Über Oxocadmate: K2Cd2O3

New obtained is K₂Cd₂O₃ (brownish red), which – according to single crystal work [487 h 01–h 41, Mo? Kα, R = 9.7₃%, R′ = 10.7₆%] – crystallises monoclinic with a = 6.41₇, b = 6.72₃, c = 6.58₆ Å, β = 116.0° in P2₁/c–C [K⁺, Cd²⁺ and O(1)^2? in 4(e), O(2)^2? in 2(a)] and is isotypic with Na₂Zn₂O₃. [Parameters see text]. The Madelung Part of Lattice Energy is calculated and discussed.     

Solid‐Liquid Equilibria in the Quinary Na+, K+//Cl−, SO2−4, B4O2−7‐H2O System at 298 K

The solid‐liquid equilibria in the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K had been studied experimentally using the method of isothermal solution saturation. Solubilities and densities of the solution of the quinary system were measured experimentally. Based on the experimental data, the dry‐salt phase diagram and water content diagram of the quinary system were constructed, respectively. In the equilibrium diagram of the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K, there are five invariant points F1, F2, F3, F4 and F5; eleven univariant curves E1F1, E2F2, E3F3, E4F5, E5F2, E6F4, E7F5, F1F4, F2F4 F1F3 and F3F5, and seven fields of crystallization saturated with Na₂B₄O₇ corresponding to Na₂SO₄, Na₂SO₄·10H₂O, Na₂SO₄·3K₂SO₄ (Gla), K₂SO₄, K₂B₄O₇·4H₂O, NaCl and KCl. The experimental results show that Na₂SO₄·3K₂SO₄ (Gla), K₂SO₄ and K₂B₄O₇·4H₂O have bigger crystallization fields than other salts in the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K.     

Oxydationsprodukte intermetallischer Phasen. III. Tieftemperaturformen von K2Sn2O3 und Rb2Sn2O3 und eine Notiz über K2Ge2O3

Oxidation Products of Intermetallic Compounds. III. Low Temperature Forms of K₂Sn₂O₃ and Rb₂Sn₂O₃ and a Notice about K₂Ge₂O₃ By controlled oxidation of KSn (at 320°C) and RbSn (at 410°C) with O₂ the hitherto unknown low temperature forms of K₂Sn₂O₃ (a = 8.4100(8) Å) and Rb₂Sn₂O₃ (a = 8.6368(8) Å) are obtained, which are isotopic with cubic K₂Pb₂O₃. Oxidation at higher temperatures (at 510–5207°C) leads to the well-known HT-forms. The Madelung Part of Lattic Energie, MAPLE, is calculated for both compounds. K₂Pb₂O₃, Rb₂Pb₂O₃, Cs₂Pb₂O₃, and Cs₂Sn₂O₃ have been prepared too by oxidation of KPb, RbPb, CsPb, and CsSn. Oxidation of KGe (at 400°C) leads to the first oxogermanate(II), K₂Ge₂O₃ (cubic a = 8.339(1) Å, isotypic with K₂Pb₂O₃) together with K₆Ge₂O₇.     

K2Zn3O4 und Rb2Zn3O4, zwei neue Oxozincate mit Gerüststruktur [1]

K₂Zn₃O₄ and Rb₂Zn₃O₄, Oxozincates with Framework Structure For the first time single crystals of K₂Zn₃O₄ were obtained by heating mixtures of the binary oxides (K: Zn = 2.2:3) in sealed Ag- or Pt-capsules at 800°C (5 w). Powder of this colourless and moisture-sensitive oxide was prepared analogously at 500°C. It crystallizes monoclinic, space group C2/c with a = 1482.7(2), b = 637.3(1), c = 571,9(1) pm, β = 102.79(1)°, Z = 4, d_x = 4.265 g/cm³, d_pyk = 4.00 g/cm³. The crystal structure was determined from four-circle diffractometer data (MoKα, 730 unique hkl) and refined to R = 5.9%, R_w = 6.4%. It shows a Zn₃O₄ framework which consists of SiS₂-like chains [ZnO_4/2] connected by puckered layers of [ZnO_3/3]. The crystal structure can be derived from a cubic closet packing of O^2? and K⁺. Effective Coordination Numbers and the Madelung Part of Lattice Energy (MAPLE) are calculated. Rb₂Zn₃O₄ was prepared from the binary oxides at 400°C (colourless hygroscopic powder). According to powder data it crystallizes isostructural to K₂Zn₃O₄ with a = 1523.5(4), b = 649.8(2), c = 574.0(2) pm, β = 101.43(3)°, Z = 4, d_x = 5.141 g/cm³, d_pyk = 5.20 g/cm³.     

