Zwei Chloridsilicate des Yttriums: Y3Cl[SiO4]2 und Y6Cl10[Si4O12]

Two Chloride Silicates of Yttrium: Y₃Cl[SiO₄]₂ and Y₆Cl₁₀[Si₄O₁₂] The chloride‐poor yttrium(III) chloride silicate Y₃Cl[SiO₄]₂ crystallizes orthorhombically (a = 685.84(4), b = 1775.23(14), c = 618.65(4) pm; Z = 4) in space group Pnma. Single crystals are obtained by the reaction of Y₂O₃, YCl₃ and SiO₂ in the stoichiometric ratio 4 : 1 : 6 with ten times the molar amount of YCl₃ as flux in evacuated silica tubes (7 d, 1000 °C) as colorless, strongly light‐reflecting platelets, insensitive to air and water. The crystal structure contains isolated orthosilicate units [SiO₄]^4– and comprises cationic layers {(Y2)Cl}²⁺ which are alternatingly piled parallel (010) with anionic double layers {(Y1)₂[SiO₄]₂}^2–. Both crystallographic different Y³⁺ cations exhibit coordination numbers of eight. Y1 is surrounded by one Cl^– and 7 O^2– anions as a distorted trigonal dodecahedron, whereas the coordination polyhedra around Y2 show the shape of bicapped trigonal prisms consisting of 2 Cl^– and 6 O^2– anions. The chloride‐rich chloride silicate Y₆Cl₁₀[Si₄O₁₂] crystallizes monoclinically (a = 1061,46(8), b = 1030,91(6), c = 1156,15(9) pm, β = 103,279(8)°; Z = 2) in space group C2/m. By the reaction of Y₂O₃, YCl₃ and SiO₂ in 2 : 5 : 6‐molar ratio with the double amount of YCl₃ as flux in evacuated silica tubes (7 d, 850 °C), colorless, air‐ and water‐resistant, brittle single crystals emerge as pseudo‐octagonal columns. Here also a layered structure parallel (001) with distinguished cationic double‐layers {(Y2)₅Cl₉}⁶⁺ and anionic layers {(Y1)Cl[Si₄O₁₂]}^6– is present. The latter ones contain discrete cyclo‐tetrasilicate units [Si₄O₁₂]^8– of four cyclically corner‐linked [SiO₄] tetrahedra in all‐ecliptical arrangement. The coordination sphere around (Y1)³⁺ (CN = 8) has the shape of a slightly distorted hexagonal bipyramid comprising 2 Cl^– and 6 O^2– anions. The 5 Cl^– and 2 O^2– anions building the coordination polyhedra around (Y2)³⁺ (CN = 7) form a strongly distorted pentagonal bipyramid.     

Analysis of electric properties of ZrO2-Y2O3 single crystals using teraherz IR and impedance spectroscopy techniques

The data obtained by impedance spectroscopy (1 Hz to 32 MHz) and broad-band dielectric spectroscopy (30 GHz-150 THz) are presented for crystals based on zirconia doped by 1.5–30 mol % Y₂O₃ or 10 mol % Sc₂O₃ and 1 mol % Y₂O₃. The maximum of ionic conductivity is confirmed for the latter composition in the working temperature range of solid oxide fuel cells where the doping by scandium and yttrium oxides makes it possible to obtain isotropic single crystals. Dependences of dielectric permeability and high-frequency conductivity of materials on the composition of crystals and temperature are presented.     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Protective yttria coatings of melting crucible for metallic fuel slugs

As one of the candidate coating materials for a melting crucible, yttrium oxides were deposited on graphite and niobium substrates using slurry and plasma spraying methods. Thermal cycling tests and interaction studies between U–Zr/U–Zr–RE fuel melt and the Y₂O₃ coatings were carried out to evaluate the performance as reusable coatings for a melting crucible. A multi‐layer coating method was also applied to overcome the issue of a thermal expansion mismatch between the coating and substrate. The results showed that the plasma‐sprayed coatings showed a good consolidation after deposition compared to slurry coating. The plasma‐sprayed Y₂O₃ coating on the niobium substrate showed better thermal cycling resistance than those coated on a graphite substrate. The proposed TaC/Y₂O₃ double‐layer coating which was plasma‐sprayed on the niobium substrate showed improved characteristics with no reaction layer formation and no separation from the substrate after the interaction with the U–Zr–RE melt. Copyright © 2014 John Wiley & Sons, Ltd.     

