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.     

Zur Kenntnis von Na4[CrO4]

On Na₄(CrO₄) Dark-green single crystals of Na₄[CrO₄] were obtained for the first time. (Na₂O/Cr₂O₃; Na:Cr = 4:1 not exactly closed Ni-tube; 1000°C; 30 d). It is isostructural to Na₄(CoO₄); space group P1 , a = 859.7 pm, b = 569.8 pm, c = 640 pm, α = 124°C, β = 98.4°, γ = 98.9°, Z = 2. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Effective Ionic Radii, MEFIR, are calculated.     

Zur Kenntnis der Oxoberyllate der Alkalimetalle [1, 2]

On Oxoberyllates of the Alkali-Metals The existence of the phases K₂Be₂O₃ (2 forms), K₄BeO₃, Rb₂Be₃O₄, Rb₂Be₂O₃,Rb₄BeO₃, Cs₂Be₃O₄ and Cs₂BeO₂ is proved by powder-datas according to GUINIER -SIMON . In single crystal form we obtained Li₄BeO₃ [a = 5.49; b = 9.53; c = 4.93 Å; a = 114.₁; ß = 105.₀; γ = 106.₆°; triclinic], Na₂Be₂O₃ [;a = 6.32; b = 8.53; c = 2.71 Å; α = 107.₇; ß = 105.₅; γ = 78.₄°; triclinic], Na₆Be₂O₅ [a = 5.67₂; c = 10.2₁ Å; tetragonal] as also K₂BeO₂ [a = 7.09₈; b = 10.57₇; c = 5.70₆ Å; γ = 131.₃°; monoclinic] and Rb₂BeO₂ [a = 7.46₃; b = 11.17₀; c = 5.88₁ Å; γ = 131.₈°; monoclinic].     

Zur Kenntnis von Cs4Fe3F10 [1] sowie Cs3TINi3F10 [2]

On Ca₄Fe₃F₁₀ and Cs₃TINi₃F₁₀ Single crystals of Cs₄Fe₃F₁₀ (orthorhombic, a = 629.4, b = 1450,7, c = 1410.9 pm) and Cs₃TlNi₃F₁₀ (orthorhombic, a = 610.1, b = 1442.0, c = 1366.8 pm) have been prepared. Results of X-ray investigation: Cs₄Fe₃F₁₀ is isotypic to Cs₄Mg₃F₁₀ and crystallizes in the space group Cmca (R = 3.97%, R_w = 2.75%, 1020 of 1020 I₀(hkl), fourcircle diffractometer AED 2, Fa. Siemens). A monoclinic distortion could not be observed as supposed present. Cs_4?xTl_xNi₃F₁₀ (x≈?1), R = 7.75%, R_w = 4.96%, 1079 of 1294 I₀(hkl), fourcircle diffraktometer PW 1100, Fa. Philips) confirm the possibility to substitute Cs against Tl in the Cs₄Mg₃F₁₀-type.     

Über neue Oxoniccolate: Zur Kenntnis von Na2[NiO2]

New Oxoniccolates: On the Knowledge of Na₂[NiO₂] The low temperature form of Na₂NiO₂, dark-red single crystals, obtained by heating Na₂O and ?NiO’? [Na:Ni = 2,2:1; 680°C, 3d, Ni cylinders] crystallizes orthorhombic with a = 2.82₀ b = 10.14₁ c = 8.28₃ Å, Z = 4 in the space group Cmc2₁. Due to fourcycle diffractometer data (290 hkl, MoKα, R = 2.8%) a new type of structure occurs, the NiO₂ part of which shows the PdCl₂ motive like in Li₂NiO₂. The coordination number of \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm 2}{\rm a} $\end{document} towards O is 4, of \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm 1}{\rm a} $\end{document} is 5. Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are discussed.     

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 CsLiCl2

On CsLiCl₂ CsLiCl₂ crystallizes with a = 492.35(9), c = 950.0(3) pm (Guinier data), tetragonal, P4/nmm, Z = 2. The crystal structure was determined and refined from single crystal data (R = 5.2, R_w = 4.0%). It is essentially that proposed earlier for KCoO₂ which is isotypic with CsLuO₂. In CsLiCl₂ Cs⁺ has C.N. = 9 (d? = 363 pm), Li⁺ C.N. = 5 (tetragonal pyramid) with d(Li? Cl) = 231 and 4 × 260 pm, respectively.     

Zur Konstitution von Cs2K[CuF6] [1]

On the Structure of Cs₂K[CuF₆] By annealing of powder preparations under carefully dried Ar, [closed Cu-tube, 540°C, 100 d] for the first time we received single crystals of Cs₂K[CuF₆], a fluoride with copper in oxidation state +3. The pale blue-green single crystals were transparent and of irregular habitus. In accordance with single-crystal studies we found as supposed by us spcgrp. O_h⁵ – Fm3m No. 225 – a = 889.4 pm. The determining parameter of the structure, z_F = 0.206₀, leads to unexpected short distances: d(Cu–F) = 183.3 pm (previously presumed: 193 pm). The Madelung part of Lattice Energy, MAPLE, is calculated. We try to appreciate ΔH(CuF₃, solid), just so Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR.     

Über Thiomercurate. 3. Zur Kenntnis von Ba[HgS2]

On Thiomercurates. 3. About BaHgS₂ The hitherto unknown carminred BaHgS₂ was prepared by heating binary sulfides [intimate mixtures, Ba:Hg = 1.00:1, in quartz-seales, 600–650°C, 2–3 d (powder), or 700–750°C, 8–10 d (single crystals)]. BaHgS₂ crystallizes orthorhombic with a = 4.21₅, b = 14.38₈, c = 7.33₈ Å, space group Pmc2₁. The new structure was elucidated by diffractometer data (MoKα), 1199 of 1228 independent hkl, R = 8.8, R_W = 9.2% as final result (Parameter see text). Effective Coordination Numbers, ECoN, Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE are discussed.     

