Über Oxocuprate. XVIII. Zur Kenntnis von Sr2CuO2Br2 mit einem Beitrag über La2NiO4

About Oxocuprates. XVIII. On Sr₂CuO₂Br₂ and a Contribution about La₂NiO₄ Sr₂CuO₂Br₂ (A) and La₂NiO₄ (B) were prepared and investigated by single crystal X-ray technique. (A) is isotypic with Sr₂CuO₂Cl₂, (B) with K₂NiF₄. Both compounds crystallize in the space group D–I4/mmm with the lattice constants (A): a = 399.1, c = 1 713.6 pm, (B): a = 387.6, c = 1 268.3 pm. A discussion about the octahedral distortion of Cu²⁺ and Ni²⁺ respectively in respect to other isotypic compounds is given.     

Ein Beitrag über Sr2RuO4 und Sr3Ru2O7 Zur Oktaederstreckung von M4+ in K2NiF4- und Sr3Ti2O7-Typ-Verbindungen

On the Thermal Decomposition of Hg₂I₂ and the Hg? I State Diagram Solid Hg₂I₂ decomposes congruently in Hg and HgI₂. The entropy S°(Hg₂I₂,s,298) = (55,5 ± 1) cal/K · mol and the enthalpy of formation ΔH_f°(Hg₂I₂, s, 298) = (?30,0 ± 2) kcal/mol are derived from the decomposition equilibrium. The phase diagram of the whole system Hg? I was constructed from investigations by DTA and total pressure measurements in the partial systems Hg? Hg₂I₂, Hg₂I₂? HgI₂, and HgI₂? I₂. It follows, that Hg₂I₂ melts incongruently at 297°C and decomposes in a Hg-rich and HgI₂-rich melt. The emerging miscibility gap is assumed to close at a temperature near 500°C.     

über Erdalkalimetalloxocuprate,VIII Zur Kenntnis von Sr2CuO2Cl2

On Alkaline Earth Oxocuprates VIII. About Sr₂CuO₂Cl₂ Sr₂CuO₂Cl₂ was prepared and investigated by single crystal X – ray work (space group D–Immm, a = 3.975, c = 15.618 Å). Sr₂CuO₂Cl₂ is isotypic with K₂NiF₄ – compounds and shows an octahedral configuration for Cu²⁺. Cl^? occupies trans-positions of the octahedral Cu²⁺/O^2? polyhedron. A discussion with related compounds (Sr₂CuO₃ and Nd₂CuO₄) explains the observed distribution of O^2? and Cl^?.     

Berylliumoxometallate. II. Zur Kenntnis von Be4Pr9O20

Oxometallates with Beryllium. II. About Be₄Pr₉O₂₀ High temperature reactions yield single crystals of the new compound Be₄Pr₉O₂₀. X-ray investigations show orthorhombic symmetry (space group C_2v⁹? Pna2₁; a = 954.1, b = 655.7, c = 722.7 pm). Structure and coordination of Be⁺⁺ and Pr^3+/4+ are discussed in respect to the chemical composition.     

Über Oxoindate der Alkalimetalle Zur Kenntnis von Rb2In4O7

Oxoindates of Alkali Metals. On Rb₂In₄O₇ The hitherto unknown Rb₂In₄O₇ crystallizes trigonal with a = 5.62₈, c = 7.34₀Å, c/a = 1.30, z = 1 in thespacegroupD–P3 1m. The atomic parameter see text. The structure derives from a cubic closest packing of O²- with In³⁺ in 1/9 of the tetra-hedral and 2/9 of the ovtahedral sites. Rb substituates 2/3 of the O²- ions of each third layer. The MADELUNG Part of Lattice Energy is calculated and discussed.     

Bor-Stickstoff-Verbindungen. XXXIX. Untersuchungen über die Bildung von Borazolen: Zur Kenntnis der Reaktionsprodukte der Umsetzung von Bortrichlorid mit Methylamin

The reaction boron trichloride with methylamine can be directed to yield either tris(methylamino)borane or B-tris(methylamino)-N-trimethylborazine depending upon the molar ratio of the reactants. The vibrational spectrum of tris(methylamino)borane is discussed and the reaction of the compound with boron trichloride has been studied. Interpretation of the experimental data permits to suggest a possible mechanism for the formation of borazines.     

