Internal Mobility, Structure, Phase Transitions, and Ionic Conductivity in Thallium Fluoroantimonates(III) TlSb4F13 and TlSb3F10

Internal mobility in TlSb₄F₁₃ (I) and TlSb₃F₁₀ (II) was studied by ¹⁹F NMR spectroscopy in the temperature range 210-450 K. Types of ionic motion in the fluoride subsystem were determined. Phase transitions resulting in modifications with high ionic (superionic) conductivity above 420 K were established for both compounds (385-425 K). Using impedance spectroscopy, we studied the electrophysical properties of I and II in the temperature range 290-425 K ( 1.1×10^-3 and 1.0× 10^-3 S/cm for I and II, respectively; T=425 K).     

Crystal Structure of Ammonium Undecafluorotriantimonate(III) (NH4)2Sb3F11

The crystal structure of a novel antimony(III) fluoride complex, ammonium undecafluorotriantimonate(III) (NH₄)₂Sb₃F₁₁, was determined. The crystals are triclinic: a = 7.780(2) Å, b = 8.370(2) Å, c = 10.620(1) Å, = 71.06(1)°, = 89.03(1)°, = 63.58(1)°, V = 579.1(2) ų, Z = 2, (calcd) = 3.500 g/cm³, (exp) = 3.51 g/cm³, F(000) = 548.0, space group P . The structure consists of anionic [Sb₃F₁₁]^2– chains and ammonium cations combined into a framework by the N–H···F hydrogen bonds.     

Thallium(III)

Ohne Zusammenfassung     

Synthesis,Crystal Structure and Band Structure of Tb3Co4Sn（13）

A new intermetallic compound,Tb3Co4Sn13,has been synthesized by solid-state reaction of the corresponding pure elements in a welded tantalum tube at high temperature.Its crystal structure was established by single-crystal X-ray diffraction.Tb3Co4Sn13 crystallizes in cubic,space group Pm3n(No.223) with a = 9.5072(2) ,V = 859.33(3) 3,Z = 2,Mr = 2255.45,Dc = 8.717 g/cm3,μ = 34.369 mm-1,F(000) = 1906,and the final R = 0.0140 and wR = 0.0312 for 199 observed reflections with I > 2σ(I).The structure of Tb3Co4Sn13 belongs to the Yb3Rh4Sn13 type.It is isostructural with RE3Co4Sn13(RE = La,Ce),featuring a 3D [Co4Sn12] framework based on [CoSn6] trigonal prisms.The [CoSn6] trigonal prisms are interconnected via corner-sharing and Sn-Sn bonds to form a 3D [Co4Sn12] framework.The other Sn and Tb atoms are located in the spacers of the 3D framework.Band structure calculations indicate that Tb3Co4Sn13 is metallic.     

The Crystal Structure of Tetra-n-Butylammonium Tetraiodoindate(III)

The crystal structure of tetra-n-butylammonium tetraiodoindate(III) Bu₄N[InI₄] has been determined by x-ray diffraction. The crystal is monoclinic, the space group P2₁/n, Z = 4 and the cell dimensions are: a = 11.699(2), b = 20.994(4), c = 11.745(2) ų. Final R1 = 0.0338 for 1673 observed reflections. The structure consists of distorted tetrahedral InI₄ anions and Bu₄N₊ cations. In the tetrahedral anion there are four In - I distances: 2.695(2), 2.699(2), 2.704(1) and 2.709(1) Å. Comparison with published data on other tetrahaloindates has shown that the average In - X distance increases with decreasing size of the cation, and that distortion of the tetrahedron in the Bu₄N[InX₄] salts is accompanied by decreasing symmetry of the space group from Pnna to P2₁/n.     

Synthesis and Crystal Structure of a New Lanthanum(III) 4-Cyanobenzoate Complex

A new dinuclear La(III) complex [La2(4-cba)4[H(4-cba)2]2(phen)2(H2O)4] (4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline) 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single- crystal X-ray diffraction. Crystallographic data: C88H58La2N12O20, Mr = 1881.28, triclinic P1, a = 7.518(3), b = 17.033(6), c = 17.551(6), α = 115.333(4), β = 92.9910(10), γ = 99.366(5)°, V = 1985.3(12)3, Z = 1, Dc = 1.574 g/cm3, F(000) = 944 μ = 1.145 mm–1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with I > 2σ(I). In 1, two nine-coordinated La(III) ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La(III) ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.     

Crystal Structure and Vibrational Spectrum of Thallium(I) Europium(II) Tetrathiophosphate(V), TIEu[PS4]

TlEu[PS₄] was synthesized from the elements in a sealed quartz ampoule at 1 150 K. The compound forms transparent orange needles, stable in air and moisture. It crystallizes in the orthorhombic system, space group Pnma (No. 62), with cell dimensions a = 12.157(2), b = 6.581(1), c = 8.802(2) Å, Z = 4. The crystal structure consists of discrete [PS₄]^3? anions interconnected by Tl⁺ and Eu²⁺. The tetrahedral [PS₄]^3? groups are slightly distorted with P? S bond lengths in the range 2.028 to 2.043 Å. These tetrahedral anions are arranged in such a way that the sulfur atoms form columns of distorted trigonal S₆ prisms along [0 0 1]. The columns are condensed via common edges to puckered layers parallel to (1 0 0). The interlayer region consists of empty distorted half-cubes and tetrahedral holes, half of them filled by P atoms. The trigonal prisms in the columns are centered alternately by Tl⁺ and Eu²⁺. In this way, the structure can be regarded as an ordered superstructure of the InNi₂ type, where half of the tetrahedral holes are filled by phosphorus atoms: InInNi₄□ ? TlEuS₄P□. TlEu[PS₄] is a centrosymmetric variant of the TlSn[PS₄] structure type (space group Pna2₁). The vibrational spectrum is in accordance with the X-ray crystal structure, the Raman and infrared vibrations are assigned on the basis of [PS₄]^3? units with C_2v symmetry.     