Ein neues Periodat Zum Aufbau von K9Li3I2O13 = K9Li3O[IO6]2

A Novel Periodate: On the Structure of K₉Li₃I₂O₁₃ = K₉Li₃O[IO₆]₂ New obtained are weakly dichroitic (pale yellow/bluish) single crystals of K₉Li₃I₂O₁₃ by reaction of KIO₄, K₂O, and Li₂O (KIO₄:K₂O:Li₂O = 1:1:1.5; 800°C, 42 d). Space group P62c, Z = 2, a = 954.9 pm, c = 1172.2 pm, R = 6.2%, Rw = 5.6%, 957 symmetry independend I₀(hkl), MoKα . Characteristic for this structure are ?isolated”? O^2? and octahedral groups [IO₆]. The crystal structure has been determind. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

K2[(UO2)As2O7] – the First Uranium Polyarsenate

Yellowish crystals of K₂[(UO₂)As₂O₇] ( 1 ) have been synthesized by solid‐state reactions method. The structure of 1 [orthorhombic, Pmmn, a = 12.601(2), b = 13.242(2), c = 5.621(1) Å, V = 937.9(3) ų, Z = 4] has been solved by direct methods and refined to R₁ = 0.049, wR₂ = 0.1060 for 1059 observed reflections. The structure of 1 is based upon [(UO₂)As₂O₇]^2? sheets formed by corner sharing between [UO₆]^6? distorted octahedra and [As₂O₇]^4? polyarsenate groups. The K⁺ cations are either in eightfold or tenfold coordination and are located between the sheets. The topology of the uranyl arsenate sheet is related to silicate minerals of the melilite group and related synthetic silicate, aluminate and germanate compounds.     

Über gemischtvalente Oxoplumbate. Zur Kenntnis von Rb2Pb4O7 = Rb2PbPbO7

On Mixed-valent Oxoplumbates. On Rb₂Pb₄O₇ = Rb₂Pb Pb O₇ For the first time, Rb₂Pb₄O₇ has been prepared by annealing mixtures of Rb₂O₃ and PbO with Rb:Pb = 1:2 [Ag-cylinders, sealed under vacuum in Duran-glass ampoule, 450°C, 30 d (single crystals)]. The rubin red single crystals are of longish [001] shape. The structure determination [5162 symmetry independent hkl, four-circle-diffractometer CAD 4 (Fa. Enraf-Nonius), ω-2Θ—scan, AgKα, ψ-scan absorption correction, R = 7.54%, R_W = 7.71%] confirms the space group P1 with a = 1036.00(10), b = 733.72(8), c = 663.54(10) pm, α = 90.049(12)°, β = 99.236(12)°, γ = 101.641(12)°, Z = 2, d_rö = 7,58 g · cm^?3, d_pyk = 7,55 g · cm^?3. The structure is characterized by a layer-lattice. The coordination number is three for Pb²⁺, six for Pb⁴⁺. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Effective Ionic Radii, MEFIR, are calculated.     

Zur Konstitution von ‚KPbO2’︁

On the Constitution of ‘KPbO₂’ Transparent, orangered single crystals of K₂Pb₂O₄ have been obtained by heating mixtures of K₂O₂ and PbO (K:Pb = 1:1) [Ag-cylinders, 560°C, 40 d, after cooling (15°C/h)]. The space group is P1 , a = 1295.94(9), b = 753.35(7), c = 697.12(8) pm, α = 118.00(1)°, β = 106.15(1)°, γ = 93.44(1)°, Z = 4, d_x = 6.573 und d_pyk = 6.54 g · cm³. The structure is characterized by rutilanalogous chains of edge-connected [PbO₆] octahedra along [001] according to [PbO_4/2O_2/1] = PbO₄. On both sides of such a chain there are respectively three O^2?, which belong to two octahedra, alternating capped with Pb²⁺ or not capped, corresponding to [PbO₄]Pb₂[PbO₄]□₂… = Pb₂O₄. Those capped chains are held together by K(1)…K(4), each of them with C.N. 6. The order of the chains corresponds to the motive of a closest packing. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Zur Kenntnis ternärer Oxide des Bleis: Über Na2PbO2

On Ternary Oxides of Lead. The Na₆PbO₅ Na₆PbO₅ (pale yellow) crystallizes orthorhombic in Cmcm with a=10.6₈, b=5.70₉, c=10.9₉, å; Z=1. Parameters were refined by least-squares (479 hkO–hk7, MO–K_α) R=0.112₄, R′=0.116, (parameters see text). Isolated PbO₅ groups of pseudotetragonal pyramids lend Pb⁴⁺ Coordination Number (CN) 5. Along [100] and [010] the pyramids are equivalent orientated, but along [001] alternately twisted by 180°. Na+ occupies holes between O^2?, leading to CN 6 (Na″+) and Na″′⁺ and CN 4 (Na′⁺). The MADELUNG part of lattice energy (MAPLE) is calculated and discussed.     

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.     

Oxide eines neuen Formeltyps: Zur Kenntnis von K3Ni2O4 und K3Pt2O4

Oxides of a New Type of Formula: On the Knowledge of K₃Ni₂O₄ and K₃Pt₂O₄ K₃Ni₃O₄, greyblack single crystals, obtained by heating K₂O and NaNiO₂ [K:Ni = 2:1, 500°C, 7d, Ag-cylinders], crystallizes orthorhombic with a = 6.04₄, b = 9.04₉, c = 10.56₇ Å, Z = 4, space group Cmcm (d_rö = 3.43, d_pyk = 3.32 g · cm^?3). Due to four cycle diffractometer data (374 hkl, MoKα, R = 8.6percnt;) a new type of structure is found with wavebands of [NiO_4/2] \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm 1} $\end{document} exhibits the C.N. 6, \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm 2} $\end{document} the C.N. 4. Effective Coordination Numbers, ECoN, calculated by means of Mean Fictive Ionic Radii, MEFIR, the Madelung Part of Lattice Energy, MAPLE and the magnetic properties are discussed. K₃Pt₂O₄, black single crystals with metallic lustre, obtained by heating KO_x (x = 1.55 or 1.88) and Pt (powder) [K:Pt = 4:1,1000°C, lh, 600°C, 2d, Pt-capsules] is isotypic to K₃Ni₂O₄ (four cycle diffractometer data: 458 hkl, MoKα, R = 12percnt;). Cellparameters are a = 6.15, b = 9.27, c = 11.51 Å (single crystal data), d_rö = 5.79 and d_pyk = 5.77 g · cm^?3.     

Potassium oxoaluminate ­antimonate(III), K2[Al2Sb2O7]

Dipotassium dialuminium diantimonate, K₂[Al₂Sb₂O₇], crystallizes in the trigonal space group . The structure is isotypic with K₂Pb₂Ge₂O₇ and consists of [Al₂Sb₂O₇]^2? layers containing Al³⁺ in a nearly regular tetrahedral and Sb³⁺ in a Ψ‐tetrahedral environment of O ligands.     

K6[Mn2O6] und K6[Fe2 O6] - ein Vergleich

K₆[Mn₂O₆] and K₆[Fe₂O₆] - a Comparison K₆[Mn₂O₆] has been prepared (dark-red single crystals). The structure (a = 8.88₆, b = 6.76₀, c = 11.39₄ Å, γ = 132.1°, space group P2₁, Z = 2, 1151 symmetry independent reflections hk0–hk9, R = 0.051) shows Al₂Cl₆-like anions [Mn₂O₆]^6?. By unit-cell transformation to the monoclinic setting P2₁/a (a = 6.76₀, b = 11.39₄, c = 6.63₈ Å, β = 96,9°) the structural similarity to K₆[Fe₂O₆] becomes evident. The Madelung Part of Lattice Energy, MAPLE, is calculated.     

