A New Compound in the Cu‐In System – the Synthesis and Structure of Cu10In7

A new binary phase, Cu₁₀In₇, was found during the investigation of the η‐phase field in the Cu‐In system. Single crystals of Cu₁₀In₇ were grown from a melt under an inert atmosphere. The compound crystallizes in the monoclinic space group C2/m with cell parameters a = 13.8453(2) Å, b = 11.8462(1) Å, c = 6.7388(1) Å and β = 91.063(1). The structure is based on a unit of face‐sharing octahedra consisting of five Cu₄In₂ octahedra terminated by Cu₅In octahedra at both ends. The crystal structure is closely related to the Cu₁₁In₉ structure type.     

New borides Er0.917Ni4.09B and ErNi7B3 and their crystal structures

New borides have been synthesized and their crystal structures have been determined using X-ray single-crystal methods, namely: Er_0.917Ni_4.09B, own structure type, space group P6/mmm, a=14.8399(3), c=6.9194(3) Å, R_F=0.0545, and ErNi₇B₃, own structure type, space group I4₁/amd, a=7.6577(2), c=15.5798(5) Å, R_F=0.0451. The relationship between these structures and the structure types of CeCo₄B, Y_0.915Ni_4.12B and Sc₄Ni₂₉B₁₀ has been discussed.     

Phase equilibria and crystal structure of the complex oxides in the Sr-Fe-Co-O system

Phase relations in the Sr-Fe-Co-O system have been investigated at 1100 °C in air by X-ray powder diffraction on quenched samples. Solid solutions of the form SrFe_1−xCo_xO_3−δ (0?x?0.7), Sr₃Fe_2−yCo_yO_7−δ (0?y?0.4) and Sr₄Fe_6−zCo_zO_13±δ (0?z?1.6) were prepared by solid-state reaction and by the sol-gel method. The structural parameters of single-phase samples were refined by the Rietveld profile method. The variation of the lattice parameters with composition has been determined for each solid solution and a cross-section of the phase diagram at 1100 °C in air for the entire Sr-Fe-Co-O system has been constructed.     

Solid state phase equilibria in the Gd-Si-B system at 1270 K

Solid state phase equilibria in the ternary Gd-Si-B phase diagram have been proposed at 1270 K using X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Prior to this work, the binary systems Gd-B, Gd-Si and Si-B have also been reinvestigated. The main characteristic of the ternary diagram is the occurrence of two new ternary compounds Gd₅Si₂B₈ and Gd₅Si₃B_0.64. The former crystallizes in tetragonal symmetry, space group P4/mbm with unit cell parameters a=7.2665(3), c=8.2229(7) Å, the second one presents hexagonal symmetry, space group P6₃/mcm with unit cell parameters a=8.5080(4),c=6.4141(2) Å. The X-ray structures of the two structurally related phases Gd₅Si₃B_0.64 and host binary Gd₅Si₃ have been refined from three-dimensional single-crystal intensity data to the final R values of 0.036 (R_w=0.046) and 0.046 (R_w=0.055) for 457 and 401 reflections, respectively with [F>4σ(F)]. Both structures exhibit the Mn₅Si₃-type structure, with in addition for Gd₅Si₃B_0.64 a partial occupancy by boron of the normally vacant interstitial site at the center of the Gd₆ octahedron, which corresponds to the origin of the unit cell. Bonding between the interstitial boron atoms and the gadolinium ones forming the Gd₆B polyhedra is indicated by the decrease in the corresponding Gd-Gd distances and consequently in the unit cell volume. Finally, the Gd-Si-B phase diagram is compared with the previously reported Er-Si-B, at 1070 K.     

