Notiz über den α-LiFeO2-Typ: NaPrO2 und NaTbO2

On the α-LiFeO₂ Type of Structure: NaPrO₂ and NaTbO₂ For the first time transparent light-green single crystals of NaPrO₂ [from PrO_1,833: KO_0,50:NaO_0,50 = 1:1.1:1.2 Ni-cylinder, 1000°C, 20 d] and colourless single crystals of hitherto unknown NaTbO₂ [from Na₂TbO₃, Ni-cylinder, 1000°C, 10 d] have been prepared and investigated by X-ray. The tetragonal α-LiFeO₂-type is confirmed. [NaPrO₂: a = 476.19(3), c = 1096.09(11) pm, c/a = 2.30; 107 I₀ (hkl); R = 4.25% R_w = 3.39%, MoKα; NaTbO₂: a = 463.11(3), c = 1037.39(12) pm, c/a = 2.24; 103 I₀ (hkl); R = 3.54%; R_w = 2,81%; MoKα; both space group I4₁/a m d; fourcircle diffractometer Philips PW 1100]. The Madelung Part of Lattice Energy, MAPLE, and the peculiarities of this type of structure are discussed.     

Notiz über Li2PdO2

Note on Li₂PdO₂ For the first time we prepared ruby-red single crystals of Li₂PdO₂ by reaction with the wall 3 Na₂O + Li₂O₂ + ?Tb₄O₇”?(+ Pd) = 3 Na₂TbO₃ + Li₂PdO₂ + ?TbO₂”?, Pd-tube, 1100°C, 7 d. Single crystal data confirm the Li₂CuO₂-type of structure [a = 375.34(5), b = 298.18(4), c = 931.58(10) pm; spacegroup Immm; d_x = 4.85 g · cm^?3; 144 I₀(hkl); R = 3.54%, Rw = 3.19%; MoKα ; four-circle diffractometer Philips PW 1100] and reveal clearly different parameters compared with those deduced by powder data. The Madelung Part of Lattice Energy, MAPLE, corresponds now to the sum of the MAPLE values of the binary oxides.     

Eine Notiz zum A-Typ der Lanthanoidoxide: Über Pr2O3

The A-type of Lanthanoide Oxides: On Pr₂O₃ . “Reductive” thermal decomposition of K₂PrO₃ [Ni-cylinder, semi-open system, 1000°C, 14 d] leads for the first time to light green single crystals of Pr₂O₃. The structure determination [105 symmetry independent hkl, four circle diffractometer Philips PW 1100; MoKα; R = 6.30%, R_w = 5.01%; space group P3m1; Z = 1; a = 385.77(3), c = 601.20(6) pm] verifies the A-type according to the proposed structure by PAULING .     

Neue Vertreter des K2Li14[Pb3O14]-Typs Cs2Li14[Tb3O14] und K2Li14[Zr3O14] [1, 2]

Inhaltsübersicht. Erstmals wurden klar durchscheinende, orange-farbene Einkristalle von Cs₂Li₁₄[Tb₃O₁₄] aus Cs₂TbO₃ und Li₂O (Tb: Li = 1:5) dargestellt [550°C, 21 d, verschlossenes AuRohr]. Es liegt der K₂Li₁₄[Pb₃O₁₄]-Typ vor [Vierkreisdiffraktometerdaten, PW 1100, MoKä-Strahlung, 660 I_o(hkl), R = 4,8%, R_w = 3,4%, Immm, a = 1293,5(8), b = 792,6(3), c = 740,4(3) pm, Z = 2, d_rö = 4,65]. Ebenfalls neu wurde K₂Li₁₄[Zr₃O₁₄] in Form farbloser Einkristalle durch Tempern inniger Gemenge von K₂O, Li₂O und ZrO₂ (K: Li: Zr = 1:4:1,5) dargestellt [900°C, 14 d, geschlossene Ni-Bombe] und röntgenographisch untersucht. Die Strukturverfeinerung [612 I_o(hkl), Vierkreisdiffraktometerdaten, PW 1100, MoKα-Strahlung, R = 5,9%, R_w = 5,3%, Immm, a = 1244,6, b = 776,4, c = 724,3 pm, Z = 2] bestätigt die Isotypie mit K₂Li₁₄[Pb₃O₁₄]. Der Madelunganteil der Gitterenergie, MAPLE, Effektive Koordinationszahlen, ECoN, diese über Mittlere Effektive Ionenradien, MEFIR, wurden berechnet. Für die nun bekannten Vertreter dieses Typs wurde ein Isotypievergleich vorgenommen. New Compounds of the K₂Li₁₄[Pb₃O₁₄] Type: Cs₂Li₁₄[Tb₈O₁₄] and K₂Li₁₄[Zr₃O₁₄] For the first time Cs₂Li₁₄[Tb₃O₁₄] has been prepared as orange single crystals from Cs₂TbO₃ and Li₂O (Tb: Li = 1:5) [550°C, 21 d, sealed Au-Tube]. Structure Refinement [four-circle diffractometer data, PW 1100, MoKα radiation, 660 I_o(hkl), R = 4.8%, R_w = 3.4%, Immm, a = 1293.5(8), b = 792.6(3), c = 740.4(3) pm, Z = 2, d_rö = 4.65] confirms isotypy with K₂Li₁₄[Pb₃O₁₄]. K₂Li₁₄[Zr₃O₁₄] has also been prepared as colorless single crystals from K₂O, Li₂O, and ZrO₂ (K: Li: Zr = 1:4:1.5), [900°C, 14 d, closed Ni-cylinder] and investigated by x-ray [612 I_o(hkl), four-circle diffractometer data, PW 1100, MoKα radiation, R = 5.9%, R_w = 5.3%, Immm, a = 1244.6, b = 776.4, c = 724.3 pm, Z = 2]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Fictive Ionic Radii, MEFIR, are calculated. A detailed comparison of the structures is carried out.     

Quaternäre Monoborate der Alkalimetalle: Na4Li5[BO3]3

Quaternary Monoborates of Alkali Metals: Na₄Li₅[BO₃]₃ We prepared hitherto unknown Na₄Li₅[BO₃]₃ in the shape of monoclinic, colourless-transparent and prismatic single crystals [a = 1238.8(5) pm, b = 729.6(3) pm, c = 973.8(3) pm, β = 107,29(4)°, Z = 4, d_x = 2,397 g/cm³, d_pyk = 2,37 g/cm³]. The crystal structure was solved by four-circle-diffractometer [PW 1100, MoKα , R = 9,02%, R_w = 5,29%, 1221 I₀(hkl)]I₀(hkl)]. Na₄Li₅[BO₃]₃ is sensitive against atmospheric moisture; hydrolysis takes place within 60 minutes. Effective Coordination numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

Zur Kenntnis des α-NaFeO2-Types: Über KPrO2 [1]

On the α-NaFeO₂-Type: On KPrO₂ For the first time we obtained yellow-green single crystals of KPrO₂ by annealing K₂PrO₃ in Ni-cylinders [1 000°C; 4 weeks]. The structure determination confirms the trigonal rhombohedral α-NaFeO₂-type: a = 365.11(3), c = 1 859.65(21) pm, c/a = 5.09, Z = 3, spacegroup R3m , fourcircle diffractometer data (Philips PW 1100), MoKα , 134 I_o(hkl), R = 2.58%, R_w = 2,42%.     

Über Li8PrO6 und Li8TbO6 (Mit einer Bemerkung über Li8CeO6)

On Li₈PrO₆ and Li₈TbO₆ (with a Remark about Li₈CeO₆) The crystal structure of transparent pale-yellow single crystals of Li₈PrO₆ [a = 560.85(3), c = 1598.24(12); space group R3 ; 388 symmetry independent h kl; R = R_w = 2.60%; AgK_α; fourcircle-diffractometer Philip PW 1100] and of bright yellow single crystals of Li₈TbO₆ [a = 554.96(3), c = 1570.97(16); space group R3 ; 274 symmetry independent hkl; R = 4.02%, R_w = 3,83%; MoK_α; fourcircle-diffractometer Philips PW 1100] has been determined. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed. A new way to compare “quantitatively” isotypic structures is introduced and applied. The result shows that oxides Li₈MO₆ (M = Sn, Pb, Pr, Tb) are “good” isotypic.     

