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.     

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 Oxocuprate. XI. Zur Kenntnis von Ba3Cu2O4Cl2

On Osocuprates. XI. Ba₃Cu₂O₄Cl₂ A new oxohalogenocuprat, Ba₃Cu₂O₄Cl₂ mas prepared and investigated by X-ray single crystal methods. The hitherto unknown compound has orthorhombic symmetry (Space group: D_2h⁵—Pmma; a = 6.653, b = 6.000, c = 10.563 Å). It shows angled chains of O^2?-squares around Cu²⁺. One of the Cu²⁺ positions is completed by Cl^minus; to a tetragonal pyramid. The coordination polyhedrals of Ba_I–III and the connection with the Cu/O-chains are described and discussed.     

Über ternäre Oxocuprate,IX Zur Kenntnis von MgCu2O3

On Ternary Oxocuprates. IX. About MgCu₂O₃ The hithertoo unknown compound MgCu₂O₃ was prepared and investigated by single crystal x-ray diffractometer data. The orthorhombic MgCu₂O₃ (a = 4.00, b = 9.35, c = 3.19 Å; space group D–Pmmn) is isotypic with CaCu₂O₃. Cu²⁺ has a distordet octahedral configuration by O^2?.     

Über Tetrabromothallate MTlBr4 (M = K,Rb, Cs,NH4)

On the Tetrabromothallates MTlBr₄ (M = K, Rb, Cs, NH₄) The tetrabromothallates MTlBr₄ (M = K, Rb, Cs, NH₄) were obtained by dehydratisation of the appropriate hydrates MTlBr₄ · nH₂O and by the reaction of TlBr, MBr, and Br₂ in closed glass tubes at 400°C. KTlBr₄ and NH₄TlBr₄ crystallize orthorhombic in the Ga[GaCl₄]-type with the following lattice constants a = 795.2(3), b = 1036.0(4), c = 1042.1(5) pm (KTlBr₄), and a = 812.6(3), b = 1070.1(13), c = 1110.6(10) pm (NH₄TlBr₄), respectively.     

Über ternäre Oxocuprate. X. Zur Kenntnis von Ba2Cu3O4Cl2

About Ternary Oxocuprates. X. On Ba₂Cu₃O₄Cl₂ The preparation of Ba₂Cu₃O₄Cl₂ and results by single crystal X-ray methods are described (a = 5.517, c = 13.808 Å; Space group D–I4/mmm). A so far unknown arrangement of square coordinated Cu²⁺ was detected. The Cu²⁺/O^2?-squares are partly completed to a distorted octahedral coordination by two Cl^?.     

Neue Oxogallate der Alkalimetalle: Über K6[Ga2O6] und Rb6[Ga2O6], sowie Na3GaO3 und Cs6[Ga2O6]

New Oxogallates of Alkaline Metals: On K₆[Ga₂O₆] and Rb₆[Ga₂O₆] as well as Na₃GaO₃ and Cs₆[Ga₂O₆] Due to powder and single crystal data K₆[Ga₂O₆] a = 7.09₉; b = 11.11₆; c = 6.48₄ Å; ß = 101.6₆° and Rb₆[Ga₂O₆] a = 7.39₃; b = 11.47₅; c = 6.79₈ Å; ß = 103.5° crystallize isotypic with K₆[Fe₂O₆]; space group C2/m-C₃^2h; As well has been prepared the hitherto unknown Na₃GaO₃ a = 11.48, b = 10.82, c = 6.13 Å, space-group Imcm or I2cm Z = 8; and Cs₆[Ga₂O₆] a = 7.2₆, b = 12.1, c = 7.6₈ Å, ß = 105°, Z = 4, space-group P2₁/a.     

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.     

Über Oxostannate(II). I. Zur Kenntnis von K2Sn2O3

On Oxostannates(II). I. Information on K₂Sn₂O₃ Hitherto unknown K₂Sn₂O₃ was obtained by heating mixtures of binary Oxides [KO_0.48 + SnO, K:Sn = 1.1:1] under Argon [Al₂O₃ cylinders, 550°C, 24 h or 7 d] as yellow powder or brownish-yellow single crystals, respectively. It crystallizes trigonal-rhombohedral in R3m—D, with a = 6.00₁ Å, c = 14.32₇ Å, Z = 3, d_rö = 4.05 and d_pyk = 3.98 gcm^?3, positions are given in text, R = 2.1₁% for 219 hkl (MoKα, 4-circle diffractometer data).     

Über die Trithiocyanatoargentate Rb2Ag(SCN)3 und Cs2Ag(SCN)3

On the Trithiocyanatoargentates Rb₂Ag(SCN)₃ and Cs₂Ag(SCN)₃ The trithiocyanatoargentates Rb₂Ag(SCN)₃ and CsAg(SCN)₃ are obtained by crystallization from highly concentrated aqueous solutions. In the crystal structures the Ag atoms are surrounded tetrahedrally by the S atoms of 4 SCN groups. These Ag(SCN)₄ tetrahedra are connected by common corners to polymer \documentclass{article}\pagestyle{empty}\begin{document}$ {}_\infty ^1 \left[{{\rm Ag}\left({{\rm SCN}} \right)_2 \left({{\rm SCN}_{2/2}} \right)} \right] $\end{document}¹[Ag(SCN)₂(SCN)_2/2] anion in Rb₂Ag(SCN)₃, whereas dimeric Ag₂(SCN)₆ anions were found in the Cs compound.     

Über Hexafluorovanadate(III). Cs2MVF6 und Rb2MVF6 (MTl,K und Na); mit einer Bemerkung über Na3VF6

On Hexafluorovanadates(III). Cs₂MVF₆ and Rb₂MVF₆ (M?Tl, K. and Na); with a Remark on Na₃VF₆ By heating the binary fluorides in a closed system we obtained Cs₂TlVF₆ (a = 9.23₄ Å), Cs₂KVF₆ (a = 9.04₇ Å), Rb₂KVF₆ (a = 8.85₅ Å) and Rb₂NaVF₆ (a = 8.46₈ Å), all cubic Elpasolithes of soft green colour as well as Cs₂NaVF₆ (hexagonal a = 6.24 Å, c = 30.58 Å, isotypic with Cs₂NaCrF₆) and Na₃VF₆ (monoclinic a = 5.51₃ Å, b = 5.72₁ Å, c = 7.96₃ Å, β = 90.4₇°, isotypic with Na₃AlF₆). VF₃ (3.0–296.2°K), Cs₂TlVF₆, Cs₂KVF₆ and Rb₂KVF₆ (all from 70–299°K) have been measured magnetically. The spectra of reflection in the range of 9 000 to 33 000 cm^?1 of VF₃ and the new quaternary fluorides are measured and discussed. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Über K2PbO3 [1,2] Rb2PbO3 [3–5] und Cs2PbO3 [6,7]

On the Oxides A₂PbO₃ (A = K, Rb, Cs) The oxides A₂PbO₃ (A = K, Rb, Cs) have been reinvestigated [four-circle diffractometer PW 1100 (Fa. Philips), all particles ?anisotropically”? refined, parameters see text]. The structural features are confirmed, whereas the results on space group and parameters have to be partially corrected.     

Über Oxostannate(II). II. Zur Kenntnis von Cs2Sn2O3

On Oxostannates(II). II. On the Knowledge of Cs₂Sn₂O₃ Cs₂Sn₂O₃ has been prepared for the first time by heating of mixtures of CsO_0.46 and SnO with Cs:Sn = 1.0:1 [under Argon, Al₂O₃ or Ag cylinders, 480°C, 3 d or 18 d as pale light yellow powder or light yellow transparent single crystals, respectively]. According to four-circle-diffractometer data [955 of 1199 I₀(hkl), Mo-Kα, not corrected for absorption, R = 8.1₇%, R_w = 7.9₇%] the compound crystallizes in Pnma with a = 13.70₈; b = 6.09₈; c = 8.92₁ Å, Z = 4, d_pyk = 4.84 g · cm^?3, d_calc = 4.91 g · cm^?3. Parameters see text. Cs₂Sn₂O₃ has a layer structure like K₂Sn₂O₃ but with an undulated instead of a flat O₃ part of the structure and different coordination of Cs versus O.     

Über Oxoniccolate(II) der Alkalimetalle:K2NiO2, Rb2NiO2 und Cs2NiO2

On Oxoniccolates(II) of Alkali Metals: K₂NiO₂, Rb₂NiO₂, and Cs₂SiO₂. The hitherto unknown K₂NiO₂ (dichroic single crystals: redviolet/green, a=3.95₃, c=12.85₃ Å), Rb₂NiO₂ (analogous yellowred/green, a=4.17₄, c=13.18₆ Å) and Cs₂NiO₂ (analogous: darkgreen/green, a=4.41₃, c=13.59₀ Å) have been obtained, which surprisingly crystallize in the tetragonal Na₂HgO₂-type of structure with [O–-Xi –-O]-dump-bells. The distance Ni –-O is very short: 1.68 Å. The K₂SiO₂-structure was determined using single crystal data, R=7.98% and R′=10.6% for 131 reflections hhl–- (h+3)hl. The magnetic datas for K₂NiO₂ and Cs₂NiO₂ obey the CURIE -WEISS -law (μ=3,0 μ_B. Θ ? ?30°K). The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Über Alkalimetallmanganchalkogenide A2MnX2 mit A K,Rb oder Cs und X S,Se oder Te