Neue Alkalioxoarsenate (V) Zur Kenntnis von Rb2Li[AsO4] und Cs2Li[AsO4]

New Alkalioxoarsenates (V). On Rb₂Li[AsO₄] and Cs₂Li[AsO₄] By heating of well-grounded mixtures of the binary oxides (A₂O, Li₂O₂, and As₂O₃; A : Li : As = 2 : 1 : 1; Ni-tube, 550°C, 21 d; A = Rb, Cs) colourless single crystals of Rb₂Li[AsO₄] and Cs₂Li[AsO₄] were obtained for the first time. These new orthoarsenates(V) crystalize orthorhombic (space group C mc2₁? C, No. 36) with Z = 4. As expected they are isotypic with the according orthovanadates(V) [2] A₂Li[VO₄], A = Rb, Cs. The lattice constants of Rb₂Li[AsO₄]: a = 582.1(4) pm, b = 1171.1(7) pm, c = 792.4(5) pm and Cs₂Li[AsO₄]: a = 596.4(2) pm, b = 1223.4(2) pm, c = 819.7(3) pm were taken from Guinier-Simon powder data. The structure was determined by four-circle-diffractometer data [Siemens AED II, MoKα , 6290 I₀ (hkl), R = 3.5%, R_w = 3.2% to Rb₂Li[AsO₄]; 3518 I₀ (hkl), R = 2.8%, R_w = 2.6% to Cs₂Li[AsO₄]; parameters see text]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, as well as charge distribution CHARDI are calculated and discussed.     

Zur kenntnis von kubischem Rb2MnF6 [1]

Rb₂MnF₆ cubic (Fm3m) with a=852,7(1) pm has been isolated for the first time as light yellow, stable (when exposed to air) single crystals. X_F was refined from the four circle diffractometer data (Philips PW 1100; Mo-K_α; 69 I_o(hkl), R=5,8 R_w=3,3%]), leading to d(Mn-F) = 178.5 pm (6x). The Madelung Part of lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are discussed.     

Neue Oxocobaltate (IV): Zur Kenntnis von K6[Co2O7]

New Oxocobaltates(IV): On K₆[Co2O₇] K₆Co₂O₇ is another new oxide containing tetravalent Co (red-violet single crystals). According to precession- and WEISSENBERG-photographs the space group is P2₁/c; a = G.58₅, b = 9.12₃. c = 11.47₉ Å, β = 127.1°. The crystal structure shows Co₂O₇-groups (two tetrahedron connected by a common corner, symmetry ≈ S₆). The Madelung Part of Lattice Energy (MAPLE) is computed and compared with MAPLE of Cs₂CoO₃. The magnetic properties are reported (measurements of susceptibility by the method of FARADAY in a temperature range of 3–300°K).     

Zur Kenntnis von Sr2CrMnO6

About the New Compound Sr₂CrMnO₆ Sr₂CrMnO₆ was prepared and investigated by X-ray single crystal data (a = 541.6; c = 664.0 pm; space group C–P3 ). The structure is related to the distorted perovskites, the differences to SrCrO₃ and SrMnO₃ are discussed.     

Zur Kenntnis von K2GeO3

On K₂GeO₃ Single crystals of K₂GeO₃ have been prepared by heating K₂O and GeO₂ (K:Ge = 3.0:1.0; Ag-cylinder, 10 d, 700–800°C). The structure has been refined. K₂GeO₃: a = 2302.5(3), b = 3286.3(5), c = 545.2(1) pm; Pbca; R = 13.83%; R_w = 9.60% (different parameters see text). The structure of K₂GeO₃ will be discussed. The Effective Coordination Numbers, ECoN, the Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattic Energy, MAPLE, are calculated.     

Neue Oxocuprate(I). Zur Kenntnis von Rb3Cu5O4 [1]

New Oxocuprates(I). On Rb₃Cu₅O₄ New obtained is Rb₃Cu₅O₄, powder as well as transparent single crystals greenish yellow. The monoclinic structur [P2₁/c, a = 9.886(1), b = 7.508(1), c = 14.401(2) Å, β = 106.85(7)°, Z = 4, four-circle diffractometer data, R = 10.6% for 1 453 hkl, MoKα] is characterized by spiralic chains ? O? Cu? O? Cu? parallel to [100], which are tied together by additional Cu⁺. Motifs of mutual adjunction, Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

Zur Kenntnis von cis-Natriumhyponitrit

To the Knowledge of cis-Sodium Hyponitrite Surprisingly, cis-sodium hyponitrite can be prepared by reacting gaseous N₂O and solid Na₂O. For the first time, the structure of a simple salt of cis hyponitrous acid has been determinated unambigously. According to an abinitio structure determination based on powder data, cis-Na₂N₂O₂ crystallizes monoclinic (P2₁/c, a = 5.107(1); b = 9.211(1); c = 6.159(1) Å; β = 97.91(1)°; Z = 4). Results of spectroscopic investigations (vibrational spectroscopy, ¹⁵N-MAS-NMR) agree with the symmetry of the cis-N₂O₂^2? anion as it has been proved by the crystal structure. Consider able differences regarding some chemical and physical properties have been observed for samples of cis-Na₂N₂O₂ synthesized via different routes.     

Zur Kenntnis von Harzbestandteilen

Ohne Zusammenfassung     

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.