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.     

Zur Verbindungsbildung von MeO:M2O3. VI. Darstellung und Strukturaufklärung von Sr1,33 Pb0,67 Al6O11

Compound Formation MeO: M₂O₃. VI. Synthesis and Structure Determination of Sr_1,33 Pb_0,67 Al₆O₁₁ Single crystal of Sr_1,33Pb_0.67Al₆O₁₁ could be prepared with a PbO flux. (Space group D–Pnnm, a = 22.13, b = 4.88, c = 8.42 Å, Z = 4) Sr²⁺ and Pb²⁺ are statistically intercalated into a framework of AlO₆ octahedra and AlO₄ tetrahedra. The typical coordination of Sr²⁺ and Pb²⁺ is realized by occupying different positions in the same cavern.     

Ba5AlIr2O11: Eine neue Verbindung mit Iridium(IV,V)

Ba₅AlIr₂O₁₁: A New Compound with Iridium(IV, V) The hitherto unknown compound Ba₅AlIr₂O₁₁ was prepared and investigated by X-ray technique (space group D–Pnma, a = 18.8360; b = 5.7887; c = 11.1030 Å; Z = 4). Iridium has an octahedral coordination in each case two octahedra are connected by a plane. These double octahedra form with corner connected AlO₄ tetrahedra [Ir₂AlO₁₁]^10? units. Ba₅AlIr₂O₁₁ is not related to the perovskite type compounds.     

Synthese und Aufbau von Ba2MnO3

Synthesis and Structure of Ba₂MnO₃ Single crystals of Ba₂MnO₃ could be prepared by solid state reaction in hydrogen atmosphere. X-ray structure investigations gave a monoclinic unit cell (a = 584; b = 1157.₉; c = 1270.₇ pm; β = 93.7₄°; space group C? Cc). Mn²⁺ forms isolated tetrahedron chains connected by 7-fold coordinated Ba²⁺.     

Mononuclear Thiolatecobalt Carbonyls

A Partial Statistically Incorporation of Ca²⁺ into the Ba₆Nd₂Al₄O₁₅-Type: Ba₅CaLa₂Fe₄O₁₅ Using high temperature reactions we succeeded in incorporating Ca²⁺ into the Ba₆Nd₂Al₄O₁₅ type. Single crystal X-ray methods reveal a partly ordered alkaline earth distribution. Ba²⁺ and Ca²⁺ occupy face connected MO₆-octahedra as well as a further point position together with La³⁺ ions (space group C−P6₃mc; a = 11.770; c = 7.039 Å; Z = 2).     

Stability of Complex Metal Bromides in the gas phase and in toluene

The equilibrium constants of the reactions MBr₂(s) + Al₂Br₆(sln) ? MAl₂Br₈(sln) M = Cr, Mn, Co, Ni, Zn, Cd have been measured at 298 K in toluene. Ni: 0.017 ± 0.0024, Co: 0.54 ± 0.07, Zn: 1.5 ± 0.2, Mn: 2.1 ± 0, 7, Cr: 2.2 ± 1, Cd: 7 ± 5. They are compared with literature values of the equilibrium constants of analogous reactions in the gas phase MX₂(s) + Al₂X₆(g) ? MAl₂X₈(g), X = Cl, Br. For CoAl₂Br₈(sln) the temperature dependence of the equilibrium constant yielded Δ_fH = ?9.4 ± 1 kJ mol^?1 and Δ_fS = ?39.5 ± 3 J mol^?1 K^?1 while literature values for CoAl₂Br₈(g) are Δ_fH = 42.4 ± 2 kJ mol^?1 and Δ_fS = 42.9 ± 2 J mol^?1 K^?1. The solubility of Al₂Br₆ in toluene as well as its enthalpy of dissolution have been measured in order to evaluate ΔH° and ΔS° of the solvation of Al₂Br₆(g) and CoAl₂Br₈(g) in toluene by a thermodynamic cycle. Solvation of Al₂Br₆(g): ΔH = ?72.7 ± 1 kJ mol^?1, ΔS = ?139.6 ± 4 J mol^?1 K^?1, solvation of CoAl₂Br₈(g): ΔH = ?124.5 ± 4kJ mol^?1, ΔS = ?222 ± 9J mol^?1 K^?1. Thus, CoAl₂Br₈ interacts more strongly with the solvent toluene than Al₂Br₆ does.     

