Synthese und Struktur einer tetragonalen Fluorperowskitvariante mit Kationendefizit — Cs4PdMn2F12

Synthesis and Structure of a Tetragonal Fluoroperovskitevariety Deficient in Cations — Cs₄PdMn₂F₁₂ Single crystals of red Cs₄PdMn₂F₁₂ were obtained by systematic investigations in the system CsF/MnF₃/Pd/PdF₃. The Compound crystallizes with a = b = 856.89(6) pm, c = 1918.35(18) pm, spcgr. I 4₁lamd — D (No. 141) and Z = 4. It is structurally related to K₄MnMn₂F₁₂, but with square arrangement (isotypic?) of F^— around Pd²⁺.     

Synthese und Struktur von Ag7M6F31 (M = Zr,Hf, Ce)

Synthesis and Structure of Ag₇M₆F₃₁ (M = Zr, Hf, Ce) Colorless single crystals of Ag₇Zr₆F₃₁ have been obtainend by heating up a mixture of AgF and ZrF₄ in a closed goldtube (T = 450 °C, t ∼ 2 d). The compound crystallizes trigonal, space group R3‐C (No. 148) with a = 1400,9(3) pm, c = 979,0(2) pm, Z = 3. Also prepared were the isotypic compounds Ag₇Hf₆F₃₁ with a = 1393,8(2) pm, c = 978,7(2) pm, and Ag₇Ce₆F₃₁ with a = 1469,8(1) pm, c = 998,5(1) pm.     

Synthese,Struktur und magnetische Eigenschaften der Verbindungen NaMIIZr2F11 (MII = Ti,V und Cu) und einem Anhang über NaPdZr2F11

Synthesis, Structure, and Magnetic Properties of Compounds NaM^IIZr₂F₁₁ (M^II = Ti, V, Cu) and a Notice on NaPdZr₂F₁₁ By synthesizing NaTiZr₂F₁₁ in form of red single crystals, it was possible to obtain a complex fluoride with Ti²⁺ for the first time. It crystallizes like the analogous greenish blue vanadium compound isotypic to AgPdZr₂F₁₁ [1] monoclinic, spacegroup C2/m–C (No. 12) with a = 918.0/911.5 pm, b = 682.6/675.7 pm, c = 780.8/776.6 pm, β = 116.2/116.2º and Z = 2. Colourless NaCuZr₂F₁₁ however crystallizes as a result of the Jahn-Teller distortion of Cu²⁺ triclinic (space group P1 –C (No. 2), a = 552.7 pm, b = 568.2 pm, c = 768.0 pm, α = 111.0º, β = 97.4º, γ = 106.4º) and is – as expected – isotypic to NaAgZr₂F₁₁ [1].     

K3Er7S12 und Rb3Er7S12: Zwei ternäre Erbium(III)‐sulfide mit Kanalstruktur

K₃Er₇S₁₂ and Rb₃Er₇S₁₂: Two Ternary Erbium(III) Sulfides with Channel Structures The isotypic ternary erbium(III) sulfides K₃Er₇S₁₂ (a = 1185.38(9), b = 2461.5(2), c = 393.59(3) pm) and Rb₃Er₇S₁₂ (a = 1203.51(9), b = 2483.0(2), c = 394.85(3) pm; both orthorhombic, Pnnm, Z = 2) are obtained by reacting erbium metal and sulfur with an excess of alkali chloride (KCl or RbCl, respectively) serving as flux and reagent within seven days at 900 °C. The rod—shaped, yellow, transparent single crystals distinguish themselves in their crystal structure by a framework of corner— and edge—linked [ErS₆] octahedra (d(Er³⁺—S^2—) = 265—285 pm), in which the alkali metal cations (K⁺ and Rb⁺, respectively; CN = 6 and 7 + 1) are inserted into channels running along [001]. Under consideration of the ionic radius quotients r_i(A⁺)/r_i(Ch^2—) (A = K—Cs, Ch = S—Te) the existence range of this Cs₃Y₇Se₁₂—type of structure is discussed.     

