Das erste Alkali-Erdalkalimetall-Oxoniccolat(II,III): NaBa2Ni22+Ni3+O6

The First Alkalinc Alkaline Earth Oxoniccolate(II,III): NaBa₂Ni₂²⁺Ni³⁺O₆ Single crystals of NaBa₂Ni₂²⁺Ni³⁺O₆ were prepared by solid state reaction. X-ray investigations led to orthorhombic symmetry, space group D-Fmmm; a = 8.310; b = 11.220; c = 14.397 Å; Z = 8. Na⁺ is coordinated by six O^2? in form of a trigonal prism and the two Ba²⁺ point positions show different coordination numbers C.N. = 6 + 4 and 8. The Ni²⁺ /Ni³⁺ ions are in square planar polygons, six of them are forming a so far unknown closed macro polyhedra.     

Zur Kenntnis komplexer Fluoride mit Cu2+ und Pd2+: MPtF6 (M  Pd,Cu) und RbCuPdF5

On Complex Fluorides with Cu²⁺ and Pd²⁺: MPtF₆ (M ? Pd, Cu) and RbCuPdF₅ For the first time single crystals of PdPtF₆ (green), trigonal-rhomboedric, a = 503.8, c = 1431.6 pm, spcgr. R3 ? C (No. 148), Z = 3, CuPtF₆ (orange), triclinic, a = 495.2, b = 498.5, c = 962.4 pm, α = 89.98, β = 104.23, γ = 120.35°, spcgr. P1 ? C (No. 2), Z = 2 and RbCuPdF₅ (orange brown, in connection with investigations on M^IPd₂F₅ [1]), orthorhombic, a = 626.9, b = 719.9, c = 1076.3 pm, spcgr. Pnma? D (No. 62), Z = 4, four circle diffractometer data, have been obtained.     

Das erste Alkali-Erdalkalimetall-Oxo/Peroxo-Aurat(III): NaBa4AuO4(O2)2

On the first Alkaline-Alkaline-Earth-Oxo/Peroxo-Aurate(III): NaBa₄AuO₄(O₂)₂ The hitherto unknown compound NaBa₄AuO₄(O₂)₂ was prepared by oxidizing of barium gold alloy with Na₂O₂ in closed Ag-bombs. X-ray single crystal investigation led to tetragonal symmetry space group DI4/mmm, a = 5.939; c = 15.393 Å, Z = 2. NaBa₄AuO₄(O₂)₂ shows a distorted square antiprismatic surrounding of Ba²⁺ by four peroxo groups on one side and four O^2? on the opposite. Au³⁺ shows the usual square planar polygons of AuO₄. Na⁺ is coordinated by four O^2? ions in the base of an octahedron and two peroxo groups in the apical positions.     

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.     

Cuprous complexes and dioxygen. Part 11. Concomitant one- and two-electron reduction of O2 by the Cu ion

The autoxidation of Cu^I in aqueous MeCN has been studied using a Clark oxygen electrode in the presence and absence of Cu¹¹. The reaction is inhibited by Cu¹¹ in the pH range of 0.5 to 5.0, reaching a lower limiting value at the highest concentrations. The reaction order changes from 1 to 2 with respect to Cu^I under the influence of Cu²⁺ ion. Detailed kinetics analysis of a total of 275 measurements has shown that an unstable primary adduct CuO⁺₂ decomoses to give ^.O or HO, depnding on pH, and also reacts directly with a second Cu⁺ ion, avoiding one-electrton reduction of O₂ by this path. Reaction of HO is faster with Cu^I than with Cu¹¹ by a factor of 20, and single-electron transfer within CuO⁺₂ to Cu²⁺ and ^.O predominates over reaction with a second copper ion for [Cu^I_tot] < 2. 10^?3M in the absence of Cu²⁺. The most likely value for the reaction of ^.O with Cu^I is 5.3 · 10⁸ M ^?1S^?1, but even this high rate constant is at the limit of significance. All secondary reactions followinfg the initial formation of CuO⁺₂ are shown to be very fast, a fact that should be properly considered in the discussion of mechanisms of copper-catalyzed oxidations and oxygenations.     

