Ungewöhnliche Koordinationspolyeder um Sauerstoff in Li4Cl(OH)3

Unusual Coordination Polyhedra around Oxygen in Li₄Cl(OH)₃ The pseudobinary system LiOH/LiCl was investigated by X-ray methods. Two compounds, Li₄Cl(OH)₃ and Li₂Cl(OH), were obtained. The crystal structure of Li₄Cl(OH)₃ solved by single-crystal methods is delt with. For Li₂Cl(OH) powder diffraction data are given: Li₄Cl(OH)₃: P2₁/m, Z = 2, a = 5.4096(8) Å, b = 7.382(2) Å, c = 6.2076(8) Å, β = 94.40(1)°, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 483, Z (parameter) = 50, R/R_w = 0.022/0.025 Li₂Cl(OH): Pmma, Z = 2, a = 7.680(8) Å, b = 4.001(7) Å, c = 3.899(6) Å The hydroxide rich compound crystallizes in a new type of structure which contains puckered layers [Li₄(OH)₃⁺] connected via chloride ions.     

Li2Br(NH2): Das erste ternäre Alkalimetallamidhalogenid

Li₂Br(NH₂): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH₂/LiBr was investigated by X-ray methods. The crystal structure of the compound Li₂Br(NH₂) was solved by single crystal data: Li₂Br(NH₂): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 348, Z (parameter) = 51, R/R_w = 0.019/0.021 Li₂Br(NH₂) crystallizes in a new type of structure. To one another isolated chains of [Li₂Li_4/2(NH₂)₂²⁺] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement.     

Rb2I(OH): Ein Hydroxidiodid im System RbOH/RbI

Rb₂I(OH): A Hydroxide Iodide in the System RbOH/RbI The pseudobinary system RbOH/RbI was investigated by X-ray methods. The crystal structure of Rb₂I(OH) was solved by single crystal data: Rb₂I(OH): Pnma, Z = 4, a = 7.748(1) Å, b = 5.654(2) Å,c = 13.254(2) Å Z(F_o) with (F_o)² ? 3σ = (F_o)² = 449, Z (parameter) = 25, R/R_w = 0.021/0.023 Rb₂I(OH) crystallizes in a new type of structure, built up by a three dimensional network of [Rb₂(OH)⁺] containing the iodide ions.     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Na7I2(OH)5: Ein Hydroxidiodid im System NaOH/NaI

Na₇I₂(OH)₅: A Hydroxide Iodide in the System NaOH/NaI The pseudobinary system NaOH/NaI is investigated by X-ray methods. The crystal structure of the compound Na₇I₂(OH)₅ was solved by single crystal data: Na₇I₂(OH)₅: P4/nmm, Z = 2, a = 7.748(2) Å, c = 10.260(3) Å, Z(F_o) = 443 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.044/0.059 Na₇I₂(OH)₅ crystallizes in a new type of structure which contains puckered layers of ∞²[Na₇(OH)₅²⁺] connected via iodide ions.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Tl4Pd3Cl10 – eine Verbindung mit neuartiger [(PdCl2Cl2/2)4]4–‐Baugruppe

Tl₄Pd₃Cl₁₀ – A Compound with a New [(PdCl₂Cl_2/2)₄]^4– Group Single crystals of Tl₄Pd₃Cl₁₀ can be obtained by hydrothermal synthesis. They show tetragonal symmetry with lattice parameters a = 15.956(1) Å and c = 14.146(1) Å, Z = 8 and space group I42d (No. 122). The atomic arrangement of Tl₄Pd₃Cl₁₀ is explored by X‐ray crystal structure analysis. Tl₄Pd₃Cl₁₀ is the first example of a new structural type with a hitherto not isolated tetramer [(PdCl₂Cl_2/2)₄]^4– group.     

Synthese und Strukturuntersuchungen von Iodocupraten(I). XV Iodocuprate(I) mit solvatisierten Kationen: [Li(CH3CN)4][Cu2I3] und [Mg{(CH3)2CO}6][Cu2I4]

Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH₃CN)₄] [Cu₂I₃] and [Mg{(CH₃)₂CO}₆][Cu₂I₄] [Li(CH₃CN)₄][Cu₂I₃] 1 and [Mg((CH₃)₂CO)₆][Cu₂I₄] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI₂ in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH₃CN)₄]⁺ cations are located between rod packings of CuI₄ tetrahedra double chains [(CuI_2/2I_2/4)₂]^? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P2₁/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH₃)₂CO)₆]²⁺ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu₂I₄]^2? occupy holes in the trigonal prismatic channels formed by the cations.     

Das erste „Litho-Manganat(V)”︁ mit Schichtstruktur: Cs2{Li[MnO4]}

The First “Litho-Manganate(V)” with Layer-Structure: Cs₂{Li[MnO₄]} By heating intimate mixtures of the oxides [CsO_1,2, Li₂MnO₃; Cs: Mn = 2,3 : 1; Ag-Zylinder, 580°C, 62 d] blue-green single crystals of Cs₂{Li[VO₄]} were obtained for the first time. The new “Litho-Manganate(V)” crystallices orthorhombic (SG: Cmc2₁) with a = 596.08(7), b = 1202.6(1), c = 816.8(1) pm (Guinier-Simon data), Z = 4. It is isotypic with Cs₂{Li[VO₄]} [1]. The structure was determined by four-circle-diffractometer data [Mo? Kα , for 496I_o(hkl) R = 3.1%, R, = 2.4%], parameters see text. The Madelung Part of Lattice Energie, MAPLE and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, are calculated and disscussed.     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).     

Bi4RuBr2 und Bi4RuI2: Zwei Varianten einer Kolumnarstruktur mit flächenverknüpften quadratischen [RuBi8/2]-Antiprismen

Bi₄RuBr₂ and Bi₄RuI₂: Two Varieties of a Column Structure with Face-Sharing [RuBi_8/2] Square Antiprisms Reaction of the elements yields black, lustrous, air insensitive crystals of the subhalides Bi₄RuI₂ (tetragonal, I4/m, a = 1183.9(2) pm, c = 669.7(2) pm, V = 938.66 · 10⁶ pm³) and Bi₄RuBr₂ (monoclinic, I112/m, a = 1211.9(2) pm, b = 1072.6(2) pm, c = 663.9(2) pm, γ = 91.63(1)°, V = 862.64 · 10⁶ pm³). The structures of the homöotypic compounds contain [RuBi_8/2] strands of face-sharing square antiprisms. Halogen atoms lie above the edges of alternate Bi₄ squares. Thereby chemical bonding differs significantly within the two types of Bi₄ squares. Though the Ru atoms on the central axis of the strand of antiprisms form pairs, extended Hückel calculations give no evidence of Ru? Ru bonds.     

Co(OH)2/Ni(OH)2复合电极材料制备及其超级电容性质

以Co(NO_3)_2·6H_2O和Ni(NO_3)_2·6H_2O为钴源和镍源,采用溶剂热法一步合成了Co(OH)_2/Ni(OH)_2复合材料,通过煅烧该复合材料可得到NiCo_2O_4。采用XRD、SEM、BET等对材料进行了表征,结果表明,Co(OH)_2/Ni(OH)_2复合材料是薄片组成的花状形貌,比表面积为37. 48m~2/g。电化学性能测试表明,Co(OH)_2/Ni(OH)_2复合材料比NiCo_2O_4具有更高的比电容值和容量保持率。在0. 5A/g的电流密度下,复合材料比电容值可达到1097. 8F/g,而NiCo_2O_4比电容值仅为86. 1F/g。因此,与煅烧后的NiCo_2O_4材料相比,Co(OH)_2/Ni(OH)_2复合材料具有更加优良的电化学性能,这为高性能超级电容器材料的制备提供了一个新思路。     

Na5Br(OH)4: Darstellung und Kristallstruktur einer Verbindung im System NaOH/NaBr

Na₅Br(OH)₄: Synthesis and Structure of a Compound in the System NaOH/NaBr The pseudobinary system NaOH/NaBr is investigated by X-ray methods. The structure of the compound Na₅Br(OH)₄ was solved by single crystal data: Na₅Br(OH)₄: Pnma, Z = 8, a = 11.846(2) Å, b = 18.782(4) Å, c = 6.431(1) Å, Z(F_o) = 1 202 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 100, R/R_w = 0.030/0.035 The compound crystallizes in a new type of structure. Pairs of octahedra around O by 5 Na and 1 H to [Na₅(OH)]₂ are orientated in such a way to one another that two ions OH^? form a parallelogram hinting to unusual bent hydrogen bridge bonding.     