Zur Kristallchemie der Oxoplumbate(II). I. Zur Kenntnis von Pb9Al8O21

Solid State Chemistry of Lead Monoxid Compounds. I. About Pb₉Al₈O₂₁ The hitherto unknown compound Pb₉Al₈O₂₁ was prepared and examined by single crystal methods (space group T? Pa3; a = 1326 pm, Z = 4). AlO₄ tetrahedra form a threedimensional network with large cavities containing [Pb₉O₂]¹⁴⁺ groups.     

Ein Beitrag über Ba3Pt4HgO11: Das erste Erdkalimetall-Oxoplatinat(II,V)/Oxomercurat

A Contribution on Ba₃Pt₄HgO₁₁: The First Alkaline-Earth Oxoplatinate(II,V)/Oxomercurate Single crystals of Ba₃Pt₄HgO₁₁ were prepared by oxygen high pressure technique (4 200–3 600 bar) and investigated by X-ray methods. It crystallizes with hexagonal symmetry, space group D? P6 2c, a = 6.021, c = 17.374 Å, Z = 2. Ba₃Pt₄HgO₁₁ represents a new structure type, showing structural relationships to Ba₂Hg₃Pd₇O₁₄ and to the precious metal 6L-perovskites. The Hg²⁺ ions show dumb-bell like coordination, Pt²⁺ a square-planar surrounding and Pt⁵⁺ face shared double octahedra.     

Geordnete Oktaederbesetzung in Ba6La2Al1,5Fe2,5O15

Ordered Occupation of Octahedra in Ba₆La₂Al_1,5Fe_2,5O₁₅ Ba₆La₂Al_1.5Fe_2.5O₁₅ was prepared and investigated by X-ray single crystal technique. It crystallizes in the space group C – P6₃mc; a = 11.814, c = 7.1003 Å; Z = 2. The M³⁺O₆ octahedra are occupied exclusively by Fe³⁺ ions, the M³⁺O₄ tetrahedra in contrast are statistically filled by Fe³⁺ and Al³⁺ ions. Ba₆La₂Al_1.5Fe_2.5O₁₅ is a partially ordered mixed crystal of the pure iron and aluminium compounds.     

Zur Kristallstruktur von Ba2ZnO3

On the Crystal Structure of Ba₂ZnO₃ Single crystals of Ba₂ZnO₃ were prepared by solid state reaction. It crystallizes monoclinic: space group C ? C12/c1; a = 5.833; b = 11.376; c = 12.585 Å; β = 93.63°; Z = 8. The crystal structure is characterised by [ZnO₃] chains along [100]. They are connected by Ba²⁺ in seven fold oxygen coordination.     

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.     

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.     

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.     

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. 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).     

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 Hexagonale Perowskite mit Kationenfehlstellen. I. Verbindungen vom Typ Ba2B□2/3ReVIIO6

On Hexagonal Perovskites with Cationic Vacancies. I. Compounds of the Type Ba₂B □_2/3Re^VIIO₆ Compounds of Type Ba₂B□_2/3Re^VIIO₆ are formed with B^III = Sm? Gd Ho? Lu, Y, Sc, In (yellow); Tb (black-brown); Dy (yellow-orange). They crystallize with B^III = Sm? Lu, Y and Sc in a rhombohedral layer structure of 12 L-type (space group R3 m; sequence: cchhcchhcchh) with 6 formula units in the unit cell.     

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 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).     

Ba6CoNb9O30: Ein neuer Vertreter der tetragonalen Wolframbronzen

Ba₆CoNb₉O₃₀: A New Compound of the Tetragonal Bronze Structure The hitherto unknown compound Ba₆CoNb₉O₃₀ was examined by X-ray single crystal work. (Space group C-P4bm; a = 1258.9; c = 400.9 pm) Co³⁺ and Nb⁵⁺ occupy a special position in an octahedral framework. The coordination of Ba²⁺ is discussed.