New quaternary carbon and nitrogen stabilized polyborides: REB15.5CN (RE: Sc, Y, Ho, Er, Tm, Lu), crystal structure and compound formation

A new family of quaternary carbon and nitrogen containing Rare Earth (RE: Sc, Y, Ho, Er, Tm and Lu) borides: REB_15.5CN, has been synthesized and structurally characterized by powder X-ray diffraction data. They are all isotypic with Sc_1−xB_15.5CN whose structure was solved based on single-crystal X-ray data and HRTEM investigations. The structure refinement converged at a R(F²) value of 0.044 for 364 reflections. The new structure type of Sc_1−xB_15.5CN is composed of a three-dimensional network based on interconnected slabs of boron (B₁₂)^ico icosahedra and (B₆)^oct octahedra. A linear [CBC] chain and nitrogen tightly bridges icosahedra. Sc partially occupies voids in the sheets of boron octahedra. It crystallizes with the trigonal space group P³m1, with Z=2. Lattice parameters (nm) are as follows: for RE: Sc, a,b=0.5568(4), c=1.0756(2); Y, a,b=0.55919(6), c=1.0873(2); Ho, a,b=0.55883(7), c=1.0878(6); Er, a,b=0.55889(5), c=1.0880(6); Tm, a,b=0.5580(1), c=1.0850(6); Lu, a,b=0.55771(9), c=1.0839(4). Magnetic characterization of ErB₁₇C_1.3N_0.6 has been performed.     

Ternary rare-earth titanium antimonides: Phase equilibria in the RE-Ti-Sb (RE=La, Er) systems and crystal structures of RE2Ti7Sb12 (RE=La, Ce, Pr, Nd) and RETi3(SnxSb1-x)4 (RE=Nd, Sm)

Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 °C. In the La-Ti-Sb system, the previously known compound La₃TiSb₅ was confirmed and the new compound La₂Ti₇Sb₁₂ (own type, Cmmm, Z=2, a=10.5446(10) Å, b=20.768(2) Å, and c=4.4344(4) Å) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La₂Ti₇Sb₁₂ consists of a complex arrangement of TiSb₆ octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi₃(Sn_xSb_1−x)₄ for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) Å, b=10.0846(7) Å, and c=24.2260(16) Å for NdTi₃(Sn_0.1Sb_0.9)₄; a=5.7590(4) Å, b=10.0686(6) Å, and c=24.1167(14) Å for SmTi₃(Sn_0.1Sb_0.9)₄). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets.     

Phase diagram of the La–Si binary system under high pressure and the structures of superconducting LaSi5 and LaSi10

The La–Si binary phase diagram under a high pressure of 13.5 GPa was experimentally constructed. New superconducting silicides LaSi₅ and LaSi₁₀ were found, which have peritectic decomposition temperatures at 1000 and 750 °C, respectively. The single crystal X-ray structural analysis revealed that there are two polymorphs in LaSi₅. The α-form obtained by heating a molar mixture of LaSi₂ and 3 Si at about 700 °C or by a rapid cooling from 1000 °C under pressure crystallizes with the space group C2/m and the lattice parameters a=15.11(3), b=4.032(6), c=8.26(1) Å, and β=109.11(1)°. The β-form obtained by a slow cooling from 800–950 °C to 600 °C under pressure has the same space group but with slightly different lattice parameters, a=14.922(7), b=3.906(2), c=8.807(4) Å, and β=107.19(1)°. The β-form is formed during the incomplete transformation of the α-form on cooling, and has always been obtained as a mixture with the α-form. The compound can be characterized as a Zintl phase with a polyanionic framework with large tunnels running along the b axis hosting lanthanum ions. In the β-form, three of the five Si sites are disordered. The two polymorphs contain one dimensional sila-polyacene ribbons, Si ladder polymer, running along the b axis. The α-form showed superconductivity with the transition temperature T_c of 11.5 K. LaSi₁₀ crystallizes with the space group 6₃/mmc and the lattice parameters a=9.623(4), c=4.723(3) Å. It is composed of La containing Si₁₈ polyhedra (La@Si₁₈) of hexagonal beer-barrel shape, which form straight columns by stacking along the c-axis via face sharing. One-dimensional columns of La@Si₁₈ barrels are edge-shared, and bundled with infinite Si trigonal bipyramid chains via corner sharing. The Si atoms in the straight chains have a five-fold coordination. LaSi₁₀ became a superconductor with T_c=6.7 K. The ab initio calculation of the electric band structures showed that α-LaSi₅ and LaSi₁₀ are metallic, and the conduction electrons mainly come from Si-3p orbitals.     