The series RE5Li2Sn7 (RE = Ce,Pr, Nd,Sm) revisited: crystal structure of RE5Li2−xSn7+x [0 ≤x≤ 0.03 (1)]

The series of RE₅Li₂Sn₇ (RE = Ce–Sm) compounds were synthesized by high‐temperature reactions and structurally characterized by single‐crystal X‐ray diffraction. The compounds are pentacerium dilithium heptastannide, Ce₅Li_1.97Sn_7.03, pentapreseodymium dilithium heptastannide, Pr₅Li_1.98Sn_7.02, pentaneodymium dilithium heptastannide, Nd₅Li_1.99Sn_7.01, and pentasamarium dilithium heptastannide, Sm₅Li₂Sn₇. All five compounds crystallize in the chiral orthorhombic space group P2₁2₁2₁ (No. 19), which is relatively uncommon among intermetallic phases. The structure belongs to the Ce₅Li₂Sn₇ structure type (Pearson symbol oP56), with 14 unique atoms in the asymmetric unit. Minor compositional variations exist, due to the mixed occupancy of Li and Sn atoms at one of the Li sites. The small occupational disorder is most evident for RE₅Li_2−xSn_7+x (RE = Ce, Pr; x≃ 0.03), while the structure of Nd₅Li₂Sn₇ and Sm₅Li₂Sn₇ show no apparent disorder.     

K2Br(OH) und Rb2Br(OH): Zwei neue ternäre Alkalimetallhalogenidhydroxide mit ausgeprägter Strukturverwandtschaft zu KOH bzw. RbOH

K₂Br(OH) and Rb₂Br(OH): Two New Ternary Alkali Metal Halide Hydroxides with a Pronounced Structural Relationship to KOH resp. RbOH Two isotypic compounds K₂Br(OH) and Rb₂Br(OH) were prepared in the systems KOH/KBr and RbOH/RbBr. Their structures were determined by single crystal X-ray methods: K₂Br(OH): P2₁/m, Z = 2, a = 6.724(1) Å, b = 4.272(4) Å, c = 8.442(2) Å, β = 108.14(2)°, Z(F_o) = 651 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.041/0.047 Rb₂Br(OH): P2₁/m, Z = 2, a = 6.918(3) Å, b = 4.483(2) Å, c = 8.850(5) Å, β = 108.08(6)°, Z(F_o) = 326 mit (F_o)² ≥ 3σ(F_o)², Z(parameter) = 27, R/R_w = 0.074/0.082. The compounds are built up by chains of [M₂(OH)⁺] connected via Br^?. The structure of the chains as well as their orientation to one another show a pronounced relationship to the structures of the room temperature modifications of the isotypic binary hydroxides KOH and RbOH.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

Das erste Titanat mit „Stuffed Pyrgoms”︁: RbNa3Li12[TiO4]4 = RbNa3Li8{Li[TiO4]}4

The First Titanate with ?Stuffed Pyrgoms”?: RbNa₃Li₁₂[TiO₄]₄ = RbNa₃Li₈{Li[TiO₄]}₄ By heating a well grounded mixture of the binary oxides Rb₂O, Na₂O, Li₂O, and TiO₂ [Rb:Na:Li:Ti = 1.1:3.1:12.5:4.0; 780°C, 41 d] we obtained RbNa₃Li₈{Li[TiO₄]}₄ as colourless platelike crystals. This first titanate with ?stuffed pyrgoms”? is isostructural with RbNa₃Li₈{Li[SiO₄]}₄, CsKNa₂Li₈{Li[SiO₄]}₄ and CsKNaLi₉{Li[SiO₄]}₄ [2]. The compound crystallizes tetragonal I4/m with a = 1 125.8(1) pm and c = 652.4(1) pm (Guinier-Simon-Data, Z = 2). The structure was determined by four-cyrcle-data (Siemens AED2, MoK) and leds to the residual values R = 3.7% and R_w = 3.1% (additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Raddii (MEFIR) and the Charge Distribution in Solids (CHARDI) are calculated and discussed.     