Crystal Structure and Catalytic Properties of Tetrakis（4-hydroxyphenyl）Porphyrinato Manganese （Ⅲ） Chloride （MnTHPPCI）

The crystal structure of meso-tetrakis （4-hydroxyphenyl） porphyrinato manganese chloride （MnTHPPC1） and its supramolecular architecture based on the hydrogen bonds of one counter C1 anion with four hydrogen atoms of four-OH groups from different MnTHPPC1 molecules cooperated by self-assembly of the porphyrin units were first repor-ted. This compound crystallized in the tetragonal space group 14/m with a = 1.39928（7） nm, b = 1.39928（7） nm, c =0.94498（10） nm, V= 1.8503（2） nm^3, and Z =2. As a catalyst, MnTHPPC1 also showed a high catalytic acti-vity in the conversion from 1-naphthylamine （1-NA） to his （4-oxo-benzo-2-cyclohexen-l-yl） amine （BOBCHA） v/a oxidative coupling under mild conditions.     

Crystal Structure of Iridium(III) trans-Trifluoroacetylacetonate

Single crystal X-ray diffraction analysis is used to determine the structure of iridium(III) trans- trifluoroacetylacetonate at 150 K. The crystallographic data for trans- C₁₅H₁₂F₉O₆Ir are as follows: a =13.4334(5) ?, b = 14.9136(6) ?, c = 19.4229(8) ?, space group Pcab, V = 3891.2(3) ?³, Z=8, d_x = 2.224 g/cm³, R = 0.0236. The structure is molecular. The metal atom coordinates six oxygen atoms of three β-diketonate ligands of β-diketone. The Ir-O distances are within the range of 2.00 ? to 2.02 ?; the average value is 2.011(6) ?; the average value of the chelate angle∠O-Ir-O is 95.2(5)°. In the crystal, the molecules are bound only by van der Waals interactions; six shortest Ir…Ir distances in the structure are within the range of 7.469-9.712 ?.     

The Crystal Structures of Thallium(I) Fluoride

The effects of temperature and pressure on the crystal structures of thallium(I) fluoride have been investigated using powder neutron diffraction, with the aim of resolving the uncertainties present in the literature. Under ambient conditions, TlF adopts an orthorhombic structure in space group Pbcm with Z=4 and cell parameters a=6.09556(8) Å, b=5.48860(7) Å, and c=5.18300(7) Å. This structure can be derived from an idealized rocksalt-type arrangement, though with extensive distortions of the anion sublattice due to the presence of the 6s² inert pair of the Tl⁺ Above 355 K TlF becomes tetragonal with Z=2, a=3.78283(2) Å, c=6.12312(5) Å, and space group P4/nmm. The behavior of the compound is also studied under hydrostatic pressure but, contrary to previous reports, no structural transition was observed and TlF remains orthorhombic up to at least 3.5 GPa. The compressibility is greatest along the a and b axes. The relationship between the ambient- and high-temperature structures of TlF is described and the influence of the inert pair discussed in relation to the massicot structured polymorph of PbO.     

Nitro,Nitrito and Nitrato Derivatives of Dicyclopentadienyl Thallium(III) Chloride and Bis Indenyl Thallium(III) Chloride

Six new complexes of thallium(III) of the formula (π-D)₂Tl(L) (where D= cyclopentadienyl or indenyl group and L=nitro, nitrito or nitrato group) have been prepared and characterised on the basis of I. R. studies and some thermal properties of these complexes.     

Structure of BaGd2（MoO4）4 Crystal

The title compound belongs to monoclinic,space group C2/c with a=5.2694(1),b=12.6659(4),c=19.4108(2) ,β=91.504(2)°,V=1295.06(5) 3,Z=4 and Dc=5.599 g/cm3. The structure of BaGd2(MoO4)4 contains a MoO4 tetrahedron,a distorted GdO8 polyhedron,and Ba2+ ions in a tenfold coordination. The GdO8 polyhedra are linked together through edge-sharing to give a two-dimensional Gd layer. The MoO4 tetrahedra connected to the Gd atoms are capped up and down the Gd layer through common oxygen apices,thus forming a new Gd-Mo layer. Finally,the Gd-Mo layers are held together through bridging BaO10 polyhedra to form a three-dimensional framework. Since the Ba-μ3-O bond has a large average distance of 2.888 ,this structural characteristic will result in a cleavage along the (001) plane.     

Thermal Decomposition of Thallium(I) Bis-oxalatodiaquaindate(III) Monohydrate

Thallium(I) bis-oxalatodiaquaindate(III) monohydrate was obtained by precipitation of indium(III) withoxalic acid from slightly acidic solution in the presence of thallium(I). The complex was subjected to chemical analysis. The thermal decomposition behavior of the complex was studied using TG, DTA and DTG techniques. The solid complex salt and the intermediate product of its thermal decomposition were characterized using IR absorption and X-ray diffraction spectra. Based on data from these physicochemical investigations the structural formula of the complex was proposed as Tl[In (C₂O₄)₂ (H₂O)₂]⋅H₂O. This revised version was published online in August 2006 with corrections to the Cover Date.     

Crystal Structure of 1，5－Bis（Ts），1，5－diaza－13－crown－4（Ts＝p－methylphenylsulfonyl）

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