Synthese und Struktur von Zr4ON3F5, einer Verbindung mit fluorit-verwandter Überstruktur vom Vernier-Typ

Synthesis and Structure of Zr₄ON₃F₅, a Compound with a Fluorite Related Superstructure of the Vernier Type Ammonolysis of β? ZrF₄ or ZrF₄ · NH₃ yields zirconium nitride fluoride ZrNF and zirconium oxide nitride fluoride Zr₄ON₃F₅. Electron diffraction and electron energy loss spectroscopy were used to distinguish these two ammonolysis products by structure and composition. ZrNF crystallizes isotypically to baddeleyite ZrO₂ in the space group P2₁/c with the lattice constants a = 522.7(3), b = 502.6(2), c = 519.1(3) pm, β = 98.98(7)°, Z = 4, while Zr₄ON₃F₅ forms an anion-excess fluorite-related structure of the vernier type. The structure of Zr₄ON₃F₅ was refined from neutron powder diffraction data. It crystallizes monoclinic in space group P112₁/b with lattice constants a = 512.17(3), b = 2 151.3(1), c = 536.69(3) pm, γ = 90.128(6)°, Z = 4. Within the homologous series M_nX_2n+1 of the vernier phases Zr₄ON₃F₅ is a member with n = 4.     

Peroxofluorokomplexe der Übergangsmetalle. IX. Kristallstruktur von Ba3[Ti(O2)F5]2 · 2 H2O

Transition Metal Peroxofluoro Complexes. IX. Crystal Structure of Ba₃[Ti(O₂)F₅]₂ · 2 H₂O The pale yellow hydrat Ba₃[Ti(O₂)F₅]₂ · 2 H₂O crystallizes tetragonal (space group P4₂/mbc, a = 1 248.5(3), c = 812.2(2) pm; Z = 4; R = 0.026 for 404 independent reflections). It contains isolated [Ti(O₂)F₅]^3? anions. Thermal decomposition leads directly to α-Ba₃Ti₂O₂F₁₀, which is isotypic to α-Ba₃Al₂F₁₂.     

Über Komplexe Fluoride des zweiwertigen Palladiums

On Complex Fluorides of Divalent Palladium For the first time single crystals of the new compounds RbPdPdF₅, KPdPdF₅, and K₂CsPdF₅ have been obtained. Orange brown RbPdPdF₅ crystallizes orthorhombic, space group Imma–D_2h²⁸ (No. 74) with a = 633.6(1) pm, b = 765.5.(1) pm, c = 1067.5(1) pm and Z = 4 and is isotypic with CsPdPdF₅ [1]. Structure related KPdPdF₅ (also orange brown) crystallizes orthorhombic too, but in space group Pnma–D_2h¹⁶ (No. 62) with a 614.12(9) pm, b = 748.7(1) pm, c = 1065.0(2) pm and Z = 4. K₂CsPdF₅, light yellow, crystallizes tetragonal with a = 736.3(1) pm, c = 628.0(1) pm, Z = 2, and is isotypic with Rb₂CsPdF₅ (space group P4/mbm? D_4h⁵ Nr. 127), an ordered structure variant of the Rb₃PdF₅-Type [1].     

Zur Kenntnis des Rb2PbO3-Typs: Über Rb2ZrO3, Rb2SnO3 und Rb2TbO3

According to X-ray powder work, orthorhombic Rb₂ZrO₃ [a = 10.7, b = 7.40, c = 5.87 Å] and Rb₂SnO₃ [a = 10.7, b = 7.49, c = 5.75 Å] are isotypic with Rb₂PbO₃. Discussion of different structural models and the Madelung Part of Lattice Energy (MAPLE) shows that the annormal Coordination Number of M⁴⁺ (CN = 5) is caused by the type of formula.     

Darstellung und Kristallstruktur von Rb4Br2O und Rb6Br4O

Syntheses and Crystal Structures of Rb₄Br₂O and Rb₆Br₄O In the quasi‐binary system RbBr/Rb₂O, the addition compounds Rb₄Br₂O and Rb₆Br₄O are obtained by solid state reaction of the boundary components RbBr and Rb₂O. Crystals of red‐orange Rb₄Br₂O as well as of orange Rb₆Br₄O decompose immediately when exposed to air. Rb₄Br₂O (Pearson code tI14, I4/mmm, a = 544.4(6) pm, c = 1725(2) pm, Z = 2, 175 symmetry independent reflections with I_o > 2σ(I), R₁= 0.0618) crystallizes in the anti K₂NiF₄ structure type; Rb₆Br₄O (Pearson code hR22, R3c, a = 1307.8(3) pm, c = 1646.6(5) pm, Z = 6, 630 symmetry independent reflections with I_o > 2σ(I), R₁ = 0.0759) in the anti K₄CdCl₆ structure type. Both structures contain characteristic ORb₆‐octahedra and can be understood as expanded perovskites, following the general systematics of alkaline metal oxide halides.     