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^?.     

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.     

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.     

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.     

Synthese und Struktur einer neuen Form von CuYMo2O8

Synthesis and Structure of a New form of CuYMo₂O₈ Single crystals of a new form of CuYMo₂O₈ were prepared and investigated by X-ray diffractometer technique [space group D-Pbca; a = 10.160 Å, b = 9.701 Å, c = 14.527 Å; Z = 8]. CuYMo₂O₈ represents a new structure type characterised by MoO₄-tetrahedrons, Cu⁺ with coordination number 2 + 1 and square antiprisms around Y³⁺. The crystal structure and the Cu⁺ coordination are discussed.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

Na2BaCuV2O8: Ein neuer Strukturtyp der Alkali-Erdalkalimetall Kupfer-Oxovanadate

Na₂BaCuV₂O₈: A New Structure Type of the Alkaline-Alkaline Earth Copper Oxovanadates Single crystals of Na₂BaCuV₂O₈ were prepared by a high temperature flux. It crystallizes with monoclinic symmetry space group C–C2/c, a = 9.4329 Å, b = 5.6858 Å, c = 14.0488 Å, β = 92.344° Z = 4 and represents a new structure type. The crystal structure show VO₄ tetrahedra, stretched CuO₆ octahedra, trigonal bipyramids around Na⁺ and a BaO₁₀₊₂ polyedron.     

Darstellung und Kristallstruktur von Na2Mn3O7

Synthesis and Crystal-Structure of Na₂Mn₃O₇ Single crystals of Na₂Mn₃O₇ have been grown hydrothermally applying high oxygen pressure (p = 2 kbar). The new compound cystallizes triclinic; space group P1 ; a = 6.636(6) Å, b = 6.854(6) Å, c = 7.548(6) Å, α = 105.76(6)°, β = 106.86(6)°, γ = 111.60(6)°; Z = 2. The crystal structure has been solved and refined to R = 7.9% and R_w = 6.2% (diffractometer data, 1044 independent reflexions). The crystal structure consists of Mn₃O₇^2? anions with manganese coordinated octahedrally by oxygen. These layered anions are hold together by Na⁺ ions (coordination numbers 5 and 6).     

Ein neues Alkali-Erdalkalimetall-Kupfer-Oxovanadat: Kba3Ca4Cu3V7O28

A new Alkaline-Alkaline-Earth-Copper-Oxovanadate: Kba₃Ca₄Cu₃V₇O₂₈ . Single crystals of Kba₃Ca₄Cu₃V₇O₂₈ were prepared by solid state reactions below the melting point of the reaction mixture. It crystallizes with hexagonal symmetry, space group C?P6₃mc, a=11.160, c=12.428 Å, Z=2. Kba₃Ca₄Cu₃V₇O₂₈ represents a new structure type with special coordination polyhedra around Ba²⁺, trigonal prisms and octahedra around Ca²⁺ and Cu²⁺ inside square pyramids. The crystal structure will be shown and discussed.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Ein neues Erdalkalimetall-Oxoplatinat-Cuprat Ca3,5Cu0,5PtO6

A new Alkaline-Earth Platinum Copper Oxide: Ca_3.5Cu_0.5PtO₆ Ca_3.5Cu_0.5PtO₆ was prepared and investigated by single crystal X-ray work. (Space group C? C12/m1; a = 9.0743; b = 9.2527; c = 6.4840 Å; β = 91.448°; Z = 4). The crystal structure of the previously unknown compound is closely related to the structure of Sr₃PtCuO₆ and Sr₃IrCuO₆ as well as the rhombohedral phases M₄PtO₆ (M = Ba, Sr, Ca). Typical features of the crystal chemistry are isolated chains of PtO₆ octahedra, alternately allyed by square CuO₄ polygones and trigonal prisms of O^2? around Ca²⁺.     