Na2Li3CoO4, das Erste quaternäre Oxocobaltat(III) der Alkalimetalle

Na₂Li₃CoO₄, the First Quaternary Oxocobaltate(III) of the Alkali Metals For the first time we obtained Na₂Li₃CoO₄ by annealing intimate mixtures of Co₃O₄, Na₂O₂, and Li₂O [Co : Na : Li = 1 : 2.2 : 10.1; 760°C; 21 d; Ag-tube] in form of transparent red single crystals. Structure Refinement [four-circle diffractometer data; AED2; MoKα-radiation; 1016 I_o(hkl); R = 2.6%; R_w = 2.0%; space group Pnnm; Z = 4; a = 818.7(3), b = 799.4(2), c = 655.1(2) pm] confirms the isotypism to Na₂Li₃GaO₄ [2] and Na₂Li₃FeO₄ [3]. Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, and the Charge Distribution were calculated. The isotypism of Na₂Li₃CoO₄ and Na₂Li₃GaO₄ is compared graphically.     

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.     

Über Oxotitanate der Alkalimetalle. Zur Kenntnis von Na4Ti5O12

On Oxotitanates of the Alkaline Metals: On Na₄Ti₅O₁₂ Colourless single crystals of the new titanate Na₄Ti₅O₁₂ (starting from mixtures Na₂O/TiO₂, 1000°C, 6 d, Au-crucible, open system) crystallize in the monoclinic system, space group C2/m, a = 26.544(9), b = 2.952(1), c = 6.322(3) Å, β = 95.79(3)°, Z = 2, d_rö = 3.45 and d_pyk = 3.38 g · cm^?3 (four-cycle-diffractometer data, PW 1100, 2?-scan, MoKα). R = 5.09% and R_w = 4.87% for 1178 independent I₀(hkl) with 3° ≤ 2? ≤ 34°. Corrugated layers of Ti₅O₁₂, held together by Na⁺, are stacked along [001]. Details about partially occupied positions of Na⁺, Effective Coordination Numbers (ECoN), the Madelung part of lattice energy (MAPLE), and the structural differences to Na₂Ti₃O₇ are discussed.     

Zur Kristallstruktur von Li8PbO6 [1]

On the Structure of Li₈PbO₆ For the first time single crystals of Li₈PbO₆ have been prepared by heating of mixtures of Na₂PbO₃ and Li₂O [Ag-cylinders, 650°C, 150 d]. The structure [382 I₀(hkl), four circle diffractometer PW 1100, ω/2Θ-scan, MoKα, R = 3.07%, R_w = 3.00%, space group R3 ; a = 555.09(4), c = 1564.13(17) pm, D_x = 4.28 g · cm^?3, D_pyk = 4.24 g · cm^?3, Z = 3] is characterized by the motive of a hexagonal-closed O^2? packing. Half of the octahedral sites are occupied by Pb⁴⁺ and Li⁺ and half of the tetrahedral sites only by Li⁺. The Madelung Part of Lattice Energy, MAPLE, and the Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Neue Oxoferrate(III). Na2Li3[FeO4] und K2Li3[FeO4]