Carbonat‐Hydrate der schweren Alkalimetalle: Darstellung und Struktur von Rb2CO3 · 1,5 H2O und Cs2CO3 · 3 H2O

Carbonate Hydrates of the Heavy Alkali Metals: Preparation and Structure of Rb₂CO₃ · 1.5 H₂O und Cs₂CO₃ · 3 H₂O Rb₂CO₃ · 1.5 H₂O and Cs₂CO₃ · 3 H₂O were prepared from aqueous solution and by means of the reaction of dialkylcarbonates with RbOH and CsOH resp. in hydrous alcoholes. Based on four‐circle diffractometer data, the crystal structures were determined (Rb₂CO₃ · 1.5 H₂O: C2/c (no. 15), Z = 8, a = 1237.7(2) pm, b = 1385.94(7) pm, c = 747.7(4) pm, β = 120.133(8)°, V_EZ = 1109.3(6) · 10⁶ pm³; Cs₂CO₃ · 3 H₂O: P2/c (no. 13), Z = 2, a = 654.5(2) pm, b = 679.06(6) pm, c = 886.4(2) pm, β = 90.708(14)°, V_EZ = 393.9(2) · 10⁶ pm³). Rb₂CO₃ · 1.5 H₂O is isostructural with K₂CO₃ · 1.5 H₂O. In case of Cs₂CO₃ · 3 H₂O no comparable structure is known. Both structures show [(CO₃^2–)(H₂O)]‐chains, being connected via additional H₂O forming columns (Rb₂CO₃ · 1.5 H₂O) and layers (Cs₂CO₃ · 3 H₂O), respectively.     

Rb3LnCl6 · 2 H2O (Ln = La?Nd): Darstellung,Kristallstruktur und thermisches Verhalten

Rb₃LnCl₆ · 2 H₂O (Ln = La? Nd): Preparation, Crystal Structure, and Thermal Behaviour The compounds Rb₃LnCl₆ · 2 H₂O (Ln = La? Nd) were prepared from acetic acid as powders. The preparation from aqueous solutions does not yield the pure products because RbCl precipitates as first compound. The structure of Rb₃LaCl₆ · 2 H₂O was determined by X-ray analysis of a single crystal obtained from aqueous solution. The compounds with Ln = La? Nd are isotypic. They crystallize hexagonally in the space group P6₃/m (Rb₃LaCl₆ · 2 H₂O: a = 1 220.4(2) pm, c = 1 688.6(3) (pm) with Z = 6. Anionic trimeric units [Ln₃Cl₁₂(H₂O)₆]^3? are stacked along the c-axis over the corners of the unit cell. In the stacking frequency the units are rotated by 60° with respect to each other around the c-axis. The coordination number (C. N.) of Ln³⁺ is 8, which is satisfied by four bridging and two terminal chloride ions and two water molecules. The coordination spheres of the three rubidium ions in the different atomic positions are composed differently, their C.N. are 9, 8(+1) and 6(+6). The thermal dehydration of the compounds occurs in one step. The hydrates decompose at ca. 100°C to form the anhydrous compounds Rb₂LnCl₅ und RbCl since the anhydrous chlorides Rb₃LnCl₆ are thermodynamically stable above ca. 400°C only.     

Synthese und Kristallstruktur von Rb3PbCl5

Synthesis and Crystal Structure of Rb₃PbCl₅ The synthesis of the hitherto unknown compound Rb₃PbCl₅ in the quasi-binary system RbCl/PbCl₂ and its structure determination is reported. This 3 : 1-phase decomposes peritectoidally at 305 °C and crystallizes in a so far unknown structure type in the orthorhombic space group Pnma (a = 863.498(5) pm, b = 1573.11(1) pm, c = 838.875(5) pm). It shows typical structural characteristics of ns²-configurated cations, although there are more noble gas-configurated cations than ns²-configurated cations in the structure.     

K2MCl5(M = La—Dy) und Rb2MCl5 (M = La—Eu): Ino-Chloride mit siebenfach koordinierten Seltenen Erden

K₂MCl₅(M = La—Dy) and Rb₂MCl₅ (M = La—Eu): Ino-chlorides with Seven—Coordinated Rare Earths K₂PrCl₅ crystallizes with a = 1263.1(8), b = 875.6(3), c = 797.3(4) pm, Z = 4, orthorhombic, Pnma, isotypic to e. g. Y₂HfS₅. Monocapped trigonal prisms (C.N. = 7) are connected to chains via common edges in [010] direction according to [PrCl_3/1^tCl_4/2^k]^2? with d?(Pr? Cl) = 281 pm. The chlorides K₂MCl₅ (M = La—Dy) and Rb₂MCl₅ (M = La—Eu) are isotypic to K₂PrCl₅. Thermal expansion of Rb₂PrCl₅ in [010] direction is remarkably smaller than parallel to (010).     