Synthesis and Crystal Structure of the Rubidium Scandium Telluride RbSc5Te8

During attempts to synthesize the rubidium dicopper triscandium hexatelluride RbCu₂Sc₃Te₆ in analogy to CsCu₂Sc₃Te₆ from 2:3:6‐molar mixtures of the elements (Cu, Sc and Te) with an excess of RbBr as flux and rubidium source, after 14 days at 900 °C in torch‐sealed evacuated silica tubes brown lath‐shaped crystals of RbSc₅Te₈ did form instead. This new compound crystallizes monoclinically in space group C2/m (no. 12) with two formula units in a unit cell of the dimensions a = 2130.61(9) pm, b = 413.94(2) pm, c = 1022.03(5) pm and β = 104.392(4)°. The crystal structure of RbSc₅Te₈ consists of a three‐dimensional anionic framework of face‐, edge‐ and vertex‐sharing [ScTe₆]⁹⁻ octahedra that provides one‐dimensional tunnels with a distorted square shape. For charge compensation they are occupied with Rb⁺ cations (CN = 10) coordinated in a trans‐face bicapped cubic fashion by Te²⁻ anions.     

Influence of heat treatment on the magnetic and magnetocaloric properties in Nd0.6Sr0.4MnO3 compound

In the present investigation, the effect of annealing temperature on the structural, electrical transport and the magnetocaloric effect of Nd_0.6Sr_0.4MnO₃ manganites have been studied. Rietveld refinement of XRD data reveals that all samples are single phase with a space group (Pnma). Heat treatment enhances the grain size and decreases the porosity. All samples suffer Curie transition from ferromagnetic to paramagnetic. Magnetocaloric parameters have been determined by the analysis of isothermal M (H) curves around Curie temperature (ΔH = 2 T) for samples. Heat treatment enhances magnetic entropy, which reaches a maximum at T_an = 900 °C. In addition, the rate cooling power records highest value at T_an = 700 °C.     

Die Einwirkung von Ammoniumfluorid auf Scandium: Synthese und Kristallstrukturen von (NH4)3[ScF6] und [Cu(NH3)4]3[ScF6]2

Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH₄)₃[ScF₆] and [Cu(NH₃)₄]₃[ScF₆]₂ The action of (NH₄)F on scandium in copper ampoules yields either (NH₄)₃[ScF₆] or ScF₃ and a small quantity of [Cu(NH₃)₄]₃[ScF₆]₂, respectively, depending upon the molar ratio of the educts (NH₄)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH₄)₃[ScF₆] crystallizes with the cryolite type of structure: monoclinic, P2₁/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH₃)₄]₃[ScF₆]₂ is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH₄)F, scandium parallels aluminium rather than gallium.     

Sr2(OLi2Sr4)[CrN4]2, ein Nitridochromat(VI)‐Oxid mit Sauerstoff in tetragonal‐bipyramidaler Koordination durch Lithium und Strontium

Sr₂(OLi₂Sr₄)[CrN₄]₂, a Nitridochromate(VI)‐Oxide with Oxygen in Tetragonal‐Bipyramidal Coordination by Lithium and Strontium Green gleaming crystals of Sr₂(OLi₂Sr₄)[CrN₄]₂ were prepared by reaction of Li, Sr and CrN/Cr₂N (approximate 1 : 1 mixture) with flowing nitrogen at 900 °C (molar overall composition Li : Sr : Cr = 6 : 1 : ∼3). The oxygen content results from a leak in the gas supply. The crystal structure was determined by single crystal methods (triclinic; P1; a = 615.87(9) pm, b = 682.50(10) pm, c = 754.30(8) pm, α = 82.302(14)°, β = 75.197(10)°, γ = 70.133(13)°; Z = 1) and contains distorted tetragonal bipyramids (OLi₂Sr₄)⁸⁺ and [Cr^VIN₄]^6–‐tetrahedra besides Sr²⁺.     