Inhaltsübersicht. Die Verbindungen K₂MnS₂, Rb₂MnS₂, Cs₂MnS₂, K₂MnSe₂, Rb₂MnSe₂, Cs₂MnSe₂, K₂MnTe₂, Rb₂MnTe₂ und Cs₂MnTe₂ wurden durch Umsetzungen von Alkalimetall-carbonaten mit Mangan bzw. Mangantellurid in einem mit Chalkogen beladenen Wasserstoffstrom erhalten. Kristallstrukturuntersuchungen an Einkristallen ergaben, daß alle neun Verbindungen isotyp kristallisieren (K₂ZnO₂-Typ, Raumgruppe Ibam). Untersuchungen zum magnetischen Verhalten zeigen antiferromagnetische Kopplungen der Manganionen in den [MnX_4/2^2–]-Ketten, On Alkali Metal Manganese Chalcogenides A₂MnX₂ with A K, Rb, or Cs and X S, Se, or Te The compounds K₂MnS₂, Rb₂MnS₂, Cs₂MnS₂, K₂MnSe₂, Rb₂MnSe₂, Cs₂MnSe₂, K₂MnTe₂, Rb₂MnTe₂, and Cs₂MnTe₂ were synthesized by the reaction of alkali metal carbonates with Mn or MnTe in a stream of hydrogen charged with chalcogen. Structural investigations on single crystals show that all nine compounds crystallize in isotypic atomic arrangements (K₂ZnO₂ type, space group Ibam). The magnetic behaviour indicates antiferromagnetic interactions of the manganese ions within the [MnX_1/2^2–] chains.     

Über Hexafluoroferrate(III): Cs2TlFeF6, Cs2KFeF6, Rb2KFeF6, Rb2NaFeF6 und Cs2NaFeF6

On Hexafluoroferrates(III): Cs₂TlFeF₆, Cs₂KFeF₆, Rb₂KFeF₆, Rb₂NaFeF₆, and Cs₂NaFeF₆ New prepared are the compounds Cs₂TlFeF₆ (a = 9.21₁ Å), Cs₂KFeF₆ (a = 9.04₁ Å), Rb₂KFeF₆ (a = 8.86₈ Å) and Rb₂NaFeF₆ (a = 8.46 ₄Å) all cubic Elpasolithes as well as Cs₂NaFeF₆ (Cs₂NaCrF₆?type, hexagonal with a = 6.28₁, c = 30.53₂ Å), all colourless. Cs₂KFeF₆ was measured magnetically (70–297,2 K). The spectra of reflection were measured (9000–36000 cm^?1). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Über die Pentachlorothallate(III) K2TlCl5 · 2 H2O und M2TlCl5 · H2O (M = Rb,NH4)

On the Pentachlorothallates(III) K₂TlCl₅ · 2 H₂O and M₂TlCl₅ · H₂O (M = Rb, NH₄) The pentachlorothallates(III) K₂TlCl₅ · 2 H₂O and M₂TlCl₅ · H₂O (M = Rb, NH₄) were obtained by crystallization from aqueous solutions of TlCl₃ and MCl. The crystal structure of the monoclinic K₂TlCl₅ · 2 H₂O contains dimeric Tl₂Cl₁₀ anions formed by two edge sharing octahedra. The orthorhombic monohydrates are isotypic with Cs₂[TlCl₅(OH₂)].     

Neue Heterocyclen: Über Tetrazinodi(heteroarene). Synthese und Struktur

Novel Heterocycles: Tetrazinodi(heteroarenes), Synthesis and Structure A series of 7 new symmetric tetrazinodi(heteroarenes) is obtained in a two-step synthesis by N-aminating heterocyclic compounds substituted with a leaving group and by treating the latter with an organic or inorganic base. The new compounds are characterized, and the postulated structures are confirmed by X-ray analysis of a representative example.     

Über die Dihydrogenphosphide der Alkalimetalle,MPH2 mit M ≙ Li,Na, K,Rb und Cs

Dihydrogenphosphides of Alkali Metals, MPH₂ (M ? Li, Na, K, Rb, Cs) The dihydrogenphosphides from lithium to cesium were obtained by the reaction of PH₃ with the corresponding solutions of the metals or the metal amides in ammonia. The compounds were examined by X-ray, IR-spectroscopic, and thermochemical techniques. LiPH₂ is not stable at room temperature, while evolving PH₃ it decomposes to yellow products. NaPH₂ is a stable, white compound; above 393 K it decomposes associated with discolouring. KPH₂ and RbPH₂ exist in the region from 110 K to ～400 K in three crystalline forms. Its high-temperature modification is of the sodium chloride-type structure; a monoclinic deformation occurs with decreasing temperature. DSC-measurements revealed a further low temperature form. CsPH₂ crystallizes in the CsCl-type structure between 110 K and ～400 K.     

Alkalioxoargentate(I). Über Na3AgO2

Oxoargentates(I) of Alkali Metals. On Na₃AgO₂ Na₃AgO₂ has been prepared anew (light pale-yellow powder samples; clear transparent single crystals). It crystallizes orthorhombic (space group Ibam) with a = 5.46₃, b = 10.92₆, c = 5.92₆ Å, Z = 4, d_rö = 3.94 g X cm^?3, d_pyk = 3.89 g X cm^?3; parameters are given in the text. The structure of Na₃AgO₂, marked by linear “dumb-bells” [O? Ag? O], d(Ag→O) = 2.09 Å is a novel variant of Na₂O. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, have been calculated and are discussed.