Über Neue Oxoruthenate vom Typ der 6 L-Perowskite: Ba3SrRu2−xTaxO9 (x = 0,8 und 1,4) mit einem Beitrag über Ba3CaRu2O9

On Novel Oxoruthenates of the 6 L-Perovskite Type: Ba₃SrRu_2?xTa_xO₉ (x = 0.8 and 1.4) with a Comment on Ba₃CaRu₂O₉ Single crystals of the phases Ba₃SrRu_2?xTa_xO₉ [(I): x = 0.8 and (II): x = 1.4] and the compound (III): Ba₃CaRu₂O₉ were prepared by a BaCl₂ flux and investigated by X-ray methods. (I)–(III) crystallizes with hexagonal symmetry space group P6 2c with lattice constants: (I) a = 6.003 Å; c = 15.227 Å; (II) a = 5.988 Å; c = 15.220 Å and (III) a = 5.891 Å; c = 14.571 Å. The crystal structures of these substances corresponds to the 6 layer perovskites with the stacking sequence (hcc)₂. All of them show a so far not described slightly distorted oxygen framework caused by the Sr²⁺ and Ca²⁺ ions.     

Neues über Oxogermanate. 1. Zur Kenntnis von K4GeO4

News on Oxogermanates. 1. On K₄GeO₄ For the first time single crystals of K₄GeO₄ have been prepared by heating KO_0.46 and GeO₂. The structure has been refined. K₄GeO₄: 2565 I₀(hkl), four circle diffractometer PW 1100, ω-scan, AgKα, R = 0.0826, R_w = 0.0837, P1 ; a = 640.56(35), b = 633.87(34), c = 933.68(45) pm; α = 80.26(5)°, β = 107.58(5)°, γ = 113.63(4)°; d_x = 2.94 g/cm³; d_pyk = 2.91 g/cm³; Z = 2. K₄GeO₄ is isotypic with K₄SnO₄. There is, however, an essential difference of the C.P. (Coordination Polyhedra) with respect to K4 and O4. The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattic Energy, MAPLE, are calculated.     

Zur Kenntnis von Cu6La4Mo9O36

About Cu₆La₄Mo₉O₃₆ Single crystals of Cu₆La₄Mo₉O₃₆ were prepared and investigated by X-ray work. It shows trigonal symmetry, space group R3c — C; a = 20.892, c = 12.754 Å; Z = 6. Cu₆La₄Mo₉O₃₆ represents a new structure type, characterized by MoO₄-tetrahedrons and three times capped trigonal prisms around La³⁺. Cu⁺ shows coordination numbers 2 + 1 or 2 + 2.     

Zur Kristallstruktur von SmZrF7 mit einem Anhang über EuSnF7 und YSnF7

On the Crystal Structure of SmZrF₇ with an Appendix on EuSnF₇ and YSnF₇ SmZrF₇ again was obtained as colourless single crystals and investigated by X-ray methods: It crystallizes in space group P 2₁/c-C (Nr. 14; P 2₁/n) with a = 1 140.9(2) pm, b = 574.6(1) pm, c = 914,4(2) pm, β = 107.32(2)°, Z = 4 but not in space group P 2₁-C (Nr. 4) [1]. In addition EuSnF₇ and YSnF₇ are isotypic with the following lattice constants: EuSnF₇: a = 1 121.8(2) pm, b = 563.7(1) pm, c = 901.7(1) pm, β = 107.35(2)° with Z = 4; YSnF₇: a = 1 106.7(2) pm, b = 556.4(1) pm, c = 884.7(1) pm, β = 107.51(1)° and Z = 4 (Powder data).     

Über Oxothorate der Alkalimetalle. Zur Kenntnis von K3NaTh2O6

On Oxothorates of the Alkaline Metals: K₃NaTh₂O₆ For a first time single crystals of a (in addition: new) oxothorate were prepared starting with the binary oxides [1 200°C, 4d, then 1 300°C, 5d, Ni-bomb; powder: 650°C, 10d, Ag-bomb]. The colourless, transparent single crystals are monoclinic, C2/c, a = 629.64 pm, b = 1 089.93 pm, c = 1 259.75 pm, β = 99.66°, z = 4, D_x = 5.458 g cm_?3 and D_pyc = 5.456 gcm_?3. It is an ordered variant of the NaCl-type; MoKα, fourcircle diffractometer data (PW 1100), R = 7.6₇ and R_w = 7.3₅% for 1 083 of 1 236 I₀ (hkl). The Madelung Part of Lattice Energy, MAPLE, is calculated and 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.     

