Neuartige Mäander mit Co3+ und Au3+: Na4[AuCoO5] = Na8 [(O2/2(CoO)O2AuO2/2)2]

Novel meander with Co³⁺ und Au³⁺: Na₄[AuCoO₅] = Na₈ ¹∞ [(O_2/2 (CoO)O₂AuO_2/2)₂] By “reaction with the wall” we obtained for the first time transparent brown single crystals of Na₄[AuCoO₅] while heating intimate mixtures of Co₃O₄, Na₂O₂, and K₂O₂ (Co: Na: K = 1.00:4.91:2.20; 650°C/44d) in a sealed gold-tube: monoclinic, P2₁/m, with a = 555.69(4) pm, b = 1042.11 (8) pm, c = 555.69(4) pm, β = 117.387(5)°, Z = 2. Characteristic features of Na₄[AuCoO₅] are meandric chains [(O_2/2 (CoO)O₂AuO_2/2)₂]. The structure has been determined by four-circle diffractometer data (Siemens AED 2; Mo? Kα , graphite, 881 I₀(hkl), R = 0.0366, R_w = 0.0316), parameters as given in the text. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, these via Mean Fictive Ionic Radii, and Charge-distribution, CHARDI, are calculated and discussed.     

Die ersten Oxocobaltate(II) mit zweikernigem Anion: Rb2Na4[Co2O5] und K2Na4[Co2O5]

The First Oxocobaltate(II) with Dinuclear Anion: Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] By heating of well ground mixtures of the binary oxides [A₂O, Na₂O, ?CoO”?, A:Na:Co = 1.00:2.00:1, (A = K, Rb); Ag-tube, 600°C, 14 d] we obtained Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] rough, transparent, red single crystals. We find a new type of structure with the anion [O₂CoOCoO₂]^6?. Space group P4₂/mnm; a = 634.4 pm, c = 1030.3 pm, Z = 2 (A = K) a = 647.6 pm, c = 1021.1 pm, Z = 2 (A = Rb); four-circle diffractometer data; MoKα -radiation; 360 from 364 I₀(hkl), R = 4.34%, R_w = 3.54% (A = K); 361 from 366 I₀(hkl), R = 6.54%, R_w = 2.70% (A = Rb). The anion is planar, the CN of Co is 3. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Neue Metalloxide mit Tetraeder-Doppel als Baugruppe: Rb6[Tl2O6] und Cs6[In2O6]

New Metal Oxides with Doubles of Tetrahedra as Building Units: Rb₆[Tl₂O₆] and Cs₆[In₂O₆] We prepared the hitherto unknown Rb₆[Tl₂O₆] and Cs₆[In₂O₆] by heating mixtures of Tl₂O₃ and RbO_0.60 (Rb:Tl = 3.5:1) as well as In₂O₃ and CsO_0.53 (Cs:In = 3.5:1) as single crystals [closed Ag-cylinder, 650°C, 14 d]. The single crystals of Rb₆[Tl₂O₆] are yellow, those of Cs₆[In₂O₆] pale yellow, all transparent and rude. The new type of structure was elucidated by 4-circle-diffractometer (PW 1100) data. Rb₆[Tl₂O₆]: P2₁/a; a = 1145,7(3), b = 713,3(1), c = 783,9(2) pm, β = 93,73° (2), Z = 2; Ag–Kα, 2100 out of 2531 I₀(hkl), R = 9,6% and R_w = 8,9%. Cs₆[In₂O₆]: P2₁/a; a = 1178,5(4), b = 730,7(2), c = 816,3(2) pm, β = 95,38° (3), Z = 2; Mo–Kα, 1584 out of 2032 I₀(hkl), R = 9,25%, and R_w = 8,44%. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Über Perrhenate. 3 Zum Aufbau des Mesoperrhenates Na3[ReO5]

About Perrhenates. 3 On the Structure of the Mesoperrhenate Na₃[ReO₅] By tempering powder samples (prepared from mixtures of binary oxides: Na₂O₂/ReO₂ and Na₂O/ReO₃ respectively, Na : Re = 3 : 1, Ar and O₂ atmosphere respectively, 400–450°C, corundum boat) in a closed Ag cylinder (500–550°C, 10 d) yellow single crystals of Na₃ReO₅, sensitive to moisture, were grown. The compound crystallizes trigonal, space group P3₁, P3₂ respectively, with a = 5.544(1), c = 13.580(7) Å, Z = 3, d_rö. = 4.62 g/cm³. The crystal structure [4-circle diffractometer data, 1091 I₀(hkl), AgKα, R = 6.14, R_w = 6.08%] is characterized by “isolated” bipyramids ReO₅. Na⁺ ions are occupying all the tetrahedral (Na2, Na3) and octahedral (Na1) holes of the pseudocubic face centred (c/a = 2.441) Re part of the lattice; resulting in a Na₃Re kation framework corresponding to the Li₃Bi type of structure. Effective Coordination Numbers (ECoN), the Madelung Part of Lattice energy (MAPLE) and the charge distribution (CHARDI) are computed and discussed.     