Sc2Te5O13 und Sc2TeO6: Die ersten Oxotellurate des Scandiums

Sc₂Te₅O₁₃ and Sc₂TeO₆: The First Oxotellurates of Scandium Sc₂Te₅O₁₃ and Sc₂TeO₆ are the first oxotellurates of scandium that could be structurally elucidated by X‐ray diffraction using single crystals. The scandium(III) oxotellurate(IV) Sc₂Te₅O₁₃ was synthesized by reacting Sc₂O₃ with TeO₂ at 850 °C and crystallizes in the triclinic system with space group (no. 2) and the lattice parameters a = 660.67(5), b = 855.28(7), c = 1041.10(9) pm, α = 86.732(8), β = 86.264(8), and γ = 74.021(8)° (Z = 2). The crystal structure contains chains respectively strands of alternatingly edge‐ and vertex‐sharing [ScO₆]^9? and [ScO₇]^11? polyhedra. These strands are connected by [TeO₃₊₁]^(2+2)? oxotellurate(IV) anions. The coordination spheres of Sc³⁺ appear markedly smaller than those of M³⁺ cations in the other known compounds of the formula type M₂Te₅O₁₃ (M = Y, Dy – Lu), therefore Sc₂Te₅O₁₃ is not really isotypic, but only isopuntal with these compounds. Single crystals of the scandium(III) oxotellurate(VI) Sc₂TeO₆ were obtained through the fusion of a mixture of Sc₂O₃ and TeO₃ at 850 °C. It crystallizes trigonally (a = 874.06(7), c = 479.85(4) pm and c/a = 0.549) with the Na₂SiF₆‐type structure in space group P321 (no. 150) and three formula units per unit cell. Its crystal structure is built up by a hexagonal closest packing (hcp) of oxide anions with the Sc³⁺ cations residing in ¹/₃ and the Te⁶⁺ cations in ¹/₆ of the octahedral interstices in a well‐ordered occupation pattern. Thus one can address the structural situation in Sc₂[TeO₆] as a stuffed β‐WCl₆‐type arrangement.     

NO(HSO4), a Fairly Ionic Solid

The colourless solid NO(HSO₄), known as “lead‐chamber crystals”, was investigated ever since its first preparation more than two centuries ago. Its overall ionic nature now is confirmed by X‐ray crystallography [Pna2₁, a = 7.3558(4), b = 6.8924(3), c = 7.7017(3) Å, Z = 4]. The next neighbours of the NO⁺ cations are four hydrogensulfate oxygen atoms, forming a distorted square at a distance of about 2.5 Å from the nitrogen atom. The square pattern next to the nitrogen atom is the most widespread coordination figure about an NO⁺ ion in a nitrosyl salt. Depending on the anion, the interaction goes along with a decrease of the N–O stretch's excitation energy.     

Einkristalle von Y3F[Si3O10] im Thalenit-Typ

Single Crystals of Y₃F[Si₃O₁₀] with Thalenite-Type Structure Colourless, diamond-shaped single crystals of Y₃F[Si₃O₁₀] (monoclinic, P2₁/n; a = 730.38(5), b = 1112.47(8), c = 1037.14(7) pm, β = 97.235(6)°, Z = 4) with thalenite-type structure are obtained upon the reaction of YF₃ with Y₂O₃ and SiO₂ (1 : 4 : 9 molar ratio) in evacuated silica tubes at 700 °C in the presence of CsCl as flux within seven days. The crystal structure consists of triangular [FY₃]⁸⁺ cations and catena-trisilicate anions [Si₃O₁₀]^8–, which exhibit a horseshoe-shape resulting from two vertex-shared terminal [SiO₄] tetrahedra with both staggered and eclipsed conformation relative to the central one. The Y³⁺ cations have coordination numbers of seven plus one (Y1) or seven (Y2 and Y3), but only one F^– anion belongs to each and vice versa, the remainder ligands being oxygen members of [Si₃O₁₀]^8– anions.     

