoms are segregated between the uranyl complexes. The large Cs⁺ ions are localized between the Mo₂O₉ groups and force the molybdenum polyhedra to rotate relative to the [(UO₂)₂O₂(MoO₅)] sheets. Such rotation is impossible for U⁶⁺ polyhedra due to their rigid edge‐sharing complexes. The distance between the U⁶⁺ polyhedra vertices of neighboring layers is 3.8 Å, that allows the Na⁺ ion to be positioned between the uranyl groups. The crystal structure of 2 is based upon a framework consisting of [(UO₂)₂O₂(MoO₅)] sheets parallel to (010). The sheets are linked into a 3‐D framework by sharing vertices with the Mo(2)O₄ tetrahedra, located between the sheets. Each MoO₄ tetrahedron shares two of its corners with two MoO₆ octahedra in the sheet above, and the other two with MoO₆ octahedra of the sheet below. Thus four MoO₆ octahedra and one MoO₄ tetrahedron form chains of composition Mo₅O₁₈. The resulting framework has a system of channels occupied by the Cs⁺ and Na⁺ ions.     

[(η5-C5Me5)WS3Cu3Br2(PPyPh2)2]四核簇合物的合成和晶体结构

以2[(η5-C5Me5)WS3(CuBr)3]2和diphenyl-2-pyridylphosphine (PPyPh2)在乙腈中反应得到标题化合物[(η5-C5Me5)WS3Cu3Br2(PPyPh2)2], 对该产物进行了元素分析、 IR、 UV-Vis和1H NMR 谱表征, 并测定了晶体结构. 该化合物晶体属三斜晶系, P1空间群, 晶胞参数: a=1.545 9(7) nm, b=1.62 0(1) nm, c=1.018 0(2) nm, α=94.18(3)°, β=97.38(3)°, γ=111.81(4)°, V=2.327(2) nm3, Z=2, Dc=1.84 g*cm-3, F(000)=1 260, μ=57.77 cm-1, 最终偏离因子R=0.029. 此簇合物结构可视为由一个[(η5-C5Me5)WS3]单元和3个Cu组成的开口立方烷, 其中2个Cu是畸变四面体配位, 第3个Cu是近似三角平面配位. W-Cu(1), W-Cu(2) 和W-Cu(3)距离分别为0.270 41(9), 0.273 27(8), 0.267 85(9) nm.     

新型杂多配合物K3H2[GeW8Mo3VO40]·4H2O的合成与晶体结构

用分步酸化、分步加料法合成出新型杂多配合物K3H2[GeW8Mo3VO40]·4H2O,并用X射线单晶衍射法测定其晶体结构,该晶体属单斜晶系,C2空间群,a＝1.894 4(4)nm,b＝3.292 0(7)nm,c＝1.249 4(2)nm,β＝90.25(3)°,V＝7.792(4)nm3,Z＝6.最终偏差因子R＝0.063.RW＝0.067.     

Selenious Acid as a Ligand: Molecular and Crystal Structure of [Co(H2O)2Cl2(H2SeO3)2]

[Co(H₂O)₂Cl₂(H₂SeO₃)₂] (monoclinic, P2₁/c, Z = 2, a = 519.82(5), b = 1462.6(1), c = 643.09(7) pm, β = 92.51(1)°, R_all = 0.0583) was obtained from CoCl₂ and H₂SeO₃ as purple plate–shaped single crystals. In the compound, the Co²⁺ ions are octahedrally coordinated by two Cl^? ions, two H₂O molecules, and two monodentate H₂SeO₃ molecules, leading to neutral complexes [Co(H₂O)₂Cl₂(H₂SeO₃)₂]. They are connected by hydrogen bonds involving both chlorine and oxygen atoms as acceptor atoms.     

Synthesis and Crystal Structure of 2-[（2-Chloropyridin-4-yl）oxy]-3,3-diphenyl-3-methoxypropionic Acid

The title compound was synthesized and its crystal structure was determined by single-crystal X-ray diffraction.The crystal is of orthorhombic system(C21H18ClNO4,Mr = 383.81),space group Pca21 with a = 13.913(3),b = 10.273(2),c = 26.488(5),V = 3786.1(13) 3,Z = 8,Dc = 1.347 g/cm3,F(000) = 1600,μ = 0.228 mm-1,the final R = 0.0550 and wR = 0.1278 for 5065 observed reflections(I > 2σ(I)).The title compound in a racemic form was found to exist as a mixture of two enantiomers in an equal ratio in the unit cell.The intermolecular hydrogen bonds link the molecules in a head-to-end manner to generate an infinite chain.     