Zur kenntnis ‚Kationen-reicher’︁ Tantalate und Niobate Über Na5TaO5 und Na5NbO5

On Tantalates and Niobates ‘rich in Cations’. On Na₅TaO₅ and Na₅NbO₅ Colourless, transparent single crystals of Na₅TaO₅ [annealed mixtures of Na₂O, Li₂O, and Ta₂O₅, Na : Li : Ta = 6.6 : 1.1 : 1, Ni-cylinder, 1000°C, 75 d] as well as Na₅NbO₅ [annealed mixtures of Na₂O, Li₂O, and Nb₂O₅, Na : Li : Nb = 6.6 : 1.1 : 1, Ni-cylinder, 1000°C, 75 d] have been prepared. Single crystal data show that both isotypic oxides represent a deformed variant of the NaCl-type of structure [Na₅TaO₅: 1154 from 1250 I₀ (hkl), four-cycle diffractometer Philips PW 1100, ω2-θ scan, Ag? Kα , R = 4.88%, space group c2/c with a = 629.3(1) pm, b = 1025.4(2) pm, c = 1004.6(2) pm, b? 106.80(2)°, z = 4 and Na₅NbO₅: 998 from 1247 I₀(hkl), four-cycle diffractometer Philips PW 1100, ω-2θ scan, Ag? Kα , R = 8.58% and R_w = 7.67%, space group C2/2 with a = 629.1(1) pm, b = 1024.4(2) pm, c = 1004.2(2) pm, b? = 106.80(2)°, Z = 4]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Fictive Ionic Radii, MEFIR, as well as Charge Distribution, CHARDI, are calculated.     

Das erste Diniobat mit ‚isolierten’︁ Anionen: KLi4[NbO5]=K2Li8[Nb2O10]

The First Diniobate with ‘Isolated’ Anions: KLi₄[NbO₅]=K₂Li₈[Nb₂O₁₀] [1] . By heating of well ground mixtures of the binary oxides [K₂O, Li₂O, Nb₂O₅, K:Li:Nb=1.1:4.4:1, Pt-tube, 1100°C, 3d] colourless, triclinic single crystals of KLi₄NbO₅ have been prepared for the first time: space group P1 (Nr. 2) with a=816.9(2) pm, b=592.2(2) pm, c=589.7(2) pm, α=121.00(2)º, β=91.78(2)°, γ=99.23(2)°, Z=2. The crystal structure was solved by four-cycle diffractometer data [Mo-Kα , 1386 from 1386 I_o(hkl), R=3.4%, R_w=2.6%], parameters see text. Characteristic for this structure are “isolated” groups of [Nb₂O₁₀] and the tetrahedral coordination of Li(1), Li(2), and Li(3). Li(4) has a tetragonal-pyramidal coordination. The structural relations are deduced by Schlegel Diagrams. The Madelung Part of Lattice Energy, MAPLE, the Effective Coordination Numbers, ECoN and the charge distribution have been calculated and discussed.     

Über Oxostannate(II). V. Na4[SnO3] – das erste Oxostannat(II) mit „Inselstruktur”︁

On Oxostannates(II). V. Na₄[SnO₃] – The First Oxostannate (II) with Island Structure The new oxid Na₄SnO₃ (yellow, transparant single crystals) has been prepared by heating of mixtures of: 1. NaO_0.45 and SnO (Na:Sn²⁺ = 4.1:1; Ag-cylinders; 600–730°C, 7–66 d); 2. NaO_0.45′ SnO₂ and Sn^±0 (Na:Sn⁴⁺:Sn^±0 = 8.2:1:1; Ag-cylinders; 650–680°C, 2–66 d); 3. NaO_0.45′ Na₂SnO₃ and Sn^±0 (Na:Na₂SnO₃:Sn^±0 = 6.1:1:1; Ag-cylinders; 650–670°C, 5 d). Na₄SnO₃:804 I₀(hkl); four circle diffractometer PW 1100; ω-scan; MoKα; R = 5.14%; R_w = 4.64%; monoclin, Cc? C; a = 582.77(11), b = 1667.44(24), c = 589.42(10) pm, β = 110.187(13)°; d_x = 3.20 g/cm³; d_pyk = 3.19 g/cm³; Z = 4; parameter look for text. It is a NaCl-variant with systemathical blanks of the anion part and “isolated” groups of [SnO₃]. \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm N}\mathop {\rm a}\limits^{\rm 1} $\end{document} has the uncommon coordination number 2. The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated. The structure is described using ?Erweiterte Schlegeldiagramme”?.     

Über Oxostannate(II). III. K2Sn2O3, Rb2Sn2O3 und Cs2Sn2O3 – ein Vergleich

On Oxostannates(II). III. K₂Sn₂0₃, Rb₂Sn₂0₃, and Cs₂Sn₂O₃ – a Comparison Hitherto unknown Rb₂Sn₂O₃ has been obtained by heating of mixtures of binary oxides [RbO_0.48 + SnO, Rb:Sn = 1.1:1, Al₂O₃?cylinders, Ar] as deep yellow powder or deep yellow single crystals. It is isotypic to K₂Sn₂O₃, R3 m-D with a = 6.086 Å, c = 15.101 Å, Z = 3, d_calc = 4.69, d_obs = 4.64 g X cm^?3. For 260 hkl it is R = 5.2₇% and R_w = 5.0₉% (MoKα, 4-circle diffractometer data). The structure of K₂Sn₂O₃ and Rb₂Sn₂O₃ is compared with that of Cs₂Sn₂O₃. For both types Effektive Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, have been calculated.     

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.