HgPb2O2Cl2, