Li2I(OH): Eine Verbindung mit eindimensional unendlich kantenverknüpften [Li4/2(OH)]+-Pyramiden

Li₂I(OH): A Compound with Onedimensional Infinite Edge Sharing [Li_4/2(OH)⁺] Pyramids The pseudobinary system LiOH/LiI was investigated by X-ray methods. Two compounds, Li₂I(OH) and Li₅I(OH)₄ exist. The structure of Li₂I(OH) was solved by single-crystal data. For Li₅I(OH)₄ lattice constants and space group symmetry are given: Li₂I(OH): Pnma, Z = 4, a = 10.339(4) Å, b = 5.567(1) Å, c = 6.643(2) Å, Z(F_o) mit (F_o)² ≧ 3σ(F_o)² = 439, Z (parameter) = 23, R/R_w = 0.030/0.040 Li₅I(OH)₄: Pmmn or P2₁mn(= Pmn2₁), Z = 2, a = 10.42 Å, b = 5.30 Å, c = 5.81 Å Li₂I(OH) crystallizes in a new type of structure. The motif of a distorted hexagonal close-packed arrangement of iodide ions is penetrated by chains of [Li_4/2(OH)⁺].     

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.     

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.     

Das erste Alkali-Erdalkalimetall-Oxo/Peroxo-Aurat(III): NaBa4AuO4(O2)2

On the first Alkaline-Alkaline-Earth-Oxo/Peroxo-Aurate(III): NaBa₄AuO₄(O₂)₂ The hitherto unknown compound NaBa₄AuO₄(O₂)₂ was prepared by oxidizing of barium gold alloy with Na₂O₂ in closed Ag-bombs. X-ray single crystal investigation led to tetragonal symmetry space group DI4/mmm, a = 5.939; c = 15.393 Å, Z = 2. NaBa₄AuO₄(O₂)₂ shows a distorted square antiprismatic surrounding of Ba²⁺ by four peroxo groups on one side and four O^2? on the opposite. Au³⁺ shows the usual square planar polygons of AuO₄. Na⁺ is coordinated by four O^2? ions in the base of an octahedron and two peroxo groups in the apical positions.     

KEu(CH3COO)3, das erste ternäre Europium(II)-acetat

KEu(CH₃COO)₃, the First Ternary Europium(II) Acetate On of EuCl₂ with a melt of dry potassium acetate yields pale greenish-yellow single crystals (300°C, sealed glass ampoule, EuCl₂ and K(CH₃COO) in a molar ratio of 1 : 3). The crystal structure determination (orthorhombic, P2₁2₁2₁ (no. 19), Z = 8, a = 1166.3(1) pm, b = 1288.4(2) pm, c = 1493.9(2) pm, R = 0.043, R_w = 0.032) revealed the composition KEu(CH₃COO)₃. The structure consists of one-dimensional chains built up by bridging acetate groups in the [100] and [001] directions in which potassium and europium alternate as central atoms. Eu²⁺ is surrounded by nine and eight and K⁺ by seven and six oxygen atoms, respectively. These chains are linked in the [010] direction so that a three-dimensional network is formed. The high coordination numbers of the acetate oxygen atoms of up to four are remarkable. Therefore, the acetate groups have highly bridging functions in addition to their chelating coordination of 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.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Das erste quaternäre Oxocobaltat(I): CsK2[CoO2]

The First Quaternary Oxide of Monovalent Cobalt: CsK₂[CoO₂] Dark-red single crystals of CsK₂[CoO₂] were obtained via ?reaction with the cyliner surface”? by heating powders of Cs₂K₂Cd₃O₅ in closed Co-cylinders at 500°C during 48 d. Structure solution and refinement (four-circle diffractometer data, MoKα , 147 independent I_o(hkl), none was omitted, R = 3.42%, R_w = 2.24%) show close relationship with RbNa₂[NiO₂] [2]. The lattice-constants are: (powder data, standard deviations in parentheses) MAPLE calculations, investigations of magnetism and EPR measurement add to the monovalence of Co.     

Ag5GeO4, das erste subvalente ternäre Silberoxid

Ag₅GeO₄, the First Subvalent Ternary Silver Oxide Applying high oxygen pressure the first subvalent ternary silver oxide Ag₅GeO₄ was obtained (for crystallographic data c.f. “Inhaltsübersicht”). Ag₅GeO₄ contains tetrahedral GeO₄^4?-ions besides [Ag₆]⁴⁺ clusters, which have not been observed in ternary silver oxides, so far. The electrical and magnetical properties prove the localisation of two paired electrons in each silver octahedron. The thermal decomposition occurs in two steps at 432.7 °C and 524.5°C.     

Na2Li3CoO4, das Erste quaternäre Oxocobaltat(III) der Alkalimetalle

Na₂Li₃CoO₄, the First Quaternary Oxocobaltate(III) of the Alkali Metals For the first time we obtained Na₂Li₃CoO₄ by annealing intimate mixtures of Co₃O₄, Na₂O₂, and Li₂O [Co : Na : Li = 1 : 2.2 : 10.1; 760°C; 21 d; Ag-tube] in form of transparent red single crystals. Structure Refinement [four-circle diffractometer data; AED2; MoKα-radiation; 1016 I_o(hkl); R = 2.6%; R_w = 2.0%; space group Pnnm; Z = 4; a = 818.7(3), b = 799.4(2), c = 655.1(2) pm] confirms the isotypism to Na₂Li₃GaO₄ [2] and Na₂Li₃FeO₄ [3]. Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, and the Charge Distribution were calculated. The isotypism of Na₂Li₃CoO₄ and Na₂Li₃GaO₄ is compared graphically.     

Zur Kenntnis von Na4Br(NH2)3: Ein Amidbromid im System NaNH2/NaBr

Na₄Br(NH₂)₃: An Amide Bromide in the System NaNH₂/NaBr The pseudobinary system NaNH₂/NaBr was investigated by X-ray methods. The crystal structure of Na₄Br(NH₂)₃ was solved by single crystal data: Pnnm, Z = 4, a = 6.579(2) Å, b = 12.755(4) Å, c = 8.776(2) Å Z(F_o) with (F_o)² ≥ 3σ = (F_o)² = 503, Z(parameter) = 39, R/R_w = 0.082/0.106. It is a new type of structure, built up by a three-dimensional network of [Na₄(NH₂)₃⁺] containing the bromide ions.     

[La2Cl3(OAc)2(H2O)7]Cl: Das erste Lanthanid-Acetat-Halogenid-Hydrat mit Chlorid in innerer Koordinationssphäre

[La₂Cl₃(OAc)₂(H₂O)₇]Cl: The First Lanthanide-Acetate-Halide-Hydrate with Chloride in Inner-Sphere Coordination [La₂Cl₃(OAc)₂(H₂O)₇]Cl has been obtained as single crystals through the reaction of LaCl₃ · 7H₂O with diluted acetic acid or from La₂O₃ with acetyl chloride. In the crystal structure (triclinic, Z = 2, P1 (no. 2), a = 919.6(2), b = 950.7(2), c = 1178.9(2) pm, α = 82.52(1), β = 84.14(1), γ = 64.69(1)°, R = 0.021, R_w = 0.020), La³⁺ is surrounded by nine ligands (O, Cl). La1 has two chloride and seven oxygen ligands whereas La2 has one chloride and eight oxygen atoms as nearest neighbours. Four of the oxygen ligands of each lanthanum cation originate from a ?tetradentate”? acetate anion, the others from crystal water molecules. The ?tetradentate”? acetate groups are coordinated not only to one central La³⁺ as chelate ligands, but also to the ?left”? and ?right”? La³⁺ neighbours. Thereby, a one-dimensional infinite cationic chain, [La₂Cl₃(OAc)₂(H₂O)₇]⁺, is formed that runs in the [011] direction. These chains are held together by ?lonesome”? chloride ions which are surrounded by (4 + 1) water molecules and connected to the chains via hydrogen bonds.     

Die Ammonolyse von (NH4)2GeF6. Darstellung und Struktur von NH4[Ge(NH3)F5]

Ammonolysis Reaction of (NH₄)₂GeF₆. Synthesis and Structure of NH₄[Ge(NH₃)F₅] (NH₄)₂GeF₆ reacts with ammonia to yield NH₄[Ge(NH₃)F₅] at 280°C. The reaction path was elucidated by in situ time and temperature resolved X-ray powder diffraction. NH₄[Ge(NH₃)F₅] crystallizes isostructurally to NH₄[Si(NH₃)F₅] in the tetragonal space group P4/n (No. 85) with lattice constants a = 619.41(1) pm and c = 724.70(1) pm. The germanium atom is coordinated by five fluorine atoms and the nitrogen atom of the ammonia molecule. The ammonium cation is located on the Wyckoff position (2 a) in P4/n. The crystal structure is stabilized by extensive hydrogen bonding.     