Über Borate der Alkalimetalle. III. Zur Kenntnis von Na4B2O5

About Borates of Alkali Metals. III. On Na₄B₂O₅ Na₄B₂O₅ was obtained as single crystals for the first time; monoclinic, C2/c? C with a = 10.61₈ (2), b = 8.01₅ (1), c = 6.28₇ (2) Å; β = 110.1₀ (1)°; Z = 4, d₀ = 2.46, d_c = 2.55₇ g/cm^?3. The structure was solved by direct methods; R = 4.6% for 1010 independend reflections. The crystal structure contains [B₂O₅] groups, which exhibit point symmetry 2. A comparison with already known groups of this kind is given. The Madelung part of lattice energy, MAPLE and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Zur Kenntnis von Zn4Ta2O9

About the New Compound Zn₄Ta₂O₉ The hitherto unknown compound Zn₄Ta₂O₉was prepared by high temperature reaction (CO₂-LASER technique). The X-ray investigation of single crystal shows monoclinic symmetry (space group C? C2/c) with a = 15.002(6), b = 8.954(1), c = 10.345(4)Å and β = 93.64(3)°. Zn₄Ta₂O₉ consists of a Zn/O-network with incorporated one-dimensional TaO₆-chains. The edge connected TaO₆-octahedrals are occupied by Ta⁵⁺ and 0.5 Zn²⁺ respectively. The crystal chemistry of this compound in respect to other Zn-oxotantalates are discussed.     

Zur Kenntnis von Sr2Bi3V3O14

On Sr₂Bi₃V₃O₁₄ Single crystals of the hitherto unknown compound Sr₃Bi₃V₃O₁₄ were prepared and investigated by X-ray work. It crystallizes with triclinic symmetry, space group P1 , a = 7.0838, b = 7.1732, c = 14.1067 Å; α = 97.46, β = 98.70, γ = 110.99°, Z = 2. The crystal structure is characterized by VO₄ tetrahedra and one side open Bi³⁺ coordination inside Bi₂O₁₁ groups.     

Über Oxobismutate. Zur Kenntnis von Na3BiO4 und Na3SbO4

On oxobismuthates. The compounds Na₃BiO₄ and Na₂SbO₄ Na₃BiO₄ crystallizes monoclinic in C⁴_2h; a = 5.87₁ b = 6.69⁶, c = 5.65₀ Å and β = 109,8° with Z = 2. We have a variant of the NaCl type, forming chains ¹_∞[BiO_4/2+2/1] along [001]. The MADELUNG part of lattice energy (MAPLE) of Na₃BiO₄ and different other structure models are calculated und discussed. Na₃SbO₄[a = 5.79₅, b = 6.59₅, c = 5.41₈ Å, β = 109.4°] is isotypic with Na₃BiO₄.     

Zur Kenntnis der Reaktion von Phenylperthiophosphonsäureanhydrid mit Schwefelchloriden und -oxidchloriden

The Reaction of Phenyl Perthiophosphonic Anhydride with Sulphur Chlorides and Oxidechlorides The reaction of phenyl perthiophosphonic anhydride with equimolar amounts of SCl₂ and S₂Cl₂ yields quantitatively bis-(phenylchlorothiophosphonyl)-tri-(II) and -tetrasulfane(VI), respectively. The corresponding disulfane XII is the primary product of the reaction between I and SO₂Cl₂ while I and SOCl₂ form compound VIII.     

Ein Beitrag Zur Verbindung Sr3Nd4O9

A Contribution on Sr₃Nd₄O₉ The metastable compound Sr₃Nd₄O₉ was prepared by high temperature reactions and investigated by X-ray single crystal methods. It crystallizes with monoclinic symmetry: a = 1147.4; b = 723.8; c = 1324.6 pm and β = 115.6°: space group C? Cs. The metal positions show a nearly statistical distribution of Sr²⁺ and Nd³⁺. The network of the polyhedrals characterizes a new structure type, which in spite of the statistical metal distribution does not belong to the high temperature X-modification of the Rare Earth sesquioxides.     

Zur Kenntnis der neuen Phosphorsulfidphase P4S9. II. Über verschiedene Methoden zur Darstellung und über die Eigenschaften und Konstitution des P4S9

Both, reaction of red phosphorus, P₄S₃ or P₄S₇ with sulphur, and elimination of sulphur from P₄S₁₀ yield the new phosphorus sulphide phase P₄S₉. This phase exists in two modifications. The properties and constitution of the P₄S₉ phase are described.