Ternäre Hydroxide. I. Synthese,Struktur und Eigenschaften von Li2[Sn(OH)6] · 2 H2O

Ternary Hydroxides. I. Synthesis, Structure, and Properties of Li₂[Sn(OH)₆] · 2 H₂O Colourless crystals of Li₂[Sn(OH)₆] · 2 H₂O were synthesized by reaction of SnCl₄ with LiOH in aqueous solution. The crystal structure was determined from single crystal data. Li₂[Sn(OH)₆] · 2 H₂O: monoclinic, P2₁/n (Nr. 14), a = 502.3(1), b = 692.3(1), c = 1020.2(3) pm, β = 99.78(1)°, V = 349.6(2) · 10⁶ pm³, Z = 2, R/Rw = 0.0192/0.0472, N(I) > 2σ(I) = 1527, N(Par.) = 54. Within the crystal structure only slightly distorted octahedrally [Sn(OH)₆]^2? ions are bonded via hydrogen bonds with water molecules forming layers, which themselve are linked by tetrahedrally coordinated Li ions; the structure is in accordance with the IR-data and the results of the ¹¹⁹Sn solid state NMR-spectroscopy; the hydrat water is eliminated at 117.1°C, the condensation reaction – forming the ternary oxide – takes place at 257.7°C.     

Hydrogensulfate mit fehlgeordneten Wasserstoffatomen – Synthese und Struktur von Li[H(HSO4)2](H2SO4)2 sowie Verfeinerung der Struktur von α-NaHSO4

Hydrogen Sulfates with Disordered Hydrogen Atoms – Synthesis and Structure of Li[H(HSO₄)₂](H₂SO₄)₂ and Refinement of the Structure of α-NaHSO₄ The structure of Li[H(HSO₄)₂](H₂SO₄)₂ has been determined for the first time whereas the structure of α-NaHSO₄ has been refined, so that direct determination of the hydrogen positions was possible. Both compounds crystallize triclinic in the space group P1 with the lattice constants a = 6.708(2), b = 6.995(1), c = 7.114(1) Å, α = 75.53(1), β = 84.09(2) and γ = 87.57(2)° (Z = 4) for α-NaHSO₄ and a = 4.915(1), b = 7.313(1), c = 8.346(2) Å, α = 82.42(3), β = 86.10(3) and γ = 80.93(3)° (Z = 1) for Li[H(HSO₄)₂](H₂SO₄)₂. In both compounds there are disordered hydrogen positions. In the structure of α-NaHSO₄ there are two crystallographically different HSO₄^? tetrahedra and two different coordinated Na atoms. The system of hydrogen bonds can be described by chains in [0–11] direction. The disordering of the H atoms reduces the differences between the S? O and S? OH distances (1.45 and 1.50 Å) while in the ordered HSO₄ unit “regular” bond lengths are observed (1.45 und 1,57 Å). In the structure of Li[H(HSO₄)₂](H₂SO₄)₂ there are two crystallographically different SO₄-tetrahedra. The first one belongs to the [H(HSO₄)₂]^? unit while the second one represents H₂SO₄ molecules. The H atom which is located nearby the symmetry centre and connects two HSO₄ units by a short O…?O distance of 2.44 Å. Li is located on a symmetry centre and is slightly distorted octahedrally coordinated by oxygen atoms of six different SO₄ tetrahedra. The system of hydrogen bonds can be regarded as consisting of double layers parallel to the xy-plane.     

Eine ‚Reduktive Austausch-Reaktion’︁: Einkristalle von Rb2[MnO4] aus Li[MnO4]

A ‘Reductive Exchange Reaction’: Single Crystals of Rb₂[MnO₄] from Li[MnO₄] By heating of well ground mixtures of the oxides RbO_0.9 and Li[MnO₄] (Rb:Mn = 1.5:1; Ag-tubes; 660°C, 56 d) dark-green, orthorhombic single-crystals of Rb₂[MnO₄] were obtained. The structural determination revealed the isotype to K₂[MnO₄]; a β-K₂SO₄-typ. Thus, for the first time by a pure solid-state-chemical way, via a reductive, complete alkali-metal exchange, single crystals of an oxomanganate(VI) of the alkali metals were prepared. The Madelung Part of the Lattice Energy, MAPLE, and the charge distribution were calculated.