Zur Kenntnis von Ba6Ru2PtO12Cl2

About Ba₆Ru₂PtO₁₂Cl₂ Single crystals of Ba₆Ru₂PtO₁₂Cl₁₂ were prepared by a BaCl₂ flux and investigated by X-ray methods (D? P3 M1; a = 5,805; c = 15.006 Å; Z = 1). The characteristic face shared M₃O₁₂-octahedratriples show an ordered (Ru/Pt/Ru) occupation. Calculation of the Coulomb term of lattice energy support the charge distribution (5⁺/4⁺/5⁺) ions engage three point sites with different coordinations. The connection to other compounds are discussed.     

Ein neuer Strukturtyp eines neuen Ruthenium(V)-Oxidchlorids: Ba5Ru2O9Cl2

Ba₅Ru₂O₉Cl₂ — a New Structure Type of a New Ruthenium(V) Oxidechloride For the first time an alkaline earth-halogenooxo-ruthenate(V) with the formula Ba₅Ru₂O₉Cl₂ was prepared and investigated by X-ray single crystal technique. It builds up a new type of structure with an orthorhombic symmetrie (space group D—Pnma, a = 15.310; b = 5.945; c = 14.197 Å). The crystal structure show a threedimensional Ba/O/Cl frame, which contains isolated Ru₂O₉-double-octahedra. The relations to other structures are discussed.     

Über hexagonale Perowskite mit Kationenfehlstellen. XXXI. Die Systeme BaO?Re2O7?MO5 mit MV = Nb,Ta

On Hexagonal Perovskites with Cationic Vacancies. XXXI. Systems BaO? Re₂O₇? M O₅ with M^V = Nb, Ta In the systems BaO? Re₂O₇? MO₅ three quaternary oxides are formed, which belong to the perovskite stacking polytypes with cationic vacancies: Ba₈Re_7/2M□₃O₂₄ (M^V = Nb, Ta; rhombohedral 24 L type; sequence (hhhhchhc)₃; space group R3 m), Ba₄Re_9/8Ta_13/8□_5/4O₁₂ (rhombohedral 12 L type; sequence (hhcc)₃; space group R3 m) and the phases Ba₅BaRe_3/2?xM □O_15?x□_x (M^V = Nb, Ta; variants of a hexagonal 5 L type).     

Die Kristallstrukturen von Mn5O8 und Cd2Mn3O8

The crystal structures of Mn₅O₈ and Cd₂Mn₃O₈ are determined from single crystal and high resolution X-ray powder data. Both structures have very similar monoclinic unit cells, space group C–C2/m, and are isotypic: Hence, the true formula of Mn₅O₈ is MnMnO₈. The crystal structure consists of pseudohexagonal Mn^IV sheets (bc) with similar oxygen sheets on either side, giving a distorted octahedral coordination to the Mn^IV. As every fourth Mn^IV is missing in these “main layers”, their composition becomes Mn₃O₈, and chains of coordination octahedra linked by common edges become distinct. Above and below the empty Mn^IV sites are either Mn^II or Cd^II completing the composition MnMnO₈ or Cd₂Mn₃O₈ respectively. Examples of similar “double layer” structures are given.     

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.     

Über ternäre Oxocuprate. X. Zur Kenntnis von Ba2Cu3O4Cl2

About Ternary Oxocuprates. X. On Ba₂Cu₃O₄Cl₂ The preparation of Ba₂Cu₃O₄Cl₂ and results by single crystal X-ray methods are described (a = 5.517, c = 13.808 Å; Space group D–I4/mmm). A so far unknown arrangement of square coordinated Cu²⁺ was detected. The Cu²⁺/O^2?-squares are partly completed to a distorted octahedral coordination by two Cl^?.     

