Ba5(Ir,Ru)3O12: Eine neue Kristallstruktur mit isolierten Oktaedertripeln

Ba₅(Ir, Ru)₃O₁₂: A New Crystal Structure with Isolated Octahedratripel A new compound, Ba₅(Ir, Ru)₃O₁₂ was prepared and investigated by single crystal X-ray work (space group D-Pnma; a = 10.853; b = 5.897; c = 19.819 Å; Z = 4). ?Isolated”? octahedratripel of face connected [Ir/RuO₆] groups are characteristic to this oxide. Ir and Ru are in statistic distribution. One of these metal positions contains an access of Ir, the other two of Ru, respectively. Coulomb Energy calculations show a dominant oxidation state +4 on one of the three Ir/Ru-point positions.     

Eine neue Verbindung vom M5TiB2O10-Typ mit geordneter Metallverteilung: Ni5SnB2O10

Summary The unknown compound Ni₅SnB₂O₁₀, prepared by using a flux of excess B₂O₃, was investigated by single crystal X-ray technique. It crystallizes with orthorhombic symmetry, space group D _2h ¹⁶ — Pnma witha=9.302,b=6.089,c=12.280 Å,Z=4. The mean result of this investigation is a hitherto unobserved strictly ordered metal distribution. Ni₅SnB₂O₁₀ is not isotypic but related to Ni₅TiB₂O₁₀.

     

Eine neue metastabile Verbindung mit eigenem Strukturtyp: BaNi2In8O15

A New Metastable Compound with a Hitherto Unknown Structure Type: BaNi₂In₈ O₁₅ A new metastable compound: BaNi₂In₈O₁₅ was prepared by high temperature technique and investigated by X-ray single crystal studies. It crystallizes with orthorhombic symmetry, space group D_2h¹⁸–Cmca (a = 12.2811, b = 11.0214, c = 9.9103 Å; Z = 4). A typical feature of the metastable property of BaNi₂In₈O₁₅ is the statistical occupation of one of the point positions with In³⁺ and Ni^2? ions. The structure, especially the InO₆/NiO₆-octahedral network are shown and discussed in respect to the metastable behavior of BaNi₂In₈O₁₅.     

Ein Halogenooxoruthenat (IV,V): Ba6Ru2, 5Mn0, 5O12Cl2 mit neuem Strukturtyp

About a Halogenooxoruthenat (IV, V): Ba₆Ru_2,5Mn_0,5O₁₂Cl₂ with a New Structure Type Ba₆Ru_2.5Mn_0.5O₁₂Cl₂ was prepared and investigated by single crystal X-ray work (space group D—P3 m1; a = b = 5.799; c = 14.853 Å; Z = 1). This structure type is characterized by «isolated», face-sharing (Ru/Mn)₃O₁₂-octahedratriple. Calculations of the Coulomb term of lattice energy support the charge distribution (5⁺/4⁺/5⁺) within the groups (Ru/Ru_0.5Mn_0.5/Ru)₃O₁₂^10?. The coordination of barium by oxygen and chlorine within three different polyhedra is discussed in detail.     

Ba4FeTa10O30, eine neue Verbindung mit Verwandtschaft zum NaNb6O15F-Typ

Ba₄FeTa₁₀O₃₀, a New Compound with Relations to the NaNb₆O₁₅F-Type Ba₄FeTa₁₀O₃₀ was prepared by high temperature reactions (CO₂-Laser-technique) and investigated by X-ray single crystal studies (space group C_2v¹⁴–Amm2, a = 3.906, b = 10.201, c = 14.990 Å, Z = 1). The new compound has a tunnel structure, related to the tungsten bronzes, but with more relationship to the NbO₆-octahedra network of NaNb₆O₁₅F.     

Zwei neue Verbindungen mit Zink in tetragonal pyramidaler Koordination: BaZnDy2O5 und Ba1,25ZnHo2O5,25 (Ba5Zn4Ho8O21)

New Compounds with Zinc in Square Pyramidal Coordination: BaZnDy₂O₅ and Ba_1.25ZnHo₂O_5.25 (Ba₅Zn₄Ho₈O₂₁). Single crystals of (I): BaZnDy₂O₅ and (II): Ba₅Zn₄Ho₈O₂₁ were prepared by high temperature reactions and investigated by X-ray technique. (I) belongs to the BaCuLn₂O₅ type, space group D-Pbnm; a = 7.084; b = 12.368; c = 5.728 Å, Z = 4. (II) is isotypic to Ba₅Mn₄Ln₈O₂₁, space group C-I4/m; a = 13.779; c = 5.707 Å, Z = 2. The two different structure types are caused by the small difference in the composition of 0.25 BaO. Analogies and differences will be discussed. In addition the lattice constants of powder samples of Ba₅Zn₄Ln₈O₂₁ (Ln = Eu, Gd, Dy, Ho, Er and Y) are given.     