Synthesis and Crystal Structure of Manganese‐tris(1,2‐ethanediamine)tetratelluride [Mn(en)3]Te4 Exhibiting Intermolecular Interactions between the Tetratelluride Anions

Air‐sensitive black crystals of the new compound [Mn(en)₃]Te₄ were synthesized by reacting MnCl₂ · 4 H₂O, K₂Te₃ and elemental Te in 1,2‐ethanediamine (en) under solvothermal conditions at 433 K. The compound crystallizes in the monoclinic space group P2₁/n with lattice parameters a = 839.51(7) pm, b = 1551.3(1) pm, c = 1432.6(1) pm, and β = 90.28(2)°. Isolated [Mn(en)₃]²⁺ cations and Te₄^2– anions are arranged in an alternating fashion parallel to the crystallographic b‐axis. One terminal Te atom of the Te₄^2– anions exhibits a short intermolecular contact to a neighboured anion thus forming Te₈^4– anions. A slightly longer interionic Te…Te separation is observed between two of the inner Te atoms of neighboured Te₈^4– anions. Taking these longer separations into account infinite Te‐chains are formed running parallel to [001]. The intermolecular Te…Te interactions affect the Te–Te bond lengths within the Te₄^2– anion leading to a lengthening of the average Te–Te distance. Short N–H…Te distances indicate hydrogen bonding between the cations and anions. DTA‐TG measurements show that at 441 K the material decomposes in one step. The resulting crystalline material consists of MnTe₂ and Te.     

Synthesis, Crystal Structure and Electrochemistry of Two Complexes(YLn)3+[PW12O40]3-(L=Me2SO, Me2NCHO)

The reaction of a-H3[PWi2O40]with Y(NO3)3 in the presence of DMF or DMSO leads to two complexes complex 1 consists of discrete [YLn]3 cations and α-Keggin heteropolyanions [PW12O40]3-, whereas, in complex 2,donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.     

[Me3SnVO3] und [(Me2Sn)4V2O9], zwei Organozinnvanadate mit neuen 3D‐Netzwerkstrukturen

[Me₃SnVO₃] and [(Me₂Sn)₄V₂O₉], two Organotin Vanadates with Novel 3D Network Structures Two new organotin vanadates [Me₃SnVO₃] ( 1 ) and [(Me₂Sn)₄V₂O₉] ( 2 ) have been prepared by the reaction of NH₄VO₃ with Me₃SnBr and Me₂SnBr₂ resp. in agar gel. The structures of 1 and 2 have been determined by x‐ray crystallography at 220 K. 1 crystallizes monoclinic in the space group P2₁/c with a = 1335.6(2), b = 1144.4(2), c = 1118.8(2) pm, β = 113.54(2)°. 2 crystallizes orthorhombic in the space group Pnnm with a = 1257.6(2), b = 1345.4(2), c = 1323.1(1) pm. 1 consists of infinite metavanadate chains which are linked by Me₃Sn⁺ cations. 2 exhibits a complex 3D‐ network structure with VO₄ tetrahedra, Me₂SnO₃ trigonal bipyramides and Me₂SnO₄ octahedra linked by common oxygen atoms.     

［（n－C_4H_9）_4N］_2［（OC_（14）H_8O）_2Mo_4O_（10）（OCH_3）_2］的合成和晶体结构

为探讨钼多酸根阴离子在有机化学反应中的催化机理，用菲醌作底物合成了［（ｎ－Ｃ_４Ｈ_９）_４Ｎ］_２［（ＯＣ_（１４）Ｈ_８Ｏ）_２Ｍｏ_４Ｏ（１０）（ＯＣＨ_３）_２］配合物。Ｘ射线单晶结构分析表明，该晶体属单斜晶系，空间群Ｐ２_１／ｃ，ａ＝１．３１４９（５）ｎｍ，ｂ＝１．８６６６（８）ｎｍ，ｃ＝１．８９０３（３）ｎｍ，β＝１０４．０６（３）°，Ｚ＝２．收集到独立衍射点３５０５个，其中１３８２个为可观测点，最终一致性因子Ｒ＝０．０７８．结构分析结果表明，菲醌与钼多酸根在不同的实验条件下，能形成配比、氧化态以及结构不同的配合物。     

有机-无机杂化材料[Na2(H2O)4]2[γ-Mo8O26·(Gly-Gly)2]·4H2O的合成及晶体结构

多金属氧酸盐因其独特的结构而具有较高的抗肿瘤及抗病毒活性,蛋白质和肽是氨基酸的聚合体,氨基酸侧链官能团能与多金属氧酸盐形成新型配合物.了解氨基酸和肽与多金属氧酸盐的相互作用对于深入研究多金属氧酸盐抗肿瘤及抗病毒机理很有意义.我们曾报道了赖氨酸、丙氨酸及甘氨酸二肽与钼磷酸所形成化合物的晶体结构.