Zur Kenntnis der Oxopalladate der Alkalimetalle [1]

On Oxopalladates of Alkali Metals According to X-ray data of single crystals there are: Na₂PdO₂ (yellow rod-shaped crystals) orthorhombic, a = 3.07₇, b = 10.35₉, c = 8.35₁ Å, Z = 4; d_x = 4.60, d_pyk = 4.6₃ g · cm^?3. ?K₂PdO₃”? (black square prism) orthorhombic, a = 6.20₂, b = 9.21₉, c = 4× 11.37₂ = 45.4₈ Å, Z = 24, d_x = 3.60, d_pyk = 3.5₀ g · cm^?3, and ?K₆PdO₄”? (orange square prism) orthorhombic (pseudotetragonal), a = b = 12.36₈, c = 13.59₃ Å, Z = 8, D₂⁴—P2₁2₁2₁. ?Rb₂PdO₃”? (black) is isostructural (Guinier data) to ?K₂PdO₃”?, a = 7.35₄, b = 9.60₅, c = 11.58₆ Å, d_x = 4.58, d_pyk = 4.4₇ g · cm^?3. Na₂PdO₃ exists in another reddish brown form, isostructural to Li₂MnO₃ (C_2h⁶—C2/c), a = 5.37₄, b = 9.30₉, c = 10.78₉ Å, β = 99.5°, Z = 8, d_x = 5.00, d_pyk = 4.7₃ g · cm^?3.     

Zur Kenntnis von Li2[CuO2] [1, 2]

On Li₂[CuO₂] At the first time single crystals of Li₂[CuO₂] are prepared by exchange reaction. The crystal structure (I mmm) with a = 365.4(0), b = 285.9(0), c = 937.4(0) pm, Z = 2, d_x = 3.73 g/cm³, d_pyk = 3.67 g/cm³ was refined (four-circle-diffractometer data PW 1100, 343 I_o(hkl), MoKα, R = 0.046, R_w = 0.041). The characteristic structure element is the planar chain \documentclass{article}\pagestyle{empty}\begin{document}$ {}_\infty ^1 \left[{{\rm CuO}_{4/2}} \right]^{2 -} $\end{document}. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Über Borati der Alkalimetalle. II. Zur Kenntnis von LiB3O5 [1]

On Borates of the Alkaline Metals. II. On the Knowledge of LiB₃O₅ Single crystals of LiB₃O₅ were obtained for the first time. LiB₃O₅ crystallizes orthorhombic in the space group Pn2₁a–C with the parameters a = 8.46₀; b = 5.13₃; c = 7.38₆. The structure was determined [404 reflections, MoKα, R = 3,6₅%, R_w = 3.3₁%]. LiB₃O₅ contains B₃O₅ groups, comparible to those in CsB₃O₅. Both compounds are not isotypic. Madelung Part of Lattice energy, MAPLE, is calculated and discussed.     

Zur Kenntnis von KLiZnO2 [1]

On KLiZnO₂ The hitherto unknown compound KLiZnO₂ has been prepared by annealing a mixture of KO_0.48, Li₂O and ZnO in the ratio K:Li:Zn = 1.1:1.1:1 [Ag-cylinder, sealed under Ar in Duran-glass tube, 500°C, 14 d (powder), or closed Pt tube, 800°C, 45 d (single crystals)]. The plate-shaped single crystals and the powder are colourless and hygroscopic. The structure determination [420 symmetry independent hkl, fourcircle-diffractometer PW 1100 (Philips), ω - 2θ-scan, MoK_α, R = 5.78%, R_w = 5.96%] proves the space group C2/m with a = 1083.2(1), b = 334.42(3), c = 823.7(1) pm and β = 120.11(1)°, Z = 4, d_x = 3.69, d_pyk = 3.57 g · cm^?3. The structure shows corrugated layers of cations and O^2? respectively. It can be deduced from a cubic closest packing of O^2? and K⁺ where Li⁺ and Zn²⁺ occupy 1/3 of the tetrahedral holes. The Effective Coordination Numbers, ECoN, Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated.     

Neue Oxoborate der Alkalimetalle: NaLi2[BO3] [1]

New Borates of the Alkali Metals: NaLi₂[BO₃] The hitherto unknown NaLi₂[BO]₃ is prepared in the shape of monoclinic, colourless-transparent and prismatic single crystals [a = 950.7(4) pm, b = 1 203.7(4) pm, c = 493.0(3) pm, β = 104.0(10)°, d_x = 2.32 g/cm³, d_pyk = 2.28 g/cm³]. The crystal structure has been solved by four-circle-diffractometer [PW 1100, MoK, R = 7.52%, R_w = 4.66%]. Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

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.     

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.     

Neue Borate der Alkalimetalle: KLi2[BO3]

New Borates of the Alkali Metals: KLi₂[BO₃] The hitherto unknown KLi₂[BO₃] is prepared in the shape of orthorhombic, colour-less-transparent, and columnar single crystals [a = 797.1(4) pm, b = 643.2(3) pm, c = 645.7(3) pm, Z = 4, d_x = 2.25 g/cm³, d_pyk = 2.20g/cm³]. The crystal structure was solved by four-cycle-diffractometer [PW 1100, MoKα, R = 5.78%, R_W = 3.83%, 452 I₀(hkl)]. Kli₂[BO₃] is sensitiv against atmospheric moisture which causes hydrolysis. Effective Coordination Numbers, ECoN, these via Mean Effective Ionic Radii, MEFIR, are calculated and discussed.     