Zur Kristallstruktur von Cu3NbTaO8

On the Crystal Structure of Cu₃NbTaO₈ Single crystals of Cu₃NbTaO₈ were prepared by solid state reaction. X-ray investigations led to triclinic symmetry, space group C? P1 with a = 5.179; b = 5.474; c = 6.003 Å; α = 72.85°; β = 83.39°; γ = 65.77°; Z = 1. Nb⁵⁺ and Ta⁵⁺ occupy one point position statistically. Both ions show an octahedral oxygen surrounding. Cu(1) is inside an elongated CuO₆ octahedra and Cu(2) is coordinated by 5 O^2? forming a distorted square pyramid. The polyhedra connection is shown and discussed.     

Synthese und Struktur des ersten ternären Blei(II)-Oxocuprats(I): PbCu2O2

Synthesis and Structure of the First Ternary Lead(II) Copper(I) Oxide: PbCu₂O₂ PbCu₂O₂ can be prepared by solid state reaction or by precipitation from a basic aqueous solution. Single crystals of the new compound were prepared by recrystallisation from a molten mixture (PbO? Cu₂O) and investigated by X-ray diffractometer technique. PbCu₂O₂ crystallizes isotypically with the homologue silver compound PbAg₂O₂ (monoclinic with a = 8.22₃ Å, b = 8.28₉ Å, c = 6.01₅ Å, β = 132.6₂°, Z = 4, space group C? C 1 2/c 1). The crystallographic data from the X-ray investigation are reported. The structure is built by endless [PbO_4/4]- and [CuO_2/4]-chains. Pb²⁺ has a one-sided asymmetric coordination with four next oxygen neighbours and Cu⁺ forms a stretched dumbbell with two oxygen atoms.     

Cuprous complexes and dioxygen. IX. Formation of a unique trimeric species Cu3L and Ligand Oxidation (L  cis,cis-1, 3, 5-cyclohexanetriamine)

The complexation of Cu⁺ by the potentially tripod like ligand cis, cis-1, 3, 5 cyclohexanetriamine (chta) has been studied potentiometrically in aqueous acetonitrile (an). The expected tetracoordinated species Cu (chta) ? (an)⁺ was formed only at rather high pH with log K (Cu (an)⁺ + chta ? Cu (chta) · (an)⁺) = 6.94. Quite unexpectedly the most stable complex in neutral solution was the trimetric species Cu³ (chta) with log K (3 Cu⁺ + 2 chta ? Cu³ (chta)) = 31.75. In addition, the ternary complexes Cu (LH²) · (an)³⁺ and Cu (LH) · (an)²⁺ (L = chta) are formed at low pH. From model considerations, Cu³ (chta) must contain two ligand molecules with all amino groups in equatorial position, linked by three linearly coordinated Cu⁺-ions. Cu₃ (chta)³⁺₂ shows no measurable reactivity towards dioxygen. At pH values above 9, very rapid O₂-uptake due to Cu (chta) · (an)⁺ is observed. In this reaction, Cu⁺-autoxidation is stoichiometrically coupled to ligand oxidation, followed by a much slower Cu-catalyzed secondary reaction of the primary oxidation product of chta. Hydrogen peroxide and likely also superoxide, are involved in the coupled Cu⁺/ligand oxidation.     

Synthese und Untersuchung von NiNb2O6-Einkristallen mit Columbit- und Rutilstruktur

Synthesis and Investigation of NiNb₂O₆ Single Crystals of Columbite and Rutil Type C-NiNb₂O₆ (columbite type) and R-NiNb₂O₆ (rutil type) single crystals were prepared by solid state reactions. C-NiNb₂O₆ a = 14.032; b = 5.687; c = 5.033 Å, space group D—Pbcn. R-NiNb₂O₆ a = 4.710; c = 3.038 Å, space group D—P4₂/mnm. The metal positions of the rutil structure are statisticaly occupied by Ni²⁺ and Nb⁵⁺ ions. R-NiNb₂O₆ is in respect to lower temperatures a metastable compound.