New germanates RCrGeO5 (R=Nd-Er, Y): Synthesis, structure, and properties

The new complex germanates RCrGeO₅ (R=Nd-Er, Y) have been synthesized and investigated by means of X-ray powder diffraction, electron microscopy, magnetic susceptibility and specific heat measurements. All the compounds are isostructural and crystallize in the orthorhombic symmetry, space group Pbam, and Z=4. The crystal structure of RCrGeO₅, as refined using X-ray powder diffraction data, includes infinite chains built by edge-sharing Cr⁺³O₆ octahedra with two alternating Cr−Cr distances. The chains are combined into a three-dimensional framework by Ge₂O₈ groups consisting of two edge-linked square pyramids oriented in opposite directions. The resulting framework contains pentagonal channels where rare-earth elements are located. Thus, RCrGeO₅ germanates present new examples of RMn₂O₅-type compounds and show ordering of Cr⁺³ and Ge⁺⁴ cations. Electron diffraction as well as high-resolution electron microscopy confirm the structure solution. Magnetic susceptibility data for R=Nd, Sm, and Eu are qualitatively consistent with the presence of isolated 3d (antiferromagnetically coupled Cr⁺³ cations) and 4f (R⁺³) spin subsystems in the RCrGeO₅ compounds. NdCrGeO₅ undergoes long-range magnetic ordering at 2.6 K, while SmCrGeO₅ and EuCrGeO₅ do not show any phase transitions down to 2 K.     

Homogeneity range of the NaTl-type Zintl phase in the ternary system Li-In-Ag

The remarkably broad homogeneity range of the NaTl-type Zintl phase in the ternary phase diagram Li-In-Ag at room temperature was determined by structure evaluation using X-ray powder diffraction. The colours of the investigated Zintl phases correlate with the valence electron concentration (VEC) as already established for the quasibinary cut Li_0.5(In_xAg_1−x)_0.5 with 0.47?x?1.00, i.e. with decreasing VECs the colour changes from grey over reddish to bright yellow. All compounds in the new quasibinary cut Li_x(In_0.5Ag_0.5)_1−x with 0.47?x?0.60 appear free from vacancies in the Li-sublattice, even for Li-deficient compositions. The partial occupation of Li-sites by excess Ag and In instead is in full agreement with the behaviour of the binary NaTl-type Zintl phases Li_xZn_1−x and Li_xCd_1−x (0.47?x?0.54) with a low VEC about 1.5.     

Assembly of Three Scandium-containing Heteropolytungstates Based on a Building-block Synthetic Strategy

Three novel scandium-containing heteropolytungstates[Sc₃(H₂O)₃NO₃(PW₉O₃₄)₂]^10-(1a),[Sc₈(H₂O)₂(GeW₉O₃₄)₂(GeW₆O₂₆)₂]^12-(2a) and[Sc₁₁(W₆O₁₀)₂(OH)₂(H₂O)₁₆(BiW₉O₃₃)₆]^27-(3a) were synthesized by reactions of Sc^III ions with trilacunary Keggin precursors,[A-α-XW₉O₃₄]^n-(X=P, Ge, n=9, 10) or[B-α-BiW₉O₃₃]^9-, in NaOAc/HOAc buffer solution under conventional synthetic condition, respectively. All the three compounds were characterized by means of single-crystal X-ray diffraction(XRD), Fourier transform-infrared(FTIR) spectroscopy ultraviolet-visible(UV-Vis) spectroscopy, elemental analysis, and thermogravimetric analysis. The aqueous solution stability of the sandwich polyanion[Sc₃(H₂O)₃NO₃(PW₉O₃₄)₂]^10- was also verified by electrospray ionization mass spectrometry(ESI-MS) due to its good solubility in water.     

Syntheses and structures of three new scandium selenites: Sc2(SeO3)3·H2O, Sc2 (SeO3)3·3H2O and CsSc3(SeO3)4 (HSeO3)2·2H2O

Three new hydrated scandium selenites have been hydrothermally synthesized as single crystals and structurally and physically characterized. Sc₂(SeO₃)₃·H₂O crystallizes as a new structure type containing novel ScO₇ pentagonal bipyramidal and ScO₆₊₁ capped octahedral coordination polyhedra. Sc₂(SeO₃)₃·3H₂O contains typical ScO₆ octahedra and is isostructural with its M₂(SeO₃)₃·3H₂O (M=Al, Cr, Fe, Ga) congeners. CsSc₃(SeO₃)₄(HSeO₃)₂·2H₂O contains near-regular ScO₆ octahedra and has essentially the same structure as its indium-containing analogue. All three phases contain the expected pyramidal [SeO₃]^2- selenite groups. Crystal data: Sc₂(SeO₃)₃·3H₂O, M_r=524.85, trigonal, R3c (No. 161), , , , Z=6, R(F)=0.018, wR(F²)=0.036; Sc₂(SeO₃)₃·H₂O, M_r=488.82, orthorhombic, P2₁2₁2₁ (No. 19), , , , , Z=4, R(F)=0.051, wR(F²)=0.086; CsSc₃(SeO₃)₄(HSeO₃)₂·2H₂O, M_r=1067.60, orthorhombic, Pnma (No. 62), , , , , Z=4, R(F)=0.035, wR(F²)=0.070.     