LaCl(BO2)2 und Er2Cl2[B2O5]: Zwei Chlorid‐Oxoborate dreiwertiger Lanthanide

LaCl(BO₂)₂ and Er₂Cl₂[B₂O₅]: Two Chloride Oxoborates of Trivalent Lanthanides Er₂Cl₂[B₂O₅] is obtained as single crystals by the reaction of ErCl₃, Er₂O₃ and B₂O₃ with an excess of ErCl₃ as flux in evacuated silica tubes after two weeks at 850 °C. The compound crystallizes as long, pale pink needles and appears to be air‐ and water‐resistant. Single‐crystalline LaCl(BO₂)₂ emerges from the reaction of La₂O₃, LaCl₃, and B₂O₃ with an excess of B₂O₃ as flux in evacuated silica tubes after four weeks at 900 °C. LaCl(BO₂)₂ crystallizes as thin, colourless, air‐ and water‐resistant needles which tend to severe twinning due to their fibrous habit. The crystal structure of Er₂Cl₂[B₂O₅] (orthorhombic, Pbam; a = 1489.65(9), b = 1004.80(6), c = 524.86(3) pm; Z = 4) contains two crystallographically different erbium cations. (Er1)³⁺ resides in pentagonal‐bipyramidal coordination of seven anions while (Er2)³⁺ is surrounded by only six anions with the shape of an octahedron. The planar oxodiborate units [B₂O₅]^4— consisting of two vertex‐shared [BO₃]^3— triangles are isolated according to {([BOO]₂)^4—}. LaCl(BO₂)₂ crystallizes isostructurally with PrCl(BO₂)₂ in the triclinic space group P1¯ (a = 423.52(4), b = 662.16(7), c = 819.33(8) pm; α = 82.081(8), β = 89.238(9), γ = 72.109(7)°; Z = 2). The characteristic unit consists of endless chains built up by corner‐linked [BO₃]^3— triangles. These quasi‐planar zigzag chains of the composition {[(B1)OO(B2)OO]^2—} (≡ {[BO₂]^—} run parallel [100]. The La³⁺ cations exhibit coordination numbers of ten and are coordinated by three Cl^— and seven O^2— anions.     

Über hexagonale Perowskite mit Kationenfehlstellen. XXVI. Ba12Ba2 2/3M 1/3□2O33□3 (MV = Nb,Ta) – die ersten Stapelvarianten eines rhomboedrischen 36 L-Typs

On Hexagonal Perovskites with Cationic Vacancies. XXVI. Ba₁₂Ba_{2 2/3}M _1/3□₂O₃₃□₃ (M^V = Nb, Ta) – the First Stacking Polytypes of a Rhombohedral 36 L-Type In the systems BaO? MO₅(M^V = Nb, Ta) for a Ba:M^V ratio of 2:1 polymorphism is observed. Here the low temperature modifications are described. They crystallize in a rhombohedral 36 L structure with three formula units Ba₁₂Ba_{2 2/3}M _1/3□₂O₃₃□₃ for the trigonal setting (M^V = Nb: a = 5.92₂ Å; c = 93.₂₅ Å; Ta: a = 5,92₂ Å; s = 93.4 Å).     

Ein neues Oxometallat mit Mangan(II): Ba5Mn4Nd8O21

On a New Oxometallate of Manganese (II): Ba₅Mn₄Nd₈O₂₁ Single crystals of Ba₅Mn₄Nd₈O₂₁ were prepared for the first time by CO₂-Laser technique using H₂-atmosphere. It was investigated by a single crystal X-ray diffractometer study. Ba₅Mn₄Nd₈O₂₁ crystallizes with tetragonal symmetry space group: C? I4/m; a = 14.2104 Å; c = 5.8581 Å; Z = 2. Mn²⁺ is found in square pyramids of oxygen.     

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.     

Zur Kenntnis von Ba10Fe8Pt2Cl2O25

About Ba₁₀Fe₈Pt₂Cl₂O₂₅ The crystal structure of Ba₁₀Fe₈Pt₂Cl₂O₂₅ has been solved by direct methods, using intensity data collected by means of an automatic diffractometer (MoKα). It crystallizes in the hexagonal space group D–P6₃/mmc: a = 5.8034(4) Å, c = 24.997(5) Å, Z = 1. Fe³⁺ ions occur in both octahedral and tetrahedral coordination. Two types of Ba²⁺ ions are formed, with ten and twelve neighbouring atoms. The structure consists of plane connected FeO₆ and PtO₆ octahedra which are connected by corner shared FeO₄ tetrahedra.     