Synthesis, crystal structures and luminescence properties of the Eu-doped yttrium oxotellurates(IV) Y2Te4O11 and Y2Te5O13

Y₂Te₄O₁₁:Eu³⁺ and Y₂Te₅O₁₃:Eu³⁺ single crystals in sub-millimeter scale were synthesized from the binary oxides (Y₂O₃, Eu₂O₃ and TeO₂) using CsCl as fluxing agent. Crystallographic structures of the undoped yttrium oxotellurates(IV) Y₂Te₄O₁₁ and Y₂Te₅O₁₃ have been determined and refined from single-crystal X-ray diffraction data. In Y₂Te₄O₁₁, a layered structure is present where the reticulated sheets consisting of edge-sharing [YO₈]¹³⁻ polyhedra are interconnected by the oxotellurate(IV) units, whereas in Y₂Te₅O₁₃ only double chains of condensed yttrium-oxygen polyhedra with coordination numbers of 7 and 8 are left, now linked in two crystallographic directions by the oxotellurate(IV) entities. The Eu³⁺ luminescence spectra and the decay time from different energy levels of the doped compounds were investigated and all detected emission levels were identified. Luminescence properties of the Eu³⁺ cations have been interpreted in consideration of the now accessible detailed crystallographic data of the yttrium compounds, providing the possibility to examine the influence of the local symmetry of the oxygen coordination spheres.     

Site Preference of Cations and Structural Variation in MgAl2–xGaxO4 (0 ≤ x ≤ 2) Spinel Solid Solution

The crystal structures of MgAl_2–xGa_xO₄ (0 ≤ x ≤ 2) spinel solid solutions (x = 0.00, 0.38, 0.76, 0.96, 1.52, 2.00) were refined using ²⁷Al MAS NMR measurements and single crystal X‐ray diffraction technique. Site preferences of cations were investigated. The inversion parameter (i) of MgAl₂O₄ (i = 0.206) is slightly larger than given in previous studies. It is considered that the difference of inversion parameter is caused by not only the difference of heat treatment time but also some influence of melting with a flux. The distribution of Ga³⁺ is little affected by a change of the temperature from 1473 K to 973 K. The degree of order‐disorder of Mg²⁺ or Al³⁺ between the fourfold‐ and sixfold‐coordinated sites is almost constant against Ga³⁺ content (x) in the solid solution. A compositional variable of the Ga/(Mg + Ga) ratio in the sixfold‐coordinated site has a constant value through the whole compositional range: the ratio is not influenced by the occupancy of Al³⁺. The occupancy of Al³⁺ is independent of the occupancy of Ga³⁺, though it depends on the occupancy of Mg²⁺ according to thermal history. The local bond lengths were estimated from the refined data of solid solutions. The local bond length between specific cation and oxygen corresponds with that expected from the effective ionic radii except local Al–O bond length in the fourfold‐coordinated site and local Mg–O bond length in the sixfold‐coordinated site. The local Al–O bond length in the fourfold‐coordinated site (1.92 Å) is about 0.15 Å longer than the expected bond length. This difference is induced by a difference in site symmetry of the fourfold‐coordinated site. The nature that Al³⁺ in spinel structure occupies mainly the sixfold‐coordinated site arises from the character of Al³⁺ itself. The local Mg–O bond length in the sixfold‐coordinated site (2.03 Å) is about 0.07 Å shorter than the expected one. Difference Fourier synthesis for MgGa₂O₄ shows a residual electron density peak of about 0.17 e/ų in height on the center of (Ga_0.59 Mg_0.41)–O bond. This peak indicates the covalent bonding nature of Ga–O bond on the sixfold‐coordinated site in the spinel structure.     