Darstellung und Struktur von Sn(NH2)2F2

Synthesis and Structure of Sn(NH₂)₂F₂ Diamido-difluoro-tin Sn(NH₂)₂F₂ can be produced by ammonolysis from (NH₄)₂SnF₆ at 613 K. The compound is a product from Sn(NH₃)₂F₄ formed during the ammonolysis reaction. Sn(NH₂)₂F₂ crystallizes in space group C2/m (No. 12) with lattice constants a = 1070.18(7), b = 325.38(3) pm, c = 505.02(3) pm and β = 105.728(3)° (V = 169.271(6) · 10⁶ pm³) containing two formula units per unit cell. Data refinement by the Rietveld method yields a Bragg R-value of R_Bragg = 0.0514 (Profile R-value R_wp = 0.177). Tin is octahedrally coordinated by two fluorine atoms and for amido groups. The octahedra are connected to one-dimensional strings by edge sharing. The NH₂ groups are in the bridging position whilst the fluorine atoms are terminal.     

Na2Mn(NH2)4: Ein neuer Schichtenstrukturtyp

Na₂Mn(NH₂)₄: A New Type of Layered Structure The structure of Na₂Mn(NH₂)₄ was solved by X-ray single crystal data including H-positions: P2₁/c, Z = 4, a = 6.331(1) Å, b = 14.542(3) Å, c = 7.212(1) Å, β = 116.29(1)°, Z(F ≥ 3σ = (F)) = 1343, Z(parameters) = 96, R/R_W = 0.023/0.029. The compound crystallizes in a new type of structure. Within layered blocks the amide ions are arranged with the motif of a hexagonal closest packing of spheres. Within these blocks alternating layers contain sodium in all octahedral sites and manganese in an ordered way in a quarter of tetrahedral sites.     

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].     

Na4AuTl,die erste ternäre Verbindung im System Natrium/Gold/Thallium

Na₄AuTl, the First Ternary Compound in the System Sodium/Gold/Thallium Silver coloured, brittle single crystals of Na₄AuTl were obtained by the reaction of NaN₃, gold sponge and TlN₃ at 773 K. The structure was determined from X-ray single-crystal diffractometry data: Na₄AuTl crystallizes in a new structure type with separated gold and thallium partial structures. These consist of linear [Au_2/2] chains and [Tl₂] dumb-bells. Structural relationships between Na₂Au and the Na Au partial structure of Na₄AuTl are discussed.     

Das neue ternäre Borid Mg8Pt4B und die neue intermetallische Verbindung PtMg2

The New Ternary Boride Mg₈Pt₄B and the New Intermetallic Compound PtMg₂ The new magnesium platinum boride Mg₈Pt₄B was obtained from a reaction of the elements in sealed niobium tubes. It crystallizes isotypically with Mg₈Rh₄B in the cubic space group with a =12.2481(1) Å and can be structurally derived from the Ti₂Ni structure type, where boron occupies cavities, which are formed by four magnesium and four platium atoms. The new intermetallic compound PtMg₂ was also prepared by reaction of the elements in a sealed Nb container and adopts the tetragonal CuAl₂ type structure, space group I4/mcm with a = 6.334(1) Å and c = 5.621(1) Å.     

Ba5[CrN4]N: Das erste Nitridochromat(V)

Ba₅[CrN₄]N: The First Nitridochromate(V) Ba₅[CrN₄]N is prepared by reaction of mixtures of Li₃N, Ba₃N₂ and CrN/Cr₂N (1 : 1) (molar ratio Li : Ba : Cr = 3 : 5 : 1) in tantalum crucibles at 700°C with flowing nitrogen (1 atm) within a period of 48 h. After cooling down to room temperature (60°C/h) black-shining single crystals of the ternary phase with a platy habit are obtained (monoclinic, C2/m; a = 1054.0(2) pm, b = 1170.9(3) pm, c = 937.7(2) pm, b? = 110,79(2)°; Z = 4). The crystal structure contains isolated complex anions [Cr^VN₄]^7? which nearly satisfy the ideal tetrahedral symmetry (Cr? N [pm]: 2 × 175.3(4), 2 × 175.8(5); N? Cr? N [°]: 106.8(2), 109.5(2), 2 × 109.9(2), 2 × 110,3(2)). The coordination sphere for each of the terminal nitride functions of the complex anions is completed by five neighbouring Ba²⁺ ions (distorted CrBa₅ octahedra). The octahedra are connected via common CrBa₂ faces as well as CrBa edges thereby forming condensed tetrameric octahedral groups. The isolated nitride ions which are also present in the crystal structure of Ba₅[CrN₄]N are in an octahedral environment of Ba²⁺ ions. The presence of a d¹-System (Cr(V)) is confirmed by magnetic susceptibility data.     

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.