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.     

RuS4Cl12 und Ru2S6Cl16, zwei neue Ruthenium(II)‐Komplexe mit SCl2‐Liganden

RuS₄Cl₁₂ and Ru₂S₆Cl₁₆, Two New Ruthenium(II) Complexes with SCl₂ Ligands Ru powder was reacted with SCl₂ in closed silika ampoules at 140 °C. From the black solution three compounds RuS₄Cl₁₂ 1 , Ru₂S₆Cl₁₆ 2 , and Ru₂S₄Cl₁₃ 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P2₁/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl₃[RuCl₃(SCl₂)₃]. In the structure the complex anions fac‐[RuCl₃(SCl₂)₃]^– and the cations [SCl₃]⁺ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl₂)₃ClRu(μ‐Cl)₂RuCl(SCl₂)₃ with two fac‐RuCl₃(SCl₂)₃‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl₂(SCl₂)Ru(μ‐Cl)₃Ru(SCl₂)₃]. The vibrational spectra and the thermal behaviour of the compounds are discussed.     

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.     

Zur Kenntnis von Ba4Ir3O10

About Ba₄Ir₃O₁₀ Single crystals of Ba₄Ir₃O₁₀ were prepared by a flux technique. X-ray investigations show monoclinic symmetry, space group C_2h⁵–P2₁/a; a = 5.788; b = 13.222; c = 7.242 Å; β = 112.98°; Z = 2. Ir₃O₁₂ tripel, built up by face-sharing of IrO₆ octahedra, are edge-connected into wave-like twodimensional planes. Ba₄Ir₃O₁₀ is related to Ba₄(Ti, Pt)₃O₁₀.     

Zur Kenntnis von Ca3IrCuO6

On Ca₃IrCuO₆ Single crystals of Ca₃IrCuO₆ were prepared by a flux technique and investigated by single crystal X-ray work. It crystallizes with monoclinic symmetry, space group C—C12/c1; a = 9.032, b = 9.295, c = 6.466 Å, β = 91.35°, Z = 4. Ca₃IrCuO₆ is isotypic to Sr₃IrCuO₆. The square planare CuO₄ polygones show probably a slightly deficit accompanied by an adequate part of iridium in the oxydation state Ir⁵⁺.     

Zur Kenntnis von Ba2As6O11

Concerning Ba₂As₆O₁₁ Ba₂As₆O₁₁ was prepared by hydrothermal reaction of BaO with As₂O₃ at a temperature of 200°C. An X-ray structural analysis demonstrated that the phase contains highly condensed polyarsenate(III) anions (As₆O₁₁^4?)_n. A zweier double chain structure was observed for the anion, in which the individual chains are bridged to one another by two Ψ-AsO₃ tetrahedra, so that As₁₀O₁₀ rings are formed. The double chains are linked into “double sheets”, perpendicular to the b-axis, through relatively strong secondary O … As bonds with an average length of 2.68 Å.     

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.     

Zur Kenntnis von Ba6La2Co4O15

About Ba₆La₂Co₄O₁₅ Ba₆La₂Co₄O₁₅ were prepared and investigated by X-ray single crystal work. It crystallizes with hexagonal symmetry, space group C–P6₃mc; a = 11.8082; c = 7.0019 Å; Z = 2. Ba²⁺ show face connected BaO₆-octahedra and larger polyhedra of C.N. = 10 and 12. Co³⁺ is surrounded by four and six (tetrahedra, octahedra) oxygen. The Ba²⁺ and La³⁺ ions occupy one point position statistically.     