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 Oxydation intermetallischer Phasen: Die Oxoplumbate(II) K6[Pb2O5] [1] und K4[PbO3] [2]

On the Oxidation of Intermetallic Phases: The Oxoplumbates(II) K₆[Pb₂O₅] [1] and K₄[PbO₃] [2] Very pale yellow crystals of K₆[Pb₂O₅] were obtained by heating a wellground mixture of LiPb und K₂O₂ (K₂O₂: LiPb = 2.5:1) in Ag-tubes (550°C; 40 d). The crystal structure, triclinic, space group P1 , a = 1 326.7(6); b = 758.8(4); c = 637.0(3) pm; α = 92.17(3)°; β = 94.41(3)°; γ = 112.85(4)°; Z = 2 was determined (four-circle diffractometer data, Mo? K, 3 270 I_o(hkl), R = 8.0%, R_w = 3.5%, parameters see text). The pale yellow crystals of K₄[PbO3] were received by heating KPb and K₂O₂ (K₂O₂: KPb = 3.3:2) in Ni-tubes (450°C; 17 d). The crystal structure (orthorhombic, space group Pbca with a = 658.2(1); b = 1 131.8(4); c = 1 872.2(6) pm; Z = 8) was refined (four-circle diffractometer data, Mo? K, 2 003 I_o(hkl), R = 4.9%, R_w = 2.8%). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), the Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution (CHARDI) are being calculated for both oxides.     

Über neue Oxoniccolate: Zur Kenntnis von K9Ni2O7

New Oxoniccolates: On the Knowledge of K₉Ni₂O₇ K₉Ni₂O₇, deep dark-red, nearly black single crystals, obtained by heating K₂O and NiO [K:Ni = 5–6:1, 430°C, 5d, Au-cylinders] crystallizes cubic with a = 10.91₈ Å (P2₁3, Z = 4, d_rö = 2.97, d_pyk = 2.95 g·cm^?3). Due to fourcycle diffractometer data (490 hkl, MoKα, R = 9.9percent;) ‘isolated’ [NiO₄]^5? (nearly tetrahedral) and [NiO₃]^4? groups (trigonal-planar) are found. The Effective Coordination Number, ECoN, calculated by means of Mean Fictive Ionic radii, MEFIR, the Madelung Part of Lattice Energy, MAPLE, and the magnetic properties are discussed.     

Über quaternäre Oxoplumbate(IV). Zur Kenntnis von Rb2Li14[Pb3O14] und Cs2Li14[Pb3O14]

On Quaternary Oxoplumbates(IV). On the Knowledge of Rb₂Li₁₄[Pb₃O₁₄] and Cs₂Li₁₄[Pb₃O₁₄] For the first time, Rb₂Li₁₄[Pb₃O₁₄] and Cs₂Li₁₄[Pb₃O₁₄] have been prepared by heating of mixtures of Li₂O, β-?PbO₂”? and Rb₂PbO₃, Cs₂PbO₃ respectively with Li:Pb:A = 14:3:2, (A = Rb, Cs). [Ag-cylinders, sealed under vacuum in Duran-glass ampoule, 590 and 550°C, 40 d, powder (650°C, 200 d, single crystals of Rb₂Li₁₄[Pb₃O₁₄])]. Rb₂Li₁₄[Pb₃O₁₄] is nearly colourless with ivory nuance, Cs₂Li₁₄[Pb₃O₁₄] is pale yellow. According to powder and single crystal investigations, both are isotypic with K₂Li₁₄[Pb₃O₁₄]. Structure refinement of Rb₂Li₁₄[Pb₃O₁₄]: 1015 symmetry independent reflexions, four-circle-diffraktometer PW 1100 (Fa. Philips), ω-scan, MoKα, R = 5.73%, R_W = 5.33%, absorption not considered, space group Immm with a = 1284.71(9), b = 793.90(4), c = 727,35(5) pm, d_x-ray = 4.99 g · cm^?3, d_pyc = 5.01 g · cm^?3, Z = 2. Cs₂Li₁₄[Pb₃O₁₄]: a = 1295.28(12), b = 796.69(8), c = 732.44(7) pm, d_x-ray = 5.31 g · cm^?3, d_pyc = 5.28 g · cm^?3, Z = 2. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Effective Ionic Radii, MEFIR, are calculated.     