Die erste Verbindung mit Mn2+ der Stoffklasse BaMLn2O5: BaMnDy2O5

The First Compound of BaMLn₂O₅-Type Containing Mn²⁺: BaMnDy₂O₅ Single crystals of the hitherto unknown compound BaMnDy₂O₅ were prepared by CO₂-Laser technique and H₂ atmosphere. Four circle diffractometer measurements led to space group D¹⁶_2h-Pnma, a = 12.428; b = 5.766; c = 7.143 Å; Z = 4. It is isotypic to BaCuSm₂O₅ and shows Mn²⁺ in square pyramids of oxygen.     

Eine Verbindung, die mit Schwermetallsalzen innere Komplexe

Ohne Zusammenfassung     

Eine neue Verbindung der Zusammensetzung 9 BaNiO2·2 BaCO3

Zusammenfassung Bei der Reaktion von BaCO₃ mit NiO bildet sich unter bestimmten Bedingungen ein kristallines Pulver der Zusammensetzung 9 BaNiO₂ · 2 BaCO₃. Die Verbindung zeigt scharfe Röntgeninterferenzen, die sich kubisch indizieren lassen. Es wurden elektronenmikroskopische Aufnahmen gemacht sowie Elektronenstrahlfeinbereichsbeugungen durchgeführt. Das IR-Spektrum wurde aufgenommen und die magnetische Suszeptibilität bestimmt.

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A new compound 9 BaNiO₂·2 BaCO₃

During the reaction of BaCO₃ with NiO under special conditions a crystalline powder with the composition 9 BaNiO₂ · 2 BaCO₃ is formed. This compound shows clear X-ray patterns which can be indexed using a cubic cell. Electron microscopic investigations have been carried out and selected area diffraction patterns have been taken. The IR-spectrum and the magnetic susceptibility have been proved.

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Mit 3 Abbildungen     

Synthese und Kristallstruktur von Te3O3(PO4)2, einer Verbindung mit fünffach koordiniertem Tellur(IV)

Synthesis and Crystal Structure of Te₃O₃(PO₄)₂, a Compound with 5‐fold Coordinate Tellurium(IV) Polycrystalline Te₃O₃(PO₄)₂ is formed during controlled dehydration of (Te₂O₃)(HPO₄) with (Te₈O₁₀)(PO₄)₄ as an intermediate product. Colourless single crystals were prepared by heating stoichiometric amounts of the binary oxides P₂O₅ und TeO₂ in closed silica glass ampoules at 590 °C for 8 hours. The crystal structure (P2₁/c, Z = 4, α = 12.375(2), b = 7.317(1), c = 9.834(1)Å, β = 98.04(1)°, 1939 structure factors, 146 parameters, R[F² > 2σ(F²)] = 0.0187, wR2(F² all) = 0.0367) was determined from four‐circle diffractometer data and consists of [TeO₅] polyhedra und PO₄ tetrahedra as the main building units. The framework structure is made up of cationic zigzag‐chains of composition [Te₂O₃]²⁺ which extend parallel to [001] and anionic [Te(PO₄)₂]^2— units linked laterally to these chains. This leads to the formation of [Te₂O₃][Te(PO₄)₂] layers parallel to the bc plane which are interconnected via weak Te‐O bonds.     

Eine β-Tonerde mit Cu2+ in tetraedrischer Koordination: (Ba,Sr)CuAl10O17

A β-Alumina Containing Tetrahedric Coordinated Cu²⁺: (Ba, Sr)CuAl₁₀O₁₇ (Ba, Sr)CuAl₁₀O₁₇ single crystals can be obtained by reaction of BaCuO₂ and SrCuO₂ with Al₂O₃ in oxygen atmosphere ar 1400°C. It crystallizes with hexagonal symmetry, space group D–P6₃/mmc, a = 5.604; c = 22.678 Å; Z = 2. X-ray single crystal investigation led to the β-Alumina-type. Cu²⁺- and Al³⁺-ions occupy tetrahedra positions within the AlO₆-octahedra blocks.     

Eine neue spektralphotometrische Eisen(III)-Bestimmung mit ɛ-Amino-acetophenon-N,N-diacetatoxim

Analytical and Bioanalytical Chemistry -     

Ba2BiV3O11 mit Bismut in geschlossener Koordination

Ba₂BiV₃O₁₁ containing Bismuth within closed Coordination A new barium bismuth oxovanadate, Ba₂BiV₃O₁₁, was prepared and investigated by X-Ray single crystal technique. It crystallizes with monoclinic symmetry space group C—P2₁/a, lattice constants a = 24.6473; b = 7.7347; c = 5.6375 Å, β = 103.16°; Z = 4. Octahedra arround Bi³⁺, tetrahedra and double tetrahedra arround V⁵⁺ form a tunnel structure. The tunnel positions are occupied by Ba(2).     