Die Oxoantimonate(III) Rb2Sb8O13 und Cs8Sb22O37: Neue Schicht‐ und Gerüststrukturen mit ‘Lone‐Pair’ ‐Kationen

The Oxoantimonates(III) Rb₂Sb₈O₁₃ and Cs₈Sb₂₂O₃₇: New Framework and Layer Structures with ‘Lone‐Pair’ Cations The oxoantimonates(III) Rb₂Sb₈O₁₃ and Cs₈Sb₂₂O₃₇ were synthezised from Sb₂O₃, the elemental alkali metals (A) and the hyperoxides (AO₂) at 500 °C. The crystal structures of Rb₂Sb₈O₁₃ (monoclinic, P2₁/m, a=743.7(12)pm, b=1724(3)pm, c=1380(2)pm, β=90.44(4) °, Z=4) and Cs₈Sb₂₂O₃₇ (monoclinic, Cc, a=1299.93(11)pm, b=719.87(6)pm, c=3089.9(3)pm, β=96.00(2) °, Z=2) exhibit complex layer (Rb) and framework oxoantimonate ions (Cs), with the Sb^III cation, due to its stereochemically active ‘lone‐pair’, in ψ‐tetrahedral (CN=3) to ψ‐trigonal‐bipyramidal (CN=4) coordination by O.     

New Fluoromanganate(III) Hydrates: Mn3F8 · 12H2O and AgMnF4 · 4H2O

Single crystals of fluoride hydrates Mn₃F₈ · 12 H₂O and AgMnF₄ · 4 H₂O have been prepared and characterized by X-ray methods. Mn₃F₈ · 12 H₂O crystallizes in the space group P1 (a = 623.0(3), b = 896.7(4), c = 931.8(4) pm, α = 110.07(2)°, β = 103.18(2)°, γ = 107.54(2)°, Z = 1); AgMnF₄ · 4 H₂O crystallizes in the space group P2₁/m (a = 700.9(2), b = 726.1(1), c = 749.4(3) pm, β = 107.17(3)°, Z = 2). Both structures contain Jahn-Teller-distorted [Mn(H₂O)₂F₄]^? anions as well as crystal water molecules and exhibit a complex hydrogen bond network between anions and cations, i. e. [Mn(H₂O)₆]²⁺ for the first and a polymeric [Ag(H₂O)₂]^? cation for the second compound.     

Neue Fluorozirconate und ‐hafnate mit V2+ und Ti2+

New Fluorozirconates and ‐hafnates with V²⁺ and Ti²⁺ During investigations of the systems MF₂/KF/MF₄ e. g. MF₂/NaF/MF₄ (M²⁺ = Ti²⁺, V²⁺, M⁴⁺ = Zr⁴⁺, Hf⁴⁺) we obtained blue crystals of VZrF₆, VHfF₆, KVZrF₇, blue‐green crystals of NaVHf₂F₁₁, yellow crystals of TiHfF₆ and NaTiHf₂F₁₁, and yellow to rubyred crystals of TiZrF₆, respectively. According to single crystal data, VZrF₆ VHfF₆ and TiZrF₆ crystalizes in the ordered ReO₃‐type (cubic, Fm3m, a = 812,1(5), 804,2(8), and 821,0(2) pm, Z = 4). TiHfF₆ crystalizes in a high‐temperature‐modification (cubic, ReO₃‐type, Pm3m, a = 392,3(2) pm, Z = 2). KVZrF₇ is isotyic to KPdZrF₇ (orthorhombic, Pnna, a = 1109,8(6), b = 788,0(7), c = 648,0(15) pm, Z = 4). NaTiHf₂F₁₁ and NaVHf₂F₁₁ crystalizes monoclinic (C2/m, a = 910,5(7), b = 675,9(7), c = 773,6(5) pm, β = 116,10(6)° and a = 917,7(5), b = 685,7(5), c = 752,4 pm, β = 118,28(1)°, Z = 2, respectively) and are also isotypic to already known AgPdZr₂F₁₁.     