Metal Ion Interaction of Two New Tritopic N2O13 Macrobicycles with B15C5 Moieties in Acetonitrile Solution

The synthesis of two new tritopic crown ligands (L1 and L2) bearing two benzo-15-crown-5 lateral moieties linked through a dibenzo-trioxa chain together with their interaction with metal ions, in acetonitrile and acetonitrile–water (50%, v/v) solutions is reported. The influence of K⁺, Na⁺, Li⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺ and Al³⁺, on the spectroscopic properties of these diaza-polyoxa ligands was investigated by absorption spectrophotometry and in some cases by fluorescence emission spectroscopy. Coordination with alkaline (Na⁺, K⁺ and Li⁺) and alkaline earth (Ca²⁺and Ba²⁺) metal ions is assumed to be weak with both macrobicyclic ligands, while the interaction with both imine and amine derivatives causes a minor effect in the absorption spectra. Coordination with Cu²⁺, Zn²⁺ and Pb²⁺ in acetonitrile solution causes a major change in the absorption spectra of the chromophores. In the case of Cu²⁺, addition of the metal to L1 or L2 leads to a blue–violet complex in solution with an absorbance maximum centred at 590 nm. Interaction of the Schiff-base L1 with Pb²⁺ leads to a short wavelength shift in the absorption bands, comparable with the ZnL1 complex. Presence of transition metal ions such as Co²⁺, Ni²⁺and Cd²⁺ do not remarkably affect the absorption spectra of L1 and L2 in solution. Trivalent aluminium has a modest effect in the absorption bands of both N₂O₁₃ donor set bismacrocyclic ligands. The fluorescence study of L2 in the presence of Na⁺, K⁺, Ca²⁺, Ba²⁺, Co²⁺, Cu²⁺, Ni²⁺, Pb²⁺ and Al³⁺shows that Cu²⁺, Pb²⁺ and Al³⁺ complexes form non-fluorescent complexes.     

Structural and Raman Spectroscopic Investigations of K4BaSi3O9 and K4CaSi3O9

The crystal structures of K₄BaSi₃O₉ and K₄CaSi₃O₉ have been characterized by X‐ray diffraction techniques as well as Raman spectroscopy. The structure of K₄CaSi₃O₉ has been refined from powder diffraction data via the Rietveld method using polycrystalline material prepared from solid state reactions. The compound is isostructural with form I of K₄SrSi₃O₉. It crystallizes with 16 formula units in a cubic primitive cell (a = 15.94014(3) Å, V = 4050.20(1) ų) and adopts space group . K₄CaSi₃O₉ belongs to the group of cyclosilicates and contains highly puckered twelve‐membered [Si₁₂O₃₆]‐rings centered on the . Five of the seven crystallographically independent alkaline and alkaline earth cations are surrounded by six oxygen ligands in the form of distorted octahedra, which share opposite triangular faces and form non‐intersecting columns parallel to the body diagonals of the cubic unit cell. This arrangement corresponds to one of the cubic cylinder or rod packings. The two remaining sites have more irregular coordination environments with eight next oxygen neighbors. High temperature X‐ray powder diffraction data have been collected to determine the thermal expansion of this material: between room temperature and 700 °C the coefficient of thermal expansion has a value of α = 12.9(2) × 10^?6 [°C^?1]. Single crystals of K₄BaSi₃O₉ have been obtained from the devitrification of a glass with the same composition. The structure was determined from a single crystal diffraction data set collected at ?100 °C and refined to a final R index of 0.0298 for 1288 observed reflections (I > 2σ(>I)). The compound is isostructural with modification II of K₄SrSi₃O₉. Basic crystallographic data are as follows: space group Ama2, a = 11.0695(15) Å, b = 8.0708(10) Å, c = 11.905(2) Å, V = 1063.6(3) ų, Z = 4. With respect to the silicate anions the material can be classified as a sechser single chain silicate. The crankshaft‐like chains run parallel to [100] and are linked by K and Ba cations, which are distributed among five crystallographically independent sites. The coordination polyhedra of two of the non‐tetrahedral cations can be described by distorted octahedra sharing opposite triangular faces. They build non‐intersecting columns parallel to [011] and [0‐11], respectively. The other sites exhibit more irregular coordination spheres with 7‐9 neighbours.