In3Ir3B, In3Rh3B and In5Ir9B4, the first indium platinum metal borides

The first indium platinum metal borides have been synthesized and structurally characterized by single crystal X-ray diffraction data. In₃Ir₃B and In₃Rh₃B are isotypic. They crystallize with the hexagonal space group and Z=1. The lattice constants are , for In₃Ir₃B and , for In₃Rh₃B. The structure which is derived from the Fe₂P type is characterized by columns of boron centered triangular platinum metal prisms inserted in a three-dimensional indium matrix. The indium atoms are on split positions. In₅Ir₉B₄ (hexagonal, space group , , , Z=1) crystallizes with a structure derived from the CeCo₃B₂ type. The structure can be interpreted as a layer as well as a channel structure. In part the indium atoms are arranged at the vertices of a honeycomb net (Schlaefli symbol 6³) separating slabs consisting of double layers of triangular Ir₆B prisms, and in part they form a linear chain in a hexagonal channel formed by iridium prisms and indium atoms of the honeycomb lattice.     

SmZn11-type derivative compound in the Yb-Zn-Al system: Crystal structure and magnetic properties

Crystal structure and magnetic properties are reported for Yb_3.50Zn_32.1Al_1.4 prepared in single-crystalline form. It adopts the SmZn₁₁-type of structure (SG P6/mmm) with lattice parameters a=0.90458(1), c=0.88547(1) nm. The phase composition was analyzed by XRD, chemical and electron microprobe analysis. The ytterbium atoms in this compound are in the non-magnetic 4f¹⁴ state.     

Synthese und Kristallstruktur von [Cr(NH3)6][Cr(NH3)2F4][BF4]2

Synthesis and Crystal Structure of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂ The action of ammonium fluoride on a mixture of boron and chromium in a sealed Monel ampoule at 300 °C yields single crystals of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂. The crystal structure (tetragonal, P4/mbm, Z = 2, a = 1056.0(1), c = 781.7(1) pm; R₁ = 0.0414; wR₂ = 0.1087 for 411 reflections with I₀ > 2σ(I)) contains [Cr(NH₃)₆]³⁺ and [Cr(NH₃)₂F₄]^– octahedra and twice as many [BF₄]^– tetrahedra that are arranged in a quadrupled super‐structure of the CsCl‐type of structure.     

Phase equilibrium and intermediate phases in the Eu–Sb system

Rapid heating rate thermal analysis, X-ray diffraction, fluorescence spectrometry, and differential dissolution method were used to study the high-temperature phase equilibrium in the Eu–Sb system within the composition range between 37 and 96 at% Sb. The techniques were effective in determination of the vapor–solid–liquid equilibrium since intermediate phases except Eu₄Sb₃ evaporated incongruently after melting. A thermal procedure was developed to determine the liquidus and solidus lines of the T−x diagram. Six stable phases were identified: two phases, EuSb₂ and Eu₄Sb₃, melt congruently at 1045±10 °C and 1600±15 °C, the Eu₂Sb₃, Eu₁₁Sb₁₀, Eu₅Sb₄, and Eu₅Sb₃ phases melt incongruently at 850±8 °C, 950±10 °C, 1350±15 °C, and 1445±15 °C, respectively. The exact composition shifting of Sb-rich decomposable phases towards Eu₄Sb₃, the most refractory compound, was determined. The topology of the Eu–Sb phase diagram was considered together with that of the Yb–Sb system.     

Density and phase diagram of the magnesium–lead system in the region of Mg2Pb intermetallic compound

The phase diagram of magnesium–lead system has been investigated by a new method for phase analysis on the basis of a strong penetrating radiation. The measurements have shown that the standard phase diagram of this system contains inaccuracy in the region of the Mg₂Pb intermetallic compound. New data on the temperature dependences of the solid and the melt densities have been obtained. The density change during the phase transitions has been directly measured.