Die Photolumineszenz der dreiwertigen Seltenen Erden in den Perowskitstapelvarianten Ba2La2−xSE MgW2□O12, Ba6Y2−xSEW3□O18 und Sr8SrGd2−x SEW4□O24

Photoluminescence of Trivalent Rare Earths in Perovskite Stacking Polytypes Ba₂La_2?x RE MgW₂□O₁₂, Ba₆Y_2?x RE W₃□O₁₈, and Sr₈SrGd_2?xRE W₄□O₂₄ Rhombohedral 12 L stacking polytypes Ba₂La_2?xREMgW₂□O₁₂ show with RE³⁺ = Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm; the 18 L stacking polytypes Ba₆Y_2?xREW₃□O₁₈ and the polymorphic perovskites Sr₈SrGd_2?xREW₄□O₂₄ with RE³⁺ = Sm, Eu, Dy, Ho, Er visible photoluminescence. The concentration dependence and the influence of the coordination number of the rare earth are reported.     

Über hexagonale Perowskite mit Kationenfehlstellen. XVI Die rhomboedrischen 12 L-Stapelvarianten Ba3AIIIM□O12 mit MV = Nb,Ta

On Hexagonal Perovskites with Cationic Vacancies. XVI. Rhombohedral 12 L-Stacking Polytypes Ba₃A^IIIM □O₁₂ with M^V = Nb, Ta The white quaternary oxides Ba₃LaM□O₁₂ with M^V = Nb, Ta belong to the group of hexagonal perovskites with cationic vacancies. They crystallize in a rhombohedral 12 L-structure (sequence (hhcc)₃; space group R3 m) with a = 5.75₁ Å; c = 28.1₁ Å (M^V = Nb); a = 5.74₆ Å; c = 28.2₀ Å (Ta) and Z = 3. Signs for the formation of isotypic compounds with A^III = Pr, Nd could be obtained as well.     

Zur Atomverteilung in Ba2SrIn2O6 mit einem Beitrag zur Existenz des Calciumferrat(III)-Typs bei Oxoindaten

On the Atomic Distribution in Ba₂SrIn₂O₆ with a Contribution to the Existence of the Calciumferrite-Type of Oxoindates (I) Ba₂SrIn₂O₆ and (II) Sr_0.93Ba_0.07In₂O₄ were prepared and investigated by single crystal X-ray technique. I crystallizes with tetragonal symmetry, space group D – I4/mmm, a = 4.168; c = 21.290 Å; Z = 2; II belongs to the orthorhombic space group D – Pnma, a = 9.858; b = 3.273; c = 11.520 Å; Z = 4. I shows in respect to the formerly investigated compound BaSr₂In₂O₆ an unexpected statistically distribution of Ba²⁺ and Sr²⁺ with the La₂SrCu₂O₆ type. II marks the range of existence of the calciumferrite type within the alkaline earth oxoindates in direction of large radii of M²⁺ ions.     

Über Verbindungen des Typs Ba2BIIIOsVO6

Compounds of Type Ba₂B^IIIOs^VO₆ The black perovskites of type Ba₂B^IIIOs^VO₆ crystallize cubic (B^III ? Pr, Nd, Sm—Lu, Y) and rhombohedral (B^III ? La) respectively; the cell volumina decrease linearily with (r_BIII)³. Intensity calculations on powder data for Ba₂YOsO₆ (space group Fm3m—O) and Ba₂LaOsO₆ (space group R3m—D) gave the intensity related R′ values of 4.6% and 5.0% respectively. The results of the vibrational spectroscopic investigations are reported in common with the bond orders, M? O distances and mean amplitudes and compared with the corresponding values of the series Ba₂B^IIIIr^VO₆ and Ba₂B^IIIRu^VO₆.     