Eu5F[SiO4]3 und Yb5S[SiO4]3: Gemischtvalente Lanthanoid‐Silicate mit Apatit‐Struktur

Eu₅F[SiO₄]₃ and Yb₅S[SiO₄]₃: Mixed‐Valent Lanthanoid Silicates with Apatite‐Type of Structure By the reaction of Eu, EuF₃, Eu₂O₃ with SiO₂ in evacuated gold ampoules, using NaF as flux, at a temperature of 1000 °C for ten hours, dark‐red, platelet‐shaped single crystals of Eu₅F[SiO₄]₃ are obtained. Similarly dark‐red, but pillar‐shaped single crystals of Yb₅S[SiO₄]₃ are obtained by the reaction of Yb, Yb₂O₃ and S with SiO₂ in the presence CsBr as flux in evacuated silica ampoules at 850 °C and an annealing time of seven days. Both compounds crystallize hexagonally (P6₃/m, Z = 2; Eu₅F[SiO₄]₃: a = 954.79(9), c = 704.16(6) pm; Yb₅S[SiO₄]₃: a = 972.36(9), c = 648.49(6) pm) in the case of Eu₅F[SiO₄]₃ analogous to the mineral fluorapatite and for Yb₅S[SiO₄]₃ as a bromapatite—type variety. The crystal structure containing isolated [SiO₄]^4— tetrahedra distinguishes two rare‐earth cation positions with coordination numbers of nine (M1) and seven (M2), in which the position M1 of the europium fluoride silicate is almost exclusively occupied by Eu²⁺ cations, whereas in ytterbium sulfide silicate it contains di‐ and trivalent Yb cations in the ratio 1 : 1. In both cases, however, the M2 position is only populated with M³⁺.     

The First Homoleptic Bis(trifluoromethanesulfonyl)amide Complex of Yttrium: [bmim][Y(Tf2N)4]

1‐Butyl‐3‐methylimidazolium tetrakis‐(bis(trifluoromethanesulfonyl)amide)yttrium(III), [bmim][Y(Tf₂N)₄], was obtained from the ionic liquid 1‐butyl‐3‐methylimidazoliumbis(trifluoromethanesulfonyl)amide, [bmim][Tf₂N] and yttrium(III)bis(trifluoromethanesulfonyl)amide, Y(Tf₂N)₃. The crystal structure [monoclinic, C2/c (no. 15), a = 2096.(1), b = 1451.5(1), c = 1608.55(9) pm, β = 109.669(6)°, V = 4608.1(5)·10⁶ pm³, Z = 4, R₁ for 3874 symmetry independent reflections with I₀>2σ(I₀): 0.0438] contains Y^III coordinated by four Tf₂N‐ligands which all adopt a transoid‐conformation with respect to their –CF₃ groups. The oxygen coordination polyhedron around Y^III can be best described as a trigonal dodecahedron.One 1‐butyl‐3‐methylimidazolium cation compensates for the charge of the complex [Y(Tf₂N)₄]^? anion.     

Synthese und Kristallstruktur von Cs3Y7Se12

Synthesis and Crystal Structure of Cs₃Y₇Se₁₂ The oxidation of yttrium metal with selenium in the presence of CsCl (7 d, 700°C, evacuated silicia tubes) results in the formation of pale yellow, lath-shaped single crystals of Cs₃Y₇Se₁₂. The crystal structure (orthorhombic, Pnnm, Z = 2, a = 1272.8(3), b = 2627.7(5), c = 413.32(8) pm) consists of edge- and vertex-connected [YSe₆] octahedra forming a rocksalt-related network [Y₇Se₁₂]^3?. One-dimensional infinite channels along [001], apt to take up extra cations, provide coordination numbers of 6 and 7 + 1, respectively, for two crystallographically different Cs⁺.     

Sodium calcium orthovanadate,NaCa4(VO4)3

Single crystals of sodium tetra­calcium trivanadium dodeca­oxide were prepared by melting a powder sample of NaCa₄(VO₄)₃ at 1673 K, followed by slow cooling to room temperature. The compound crystallizes in the Pnma space group and is isostructural with the mineral silicocarnotite, Ca₅(PO₄)₂SiO₄. The structure is composed of isolated VO₄ tetra­hedra linked by sodium and calcium cations disordered over eight‐ and seven‐coordinated sites.     