New Oxoferrates (III). Na₂Li₃[FeO₄] and K₂Li₃[FeO₄] . Na₂Li₃[FeO₄] and K₂Li₃[FeO₄] (transparent, pink or light yellow single crystals) have been prepared by heating mixtures of the oxides (Na:Li:Fe = 2.2:3.3:1; Ag-tube, 720°C, 27 d or K:Li:Fe = 2.2:3.3:1; analogous, 700°C, 40 d). Na₂Li₃[FeO₄] is isotypic with Na₂Li₃[GaO₄] (a = 832.2(1), b = 796.0(1), c = 656.3(1)pm, Pnnm) and K₂Li₃[FeO₄] with K₂Li₃[GaO₄] (a = 557.7(1), b = 880.6(1), c = 1101.8(2)pm, β = 111.51(2)°, P2₁/c). Four cycle diffractometer data: MoK_α, 525 out of 686 I₀(hkl), R = 9.36%, R_w = 5.97% or 1424 out of 1424 I₀(hkl), R = 8.45%, R_w = 5.66%. Parameters see text. The structures are characterized by calculations of the Madelung Part of Lattice Energy, MAPLE. The Effective Coordination Numbers, ECoN, which are calculated by means of Mean Fictive Ionic Radii, MEFIR, are compared with the analogous gallates.     

Neue Beryllate der Alkalimetalle: Na6Be8O11

Novel Beryllates of the Alkali Metals: Na₆Be₈O₁₁ For the first time transparent, colourless single crystals of Na₆Be₈O₁₁ have been prepared (Na₂O/BeO; Na:Be = 6:8, Ni-tube; 650°, 14 d). The compound crystallizes triclinic (P1 ) with a = 532.1(1) pm, b = 642.4(2) pm, c = 839.1(2) pm, α = 101.7°, γ = 105.8°, Z = 2, d_x = 2.42 g/cm³, d_pyk=2.51 g/cm³. The crystal structure was solved by four-circle diffractometer data [Siemens AED 2, MoKα , R = 7.9%, R_w = 6.2%, 1429 I₀(hkl)]. Effektive Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Oxydation intermetallischer Phasen: Na3[AuO2] aus NaAu und Na2O2

Oxidation of Intermetallic Phases: Na₃[AuO₂] from NaAu and Na₂O₂ The hitherto unknown Na₃[AuO₂] was prepared in transparent, colourless single crystals from NaAu and Na₂O₂[1:1; sealed Ag-cylinder, 430°C, 6 d]. The crystal structure (P4₂/mnm); a = 970.5(1), c = 457.8(1) pm; Z = 4; four-circle diffractometer PW 1100, 333 out of 380 I₀(hkl), R = 7.0% and [R_w = 6.5%] was solved. Like KAgO-Type there are planar rings [Na₂Au₂O₄]^4?. Na(1) has the uncommon coordinations number 2 . The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated.     

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.     

Zur Existenz polynärer Oxide der Alkalimetalle mit einwertigen Cobalt bzw. Nickel [1, 2]

On the Existence of Polynary Oxides of the Alkali Metals with Monovalent Cobalt and Nickel For the first time we obtained RbNa₂NiO₂, KNa₂NiO₂, Na₃CoO₂ and K₃CoO₂ [RbNa₂NiO₂: Na₂NiO₂ + Rb₂O, Rb:Ni = 1.8:1, 600°C, 28 d, Ni-tube; KNa₂NiO₂: Na₂NiO₂ + K₂O, K:Ni = 1.8:1, 600°C, 20 d, Ni-tube; Na₃CoO₂: Na₂O + CoO: Na:Co = 8.8:1, 500°C, 20 d, Co-tube; K₃CoO₂: K₂O + CoO: K:Co = 4.4:1, 550°C, 20 d, Co-tube]. According to X-ray structure analysis of single crystals monovalent Co and Ni is present [always four-circle-diffractometer data, MoKα -radiation; RbNa₂NiO₂: AED 2, all 163 I_o(hkl), R = 3.4%, R_w = 1.9%, I4/mmm, a = 461.7(1), c = 973.6(3) pm, Z = 2; KNa₂NiO₂: AED 2, all 341 I_o(hkl), R = 5.6%, R_w = 3.5%, Cmma, a = 1 048.5(3), b = 626.8(1), c = 621.9(1) pm, Z = 4; Na₃CoO₂: PW 1 100, 517 of 568 I_o(hkl), R = 2.9%, R_w = 1.8%, P4₂/mnm, a = 940.0, c = 464.5 pm, Z = 4; K₃CoO₂: PW 1 100, all 940 I_o(hkl), R = 5.0%, R_w = 3.9%, Pnma, a = 1 190.0, b = 730.4, c = 604.1 pm, Z = 4]. All samples are red, the single crystals transparent. Two O^2? coordinate Ni¹⁺ and Co¹⁺, respectively, like a dumb-bell. Mean Fictive Ionic Radii, MEFIR, and Effective Coordination Numbers, ECoN, and Madelung part of lattice energy, MAPLE, are given.     