Über Ruthenium-Perowskite vom Typ Ba2BRuO6 und Ba3BRu2O9 mit B = Indium,Rhodium

On Ruthenium perovskites of type Ba₂BRuO₆ and Ba₃BRu₂O₉ with B = Indium, Rhodium The black perovskites Ba₂InRu⁵⁺O₆ and Ba₃InRu₂O₉ (mean oxydation state of ruthenium: +4.5) adopt the hexagonal BaTiO₃ structure and form a continuous series of mixed crystals. According to the intensity calculations and analysis of the vibrational spectroscopic data an ordered distribution between indium and ruthenium is present: 1:1 order in Ba₂InRuO₆ (space group P3 m1 ? D; R′ = 5.3%); 1:2 order in Ba₃InRu₂O₉ (space group P6₃/mmc ? D; R′ = 4.6%). The corresponding black Rh compounds, Ba₂RhRuO₆ and Ba₃RhRu₂O₉, crystallize in the rhombohedral 9 L type of BaRuO₃.     

Ein neuer Strukturtyp zur Formel ABLn2O5 Zur Kenntnis von BaNiNd2O5

A New Crystal Structure of ABLn₂O₅ Compounds. About BaNiNd₂O₅ The compound BaNiNd₂O₅ was prepared by solid state reaction. Single crystal examination show a new structure type (a = 3.829(2), b = 5.932(3), c = 11.649(3) Å space group D–Immm, Z = 2) with Ni²⁺ in octahedral coordination. The surrounding of Ba²⁺ and Nd³⁺ conforms to BaPtNd₂O₅ with significant differences of the polyhedra connection.     

Strukturbestimmungen an geordneten Perowskiten des Typs Ba2BMVIO6

Determination of Structures of Ordered Perovskites of the Ba₂B M^VIO₆ Type Intensity calculations on powder patterns of Ba₂Y□_0.33M^VIO₆ with M^VI = U, W, Te und Ba₂Gd_0.67□_0.33UO₆ lead for the space group Fm3m/O with 8 Ba in 8c, 8/3 B^III and 4/3 □ in 4b, 4 M^VI in 4a and 24 O in 24e to R values between 4.3 and 7.6%. Two further models are discussed.     

Die Kristallstrukturen der hexagonalen Elpasolithe Ba3NiSb2O9 und Ba3CuSb2O9 – röntgenographische und spektroskopische Ergebnisse

The Structures of the Hexagonal Elpasolite-Type Compounds Ba₃NiSb₂O₉ and Ba₃CuSb₂O₉ The results of an X-ray single crystal study of the hexagonal elpasolite Ba(NiSb₂)⁽⁶⁾O₉ are given. (Space group: C; a = b = 5.837 Å, c = 14.392 Å; Z = 2). The structure can be described by close-packed BaO₃ layers alternating in the sequence c c h c c h … (hex. BaTiO₃ type). Groups of two octahedra with common faces are connected by SbO₆ octahedra via common corners. They are occupied alternately by Ni and Sb. The final reliability index was R = 3.0%. The Cu²⁺-compound is of the same structural type. The ligand field and EPR spectra are discussed in comparison with related Ni²⁺ and Cu²⁺ compounds.     

Über hexagonale Perowskite mit Kationenfehlstellen. XXIV. Rhomboedrische 9 L-Stapelvarianten in den Systemen Ba3W M □ O9−x/2□x/2 mit MV = Nb,Ta

On Hexagonal Perovskites with Cationic Vacancies. XXIV. Rhombohedral 9 L Stacking Polytypes in the Systems Ba₃W M □O_9?x/2□_x?2 with M^V = Nb, Ta In the system Ba₃WNb□O_9?x/2□_x/2 stacking polytypes of rhombohedral 9 L type (sequence (hhc)₃; space group R3 m) can be prepared with ～1/3 ? × ? 2. For x = 2(Ba₃Nb₂□O₈□) two modifications are formed. In the corresponding Ta system the phase with is reduced to a smaller region with x ? 1/3.