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.     

Neue Borate der Alkalimetalle: KNa2[BO3]

New Borates of Alkali Metals: KNa₂[BO₃] We prepared hittherto unknown KNa₂[BO₃] in the shape of orthorhombic, colourlesstransparent and columnar single crystals [a = 603.9(2) pm, b = 560.2(3) pm, c = 556.8(2) pm, Z = 2, d_x = 2.54 g/cm³, d_pyk = 2.50 g/cm³]. The crystal structure was solved by four-cycle-diffractometer [PW 1100, MoKα , R = 3.73%, R_w = 2.88%, 386 I₀(hkl)]. KNa₂[BO₃] is very sensitiv against atmospheric moisture, and hydrolysis takes place. Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, and the Madelung-Part of Lattice Energy, MAPLE, are calculated and discussed.     

Neue Oxozincate der Alkalimetalle: Rb2[ZnO2] und Cs2[ZnO2]

New Oxozineates of Alkali Metals: Rb₂[ZnO₂] and Cs₂[ZnO₂] Colorless single crystals of the hitherto unknown Rb₂[ZnO₂] (a = 9.55₈, b = 6.33₅, c = 15.91 Å, β = 118.6°, z = 8, d_pyk = 4.11, d_rö = 4.21 g · cm^?3) and Cs₂[ZnO₂] (a = 9.85₁, b = 6.61₉, c = 16.26 Å, β = 116.8°) have been prepared, which crystallize monoclinic, P2₁/c – D. (For parameters see text.) Unexpected there are “isolated” groups [Zn₄O₈]. Half of the Zn atoms exhibit the unusual coordination number 3 towards O^2?. The Madelung Part of Lattice Energy, MAPLE, and the Effective Coordination Number, ECoN, the latter by means of Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Zur Kenntnis der 1-Methylisatine

Ohne ZusammenfassungDer Schmelzpunkt liegt um 145°. Das Krystallisationsvermögen ist ein geringes. Das mikroskopische Bild scheint auf monokline tafelförmige Krystalle zu deuten, welche zum Teil unvollkommen ausgebildet sind. Charakteristisch für die Substanz ist die grüne Fluoreszenz der alkoholischen Lösungen.Die Arbeit wird fortgesetzt.     

Über Oxothallate der Alkalimetalle. Zur Kenntnis von Li5TlO4

New obtained is Li₅TlO₄ (light yellow), which due to single crystal data crystalises with a = 13.23, c = 4.72₈ Å; Z = 8, tetragonal P4₂/nmc. For 342 hk0–hk3, Mo–K_α, is R = R' = 0.098₄ (Parameters see text). Corresponding to Li₅□₂TlO₄, it is an ordered derivative of the Li₂O type of structure.     

Über Oxocobaltate der Alkalimetalle. Zur Kenntnis von Li8CoO6

Oxocobaltates of Alkali Metals. On Li₈CoO₆. Hitherto unknown Li₈CoO₆, rubin- red single crystals, cristallizes according to WEISSENBERG and precession photographs (MoK_α) hexagonal with a = 5.44 Å, c = 10.87 Å; c/a = 2.0; Z = 2, space group C? P6₃cm. Atomic parameters see text. The structure derives from a closest packing of O^2?, ABACA … (The tetrahedral, ?isolated”? groups [CoO₄] show remarkable short distances Co–O (1.66 Å), comparable with [CoO₄] in Li₄CoO₄, being isotypic with Li₄SiO₄. The MADELUNG Part of Lattice Energy is calculated and discussed.     

Neue Borate der Alkalimetalle: CsLi5[BO3]2

New Borates of Alkali Metals: CsLi₅[BO₃]₂ We prepared hitherto unknown CsLi₅[BO₃]₂ in the shape of monoclinic, colourless-transparent and columnar single crystals [a = 1179.5(2) pm, b = 943.3(2) pm, c = 809.6(3) pm, β = 132.76(8)°, Z ° 4, d_x = 2.859 g/cm³, d_pyk = 2,80 g/cm³].The crystal structure was solved by four-circle-diffractometer [PW 1100, AgKα, R = 5.7%, R_w = 3.8% für 1317 I₀(hkl)]. CsLi₅[BO₃]₂ is sensitive against atmospheric moisture, and hydrolysis takes place. Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

Schmelzreaktionen mit Aluminiumchlorid 3. Mitteilung [1] Zur Kenntnis der Pyridinio-anthrachinon-Derivate aus der Pyridin-Aluminiumchloridschmelze von Aminoanthrachinonen

In continuation of previous work, the behaviour of amino-anthraquinones on fusion in pyridine - aluminium chloride in the presence of oxidants is studied. Instead of dimerisation the reaction leads to salts of pyridinio-aminoanthraquinones and further to condensed “anthraimidazopyridine” derivatives.     

Zur Kenntnis der K4[Ag4O4]-Verwandtschaft

On the K₄[Ag₄O₄] Relation Single crystals of mainly new oxides A₄[M₄O₄] with M = Cu, A = Li? Rb and M = Ag, A = Na, Rb, Cs have been prepared by “reaction at the metallic substrate” (i.e. the wall) and the crystal structures were refined. For lattice constants and atomic parameters see text. The [M₄O₄]^4? ring is planar only for the M₄-part, the positions of the O^2? particles deviate in a non systematic way from this plane. Only Li₄[Cu₄O₄] contains an almost planar ring. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Zur Kenntnis der Adsorption,IV

Ohne Zusammenfassung     

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.