Gehört Na5Mn3F14 zum Chiolith-Typ?? [1]

Na₅Mn₃F₁₄: A new Variant of Chiolite Structure? For the first time red single crystals of Na₅Mn₃F₁₄ have been prepared by thermal decomposition of Na₂MnF₆ [Au-tube under Ar, 640°C, 7d]. Na₅Mn₃F₁₄ crystallizes in the orthorhombic crystal system, spcgr. Pna2₁, a = 1244.5(3), b = 748.2(1), c = 1202.1(2)pm, Z = 4. [Four-circle diffractometer: Philips PW 1100, 2578 I_o(hkl), MoKα, R = 10.4, R_w = 7.5%]. Parameters see in the text. The madelung Part of lattice energy, MAPLE, is calculated.     

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 quaternäre Oxowolframate (VI) Na6Li2[W2O10] - ein Diwolframat

On Quaternary Oxotungstates (VI). Na₆Li₂[W₂O₁₀] — a Ditungstate For the first time, Na₆Li₂[W₂O₁₀] has been prepared by annealing mixtures of WO₃, Na₂O and Li₂O with W:Na:Li = 1:3:1 [closed Pt-tube in quartz-glass ampoule, 840°C, 60 d (single crystals)]. The colourless crystals are of squatted shape. The structure determination [1813/I₀(h kl), four-cycle diffractometer PW 1100 (Fa. Philips), ω-scan, AgK_α, R = 8.32%, absorption not considered] confirms the space group P1 with a = 784.66(11), b = 602.53(7) c, = 563.81(11) pm α = 106.784(14)°, β = 114.548(14)°, γ = 91.082(13)°, Z = 2, d_x = 4.92 g · cm^?3, d^pyk = 4.85 g · cm^?3. The structure may be described as a distorted derivative of the NaCl-type. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Ein neues Oxouranat(VI): K2Li4[UO6]. Mit einer Bemerkung über Rb2Li4[UO6] und Cs2Li4UO6

A New Oxouranate(VI): K₂Li₄[UO₆]. With a Remark about Rb₂Li₄[UO₆] and Cs₂Li₄[UO₆] For the first time K₂Li₄UO₆ has been prepared by an exchange reaction of α-Li₆UO₆ with K₂O [K:U = 2.0:1, sealed au-tube; 750°C; 30 d single crystals; 680°C, 10 d powder]. The irregular shaped single crystals, which are of yellow color and sensitive to moisture crystallize in P3 m1 (Z = 1) with a = 619.27(5), c = 533.76(6) pm. The structure determination (PW 1100, AgKα R = 4.80%, R_w = 4.81% for 220 unique reflexions) reveals a new type of structure. The characteristic elements are the isolated group [UO₆] and the C.N. = 12 for K⁺. While Li(1) has a nearly regular square of 4 O^2? as coordination polyhedron, Li(2) is octahedrally surrounded. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed. In addition to K₂Li₄[UO₆] the new oxides Rb₂Li₄[UO₆] and Cs₂Li₄[UO₆] are prepared as pale yellow powders which are little sensitive to moisture (both: au-tube, 680°C, 10 d). According to powder datas both compounds are isotypic with K₂Li₄[UO₆] [Rb₂Li₄[UO₆]: a = 622.91(5), c = 535.93(6) pm; Cs₂Li₄[UO₆]: a = 626.70(6), c = 539.92(6) pm].