Neue Komplexe Fluoride mit Ag2+ und Pd2+: NaMIIZr2F11 (MII = Ag,Pd) und AgPdZr2F11

New Complex Fluorides with Ag²⁺ and Pd²⁺: NaM^IIZr₂F₁₁ (M^II = Ag, Pd) and AgPdZr₂F₁₁ For the first time single crystals of NaAgZr₂F₁₁, NaPdZr₂F₁₁ and AgPdZr₂F₁₁ have been obtained and investigated by X-ray methods. The isotypic compounds NaM^IIZr₂F₁₁ (M^II = Ag, Pd) crystallize triclinic, spcgr. P1 ? C (No. 2) with a = 780.9, b = 570.0, c = 583.2 pm, α = 106.1°, β = 112.2°, γ = 97.9° (NaPdZr₂F₁₁), AgPdZr₂F₁₁ is monoclinic, spcgr. C2/m? C_2h (No. 12) with a = 935.1, b = 699.1, c = 780.1 pm, β = 115.7°, Z = 2 (Four circle diffractometer data, Siemens AED 2). Their structure is closeley related to the Ag₃Hf₂F₁₄-type of structure.     

An Ortho‐silicate‐hydroxide: Rb5[SiO4][OH]

Rb₅[SiO₄][OH] crystallizes in the monoclinc space group C2/m with a = 737.3(1) pm, b = 1073.7(2) pm, c = 1207.2(2) pm, β = 106.07(2)° and Z = 4 (single crystal data; R1= 0.0681 all data). Layers of edge‐connected distorted trigonal prismatic [(OH)Rb₆] entities and isolated tetrahedral [SiO₄] units present the main structural features of this unprecedented structure type.     

Peroxofluorokomplexe der Übergangsmetalle. IV. Zur Strukturchemie von Diperoxo-tetrafluorotantalaten(V): K3Ta(O2)2F4 und verwandte Phasen sowie (NH4)3Ta(O2)2F4

Transition Metal Peroxofluoro Complexes. IV. Structural Chemistry of Diperoxo-tetrafluorotantalates (V): K₃Ta(O₂)₂F₄ and Related Phases and (NH₄)₃Ta(O₂)₂F₄ Dependent on the preparative conditions K₃Ta(O₂)₂F₄ crystallizes in a monoclinic (a = 908.2(1), b = 899.2(1), c = 910.0(2) pm, β = 90.37(1)°) or — with variations in stoichiometry – in cubic phases (a = 905 to 909 pm) of the elpasolite type. The i.r. data as well as the thermal decomposition to tetragonal K₃TaO₂F₄ (a = 621.0(2), c = 884.3(4) pm, with superstructure) with cis-standing O atoms indicate the cis-position also for the O₂ groups. A single crystal X-ray structure analysis of (NH₄)₃Ta(O₂)₂F₄ (space group Fm3m, a = 941.4(7) pm, Z = 4, R_w = 0.032) yielded disordered elpasolite structure. The [Ta(O₂)₂F₄] octahedra have cis-configuration. No phase transition has been observed by X-rays when cooling down to 120 K.     

Die ersten Hydrogencarbonate mit einer trimeren [H2(CO3)3]4−-Baugruppe: Zur Darstellung und Kristallstruktur von Rb4H2(CO3)3 · H2O und K4H2(CO3)3 · 1,5 H2O

The First Hydrogencarbonates with a Trimeric [H₂(CO₃)₃]^4? Group: Preparation and Crystal Structure of Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1.5 H₂O Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1,5 H₂O were prepared by means of the reaction of (CH₃)₂CO₃ with RbOH resp. KOH in aqueous methanole. Trimer [H₂(CO₃)₃]^4?-anions were found in the crystal structure of Rb₄H₂(CO₃)₃ · H₂O (orthorhombic, Pnma (no. 62), a = 1 218.0(1) pm, b = 1 572.3(6) pm, c = 615.9(1) pm, V_EZ = 1 179.5(5) · 10⁶ pm³, Z = 4, R1(I ≥ 2σ(I)) = 0.027, wR2(I ≥ 2σ(I)) = 0.055). K₄H₂(CO₃)₃ · 1,5 H₂O crystallizes in an OD-structure. The determined superposition structure (orthorhombic, Pbam (no. 55), a = 1 161.8(1) pm, b = 597.0(1) pm, c = 383.85(3) pm, V_EZ = 266.3(1) · 10⁶ pm³, Z = 1, R1(I ≥ 2σ(I)) = 0.035, wR2(I ≥ 2σ(I)) = 0.074) can be derived from the structure of the rubidium compound. The thermal decomposition of the substances is discussed.