Theoretical explanation of the quenching of luminescence in cerium‐doped ytterbium oxyorthosilicate

A remarkable result in applied solid‐state physics is that whereas Ce‐doped yttrium oxyorthosilicate, Y₂(SiO₄)O:Ce, is an excellent scintillator, the related Ce‐doped ytterbium oxyorthosilicate, Yb₂(SiO₄)O:Ce, does not scintillate at all at room temperature. These compounds, Y and Yb, besides possessing the same crystal structure, both are trivalent and yield almost identical ionic radii. In order to understand the difference between the luminescent properties of these materials, we have performed an ab initio calculation to investigate the charge‐transfer mechanism involving their first excited states. By using a representative cluster model, a crossing is found between the ground and the excited state of the ytterbium compound, though not so in the yttrium compound. This suggests that in the solid state, the luminiscence quenching can occur via a nonradiative transition, although luminescence at low temperature might thus be feasible. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 198–203, 2000     

Ca0.8Y2.4Sn0.8O6, a quaternary oxide with mixed occupations of Ca/Y and Y/Sn

A new quaternary oxide, calcium yttrium stannate, Ca_0.8Y_2.4Sn_0.8O₆, is isostructural with Mg₃TeO₆ (trigonal, R). The empirical formula can be expressed as (Ca_0.2667Y_0.7333)₆(Y_0.4Sn_0.6)SnO₁₂. The Ca/Y site has a distorted coordination octa­hedron of O atoms, with Ca/Y—O distances ranging from 2.227 (3) to 2.350 (3) Å, while the octa­hedra of O atoms that coordinate to the Sn and Y/Sn sites are nearly regular, with an Sn—O distance of 2.066 (2) Å and a Y/Sn—O distance of 2.147 (3) Å.     

Earth Alkaline Tetrathiosquarates. II. – Syntheses and Crystal Structures of SrC4S4·4 H2O and Ba4K2(C4S4)5·16 H2O

Concentrated aqueous solutions of strontium chloride and barium chloride, respectively, allow on addition of the potassium salt of tetrathiosquarate, K₂C₄S₄·H₂O, the isolation of the earth alkaline salts SrC₄S₄·4 H₂O ( 1 ) and Ba₄K₂(C₄S₄)₅·16 H₂O ( 2 ), both as dark red crystals. The crystal structure determinations ( 1 : orthorhombic, Pnma, a = 8.149(1), b = 12.907(2), c = 10.790(2) Å, Z = 4; 2 : orthorhombic, Pbca, a = 15.875(3), b = 21.325(5), c = 16.119(1) Å, Z = 4) show the presence of C₄S₄²⁻ ions with only slightly distorted D_4h symmetry having average C–C and C–S bond lengths of 1.41Å and 1.681Å for 1 and 1.450Å and 1.657Å for 2 . The structure of 1 contains concatenated edge‐sharing Sr(H₂O)₆S₂ polyhedra. The Sr²⁺ ions are in eight‐fold coordination with Sr–O distances of 2.50–2.72Å and Sr–S distances of 3.21Å, (C₄S₄)²⁻ acts as a chelating ligand towards Sr²⁺. The structure is closely related to the previously reported Ca²⁺ containing analogue, which is of lower symmetry belonging to the monoclinic crystal system. A supergroup‐subgroup relation between the space groups of both structures is present. The structure of 2 is made up of Ba²⁺ and K⁺ ions in eight and nine‐fold coordination by H₂O molecules and (C₄S₄)²⁻ ions which act as chelating ligands towards one cation and bridging between two cations. The coordination polyhedra of the cations are connected by common edges and corners in two dimensions to layers which are connected by tetrathiosquarate ions to a three‐dimensional network. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.     