Zur Kenntnis von Ba(MgZn)V2O8, BaMn2V2O8 und Ba1/2Sr1/2Ni2V2O8

On Ba(MgZn)V₂O₈, BaMn₂V₂O₈, and Ba_1/2Sr_1/2Ni₂V₂O₈ Ba(Mg, Zn)V₂O₈ (A), BaMn₂V₂O₈ (B) and Ba_1/2Sr_1/2Ni₂V₂O₈ (C) were prepared by solid state reactions (A and B) and crystallization from a melt (C) respectively. (A? C) crystallize in the space group: D-I4₁/acd, Nr. 142. [Lattice constants (A): a = 12.4524(57) Å, c = 8.4408(36) Å; (B): a = 12.5563(14) Å, c = 8.5942(9) Å; (C): a = 12.2248(20) Å, c = 8.3245(15) Å]. (A), (B) and (C) are isotypic to SrNi₂V₂O₈ but showing higher symmetry.     

ZnVSe2O7 and Cd6V2Se5O21: new d10 transition-metal selenites with V(IV) or V(V) cations

Two new metal selenites with a combination of vanadium(IV) or vanadium(V) cations, namely, ZnVSe 2O 7 and Cd 6V 2Se 5O 21, have been synthesized by hydrothermal and high-temperature solid-state reactions, respectively. The structure of ZnVSe 2O 7 features a 3D network of vanadium(IV) selenite with 1D tunnels occupied by zinc(II) ions. The 3D network of vanadium(IV) selenite is formed by corner-sharing V (IV)O 6 octahedral chains bridged by selenite groups. In Cd 6V 2Se 5O 21, the interconnection of cadmium(II) ions by bridging and chelating selenite groups led to a 3D framework with large tunnels along the b axis, and the 1D chains of corner-sharing V (V)O 4 tetrahedra are inserted in the above large tunnels and are bonded to the cadmium selenite framework via Cd-O-V bridges. Both compounds exhibit broad emission bands in the blue-light region. Results of magnetic property measurements show there is significant antiferromagnetic interaction between V (4+) centers in ZnVSe 2O 7. The electronic structure calculations for both compounds have been also performed.     

Wismutmonojodid BiJ,eine Verbindung mit Bi(O) und Bi(II)

Bismuth Monoiodide, a Compound with Bi(O) and Bi(II) Bismuth monoiodide was synthesized in closed tubes from the elements as well as from Bi and HgI₂ as a black coloured crystalline compound. With increasing temperature BiI passes two transitions. α-BiI is stable below 370 K and changes to β-BiI by a martensitic transition. γ-BiI is the stable modification above 564 K and decomposes at 585 K peritectically to BiI₃ and a lower iodide. All three modification crystallize in the monoclinic space group C2/m. The structures (single crystal studies) of α-BiI and β-BiI are characterized by onedimensional infinite chains [Bi₄I₄] with covalent bonds but only weak interactions in between. The [Bi₄I₄]-chains are built up by two completely different Bi atoms. Bi(A) is only bonded to three Bi whereas Bi(B) has bonds to one Bi and four I. The average bond lengths are Bi? Bi = 304.5 pm and Bi? I = 313.7 pm respectively. The configuration of the Bi(A) atoms is typical for Bi^O and that one of the Bi(B) atoms is characteristic for Bi²⁺ with the electron configuration s²p¹. Therefore, α-BiI and β-BiI are mixed valence compounds [Bi^OBi²⁺I₄]. The structures are variants of the simple cubic polonium type of structure and differ in the stacking of connected units. The structures and their transitions, the possible configurations for monohalides BiX on principle as well as the energy balances of the disproportionation of Bi⁺ are discussed together in detail.     

Mixed-valence uranium germanate and silicate: Cs(x)(U(V)O)(U(IV/V)O)2(Ge2O7)2 (x = 3.18) and Cs4(U(V)O)(U(IV/V)O)2(Si2O7)2

A new mixed-valence uranium germanate and the silicate analogue have been synthesized under hydrothermal conditions at 600 °C and 165 MPa. Their crystal structures contain infinite -U(V)-O-U(IV/V)-O-U(IV/V)-O-U(V)- chains that are connected by Ge(2)O(7) or Si(2)O(7) groups to form a 3D framework with six-ring channels where the Cs(+) cations are located. Two of the Cs sites in the germanate are partially occupied. Bond-valence-sum calculation and an U 4f X-ray photoelectron spectroscopy study confirm the valence states of the uranium.     

Zwei neue Oxopalladate: BaPdNd2O5 und BaPdSm2O5 mit planar koordinierten Pd2+-Ionen

Single crystals of BaPdNd₂O₅ (A), BaPdSm₂O₅ (B) and BaCuNd₂O₅ (C) were prepared by solid state reaction using BaCl₂ as a fusing assistant (A, B) or by high temperature Laser technique (C). X-ray investigations show tetragonal symmetry with A:a=6.7387 (5),c=5.9002 (25) Å, B:a=6.6667 (13),c=5.8800 (6) Å (space group D _4h ⁵ ?P4/mbm,Z=2). The formerly investigated compound (C) is refined here by single crystal data. (A) and (B) belong to the BaPtNd₂O₅-type. The results are discussed.