Zur Kenntnis von cis-Natriumhyponitrit

To the Knowledge of cis-Sodium Hyponitrite Surprisingly, cis-sodium hyponitrite can be prepared by reacting gaseous N₂O and solid Na₂O. For the first time, the structure of a simple salt of cis hyponitrous acid has been determinated unambigously. According to an abinitio structure determination based on powder data, cis-Na₂N₂O₂ crystallizes monoclinic (P2₁/c, a = 5.107(1); b = 9.211(1); c = 6.159(1) Å; β = 97.91(1)°; Z = 4). Results of spectroscopic investigations (vibrational spectroscopy, ¹⁵N-MAS-NMR) agree with the symmetry of the cis-N₂O₂^2? anion as it has been proved by the crystal structure. Consider able differences regarding some chemical and physical properties have been observed for samples of cis-Na₂N₂O₂ synthesized via different routes.     

Zur Kenntnis von Sr2CrMnO6

About the New Compound Sr₂CrMnO₆ Sr₂CrMnO₆ was prepared and investigated by X-ray single crystal data (a = 541.6; c = 664.0 pm; space group C–P3 ). The structure is related to the distorted perovskites, the differences to SrCrO₃ and SrMnO₃ are discussed.     

Über Oxocuprate. XI. Zur Kenntnis von Ba3Cu2O4Cl2

On Osocuprates. XI. Ba₃Cu₂O₄Cl₂ A new oxohalogenocuprat, Ba₃Cu₂O₄Cl₂ mas prepared and investigated by X-ray single crystal methods. The hitherto unknown compound has orthorhombic symmetry (Space group: D_2h⁵—Pmma; a = 6.653, b = 6.000, c = 10.563 Å). It shows angled chains of O^2?-squares around Cu²⁺. One of the Cu²⁺ positions is completed by Cl^minus; to a tetragonal pyramid. The coordination polyhedrals of Ba_I–III and the connection with the Cu/O-chains are described and discussed.     

Zur Kenntnis eines Erdalkalimetall-Oxopalladats(II) mit ringförmigen Pd6O12-Baugruppen: CaBa2Pd3O6

On an Alkaline-Earth Oxopalladate containing Pd₆O₁₂ Rings: CaBa₂Pd₃O₆ CaBa₂Pd₃O₆ was prepared for the first time and investigated by X-ray single crystal technique. It is isotypic to NaBa₂Cu₃O₆ and crystallizes with orthorhombic symmetry, space group D-Fmmm, a = 8.717, b = 11.47, c = 14.933 Å; Z = 2. Typical features of the crystal structure are edge connected square planar PdO₄ polygones, forming isolated Pd₆O₁₂ rings.     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Zur Kenntnis von SrCa2In2O6

About SrCa₂In₂O₆ The hitherto unknown compound SrCa₂In₂O₆ was investigated by X-ray single crystal methods (a = 1 104.6, b = 1 663.0, c = 327.9 pm, space group D—Pbam). SrCa₂In₂O₆ is isotypic with Ca₃In₂O₆, but it will be shown that Ca₂In₂O₆ may be a special case of the polyhedral occupation of the SrCa₂In₂O₆ structure.     

Synthesis and Structure of Ba7F12Cl2

Crystals of ordered and disordered Ba₇F₁₂Cl₂ were prepared by flux growth and solid state reactions. These new structures were characterized by single crystal and powder X‐ray diffraction. The disordered variant which shows disorder on one of the cation sites was obtained from a BaF₂ + BaCl₂ + NaCl/NaF flux. It has hexagonal space group P6₃/m (176) with one formula unit per unit cell. The lattice constants are a = b = 1059.55(5) pm and c = 420.10(4) pm (at 21 °C). The structure was refined to R(R_w) = 0.026(0.030) for 346 independent reflections and 26 parameters. Slow cooling of a mixture of BaF₂ and LiCl yields the ordered variant. This one crystallizes in the hexagonal space group P6 (174) with one formula per unit cell. Lattice constants at 21 °C are a = b = 1063.46(2) pm and c = 417.52(1) pm. The structure was refined to R(R_w) = 0.017 (0.017) for 638 independent reflections and 45 parameters. The structural arrangement and the interatomic distances of the two variants are mutually similar. The barium atoms have coordination number nine. Propeller‐type arrangements with a chloride ion on the axis and the fluoride ions as blades are observed. These latter ones are interconnected into ‘channels' of tricapped fluoride prisms. Occupation disorder of the barium sites in the channels of the disordered variant makes the main difference between the two. An unexpectedly high X‐ray density obtained for both variants of Ba₇F₁₂Cl₂ can be correlated to the density of other barium fluorohalides having a coordination number of nine for the barium ion.     

Zur Kristallchemie der Blei-Lanthanoid-Oxoaluminate. Zur Kenntnis von Pb2HoAl3O8 und Pb2LuAl3O8

Crystal Chemistry of the Lead Lanthanide Oxoaluminates. On Pb₂HoAl₃O₈ and Pb₂LuAl₃O₈ . Single crystals of (I) Pb₂HoAl₃O₈ and (II) Pb₂LuAl₃O₈ were prepared by flux technique and investigated by X-ray methods. It crystallizes with cubic symmetry, space group O–P4₂/n 3 2/m, (I): a = 9.4164(13) Å, (II): a = 9.3486(8) Å, Z = 4. The new structure type shows AlO₄ tetrahedra, LnO₈ hexagonal bipyramids and one sided coordinated Pb²⁺ within heterocubane units. The crystal chemical relationships to other lead oxides containing heterocubane Pb₄O₄ units are discussed.     

Zur Kenntnis von NiPtF6 und CdPtF6

Anotation to Compounds MPtF₆ (M = Ni, Cd) Yellow single crystals of M¹¹PtF₆ (M¹¹ = Ni, Cd) have been obtained for the first time and investigated by X-ray methods. The powder data of the compounds are confirmed. Both samples are isostructural to LiSbF₆, space group R3 -C (Nr. 148) with a = 500.5(3) pm, c = 1375.6(7) pm for NiPtF₆ and a = 511.56(9) pm, c = 1460.3(4) pm for CdPtF₆, Z = 3.     

Zur Kristallstruktur von MnF3 und MnPtF6

On the Crystal Structure of MnF₃ and MnPtF₆ Single crystal investigations of MnF₃ (rubyred) confirmed the crystal structure based on powder data [2]: monoclinic, space group C 2/c?C (No. 15) with a = 892.02 pm, b = 504.72 pm, c = 1 347.48 pm, β = 92.64° with Z = 12. The corresponding determination of the crystal structure of MnPtF₆, yellow, confirmed the unit cell [3] with a = 510.47 pm, c = 1 421.0 pm and γ = 120°, Z = 3 space group R 3 -C (No. 148). For both compounds detailed parameters respectively interatomic distances have been obtained.     

Zur Kristallstruktur von Ba3Al2F12

Concerning the Crystal Structure of Ba₃Al₂F₁₂ Preparing BaMnAlF₇ we obtained single crystals of Ba₃Al₂F₁₂ as a by‐product (a = 1020.3(2), b = 988.5(1), c = 952.2(1) pm, space group Pnnm, Z = 4). The redetermination confirmed the structure already known, but improved the results (R₁′ = 0.028 and wR₂ = 0.06 for 1908 and 2717 reflections, resp.). An interpretation is given for the relation of distances within the tetrameric anion [Al₄F₂₀]^8— (average Al—F: 180, 1 pm). The construction of the cationic frame [Ba₃F₂]⁴⁺ is discussed.     

Synthesis and Structure of the Ordered Modification of Ba6EuF12Cl2

Crystals of ordered Ba₆EuF₁₂Cl₂ were found to form during high temperature flux growth. The structure was refined in the hexagonal space group P 6 to R^F(R ) = 0.024(0.024) for 326 reflections and 46 parameters. Lattice parameters are a = b = 1059.27(8) pm and c = 416.36(2) pm; Z = 1. The structure is isotypic to Ba₇F₁₂Cl₂. No solid solution of Ba/Eu was observed, the Eu²⁺ ions are located in the channels formed by 3 + 6 fluorine ions, occupying only one of the three metal sites of the Ba₇F₁₂Cl₂ structure.