Pb5I2P28, $^{1}_{\infty}\rm [PbP_{14}]{\rm ^{2-}}$ Strands Coordinated to a Unique [Pb3I2]4+ Unit

Pb₅I₂P₂₈ is the first compound containing a former unseen [P₃I₂]⁴⁺ unit, connecting two crystallographically independent adjacent [PbP₁₄]^2? polyphosphide strands. The polyanion substructure is closely related to the one realized in the HgPbP₁₄ structure type, with a homo‐nuclear coordination of the cations to the polyanions. It has been prepared by using the mineralizator concept for polyphosphides from the elements and PbI₂ as the mineralizator species. The new polyphosphide has a pronounced tendency to form easy cleavable, needle shaped crystals featuring massive stacking vaults. Nevertheless, a single crystal structure determination was possible from inter‐grown crystals. Pb₅I₂P₂₈ crystallizes monoclinically in the space group P2₁/n (No. 14) with lattice parameters of a = 9.792(2), b = 17.717(2), c = 19.191(3) Å, β = 96.39(1)°, V = 3308.6(8) ų. Depending on the preparation route, the aspect ratio of the needle shaped crystals can be varied.     

Dilithium Hexaboride,Li2B6

Li₂B₆ is formed from the elements as transparent red microcrystalline compound (Li : B = 1 : 3; Mo crucible in closed Nb ampoule; 1723 K; 4 h). Single crystals are grown from a lithium silicide melt with large Li excess at 1923 K. Li₂B₆ is a semiconductor with electron as well as Li⁺ ionic conductivity which dominates above 600 K. Microcrystalline samples react with H₂O liberating gases and forming a brownish amorphous product, but larger crystals are not very sensitive. – Li₂B₆ crystallizes tetragonally in a new tP16 structure type which is a variant of the CaB₆ structure (a = 5.975 Å, c = 4.189 Å; Z = 2; space group P4/mbm). The [B₆^2–] net of the polymeric octahedro-anion is slightly distorted to give space for the insertion of a (3²434) net of the Li⁺ cations in the cavities (d(B–B)_endo = 1.766 Å; d(B–B)_exo = 1.720 Å; d(Li–B) = 2.363 Å; d(Li–Li) = 3.094 Å). The incomplete occupancy of the Li position (80%) and the electron density at a further position (20%) indicate the mobility of the Li⁺ cations.     

[Pt(Hmimt)4](NO3)2: Hydrogen Bonding Determines the Difference between the Structures of the Tetrakis[1‐methyl‐2(3H)‐imidazolinethione]platinum(II) Cation in its Chloride and Nitrate Salts

The yellow‐orange crystals of [Pt(Hmimt)₄](NO₃)₂ [Hmimt = 1‐methyl‐2(3H)‐imidazolinethione] are monoclinic [P2₁, a = 8.136(3), b = 13.978(4), c = 12.150(9)Å, β = 96.89(5)°]. They consist of [Pt(Hmimt)₄]²⁺ cations and nitrate anions. In the cation the Pt atom is coordinated by four S atoms [Pt‐S: 2.291(5)‐2.357(5)Å] in a slightly distorted square planar arrangement.     

Synthesis and crystal structure of tris(ɛ-caprolactamium) hexa(isothiocyanato)chromate(III) tricaprolactam (C6H14NO)3[Cr(NCS)6] · 3(C6H13NO)

A novel complex, tris(?-caprolactamium) hexa(isothiocyanato)chromate(III) tricaprolactam (C₆H₁₂NO)₃[Cr(NCS)₆] · 3(C₆H₁₁NO), has been synthesized and characterized by X-ray diffraction. The structure can be referred to the discrete ionic type. The coordination polyhedron of the chromium atom is a nearly regular octahedron. The crystals of the complex (C₄₂H₆₉CrN₁₂O₆S₆, FW = 1082.45) are triclinic, space group P $\overline 1 $ , Z = 1, V = 1359.3(2) ų, d _calcd = 1.322 g/cm³. Unit cell parameters: a = 11.1784(9) Å, b = 11.3196(7) Å, c = 12.580(2) Å, α = 109.347(5)°, β = 106.304(5)°, γ = 102.025(4)°. The unit cell contains three caprolactamium cations and three caprolactam molecules related by the inversion center of the space group, which leads to random occupancy of the positions of the cations and solvation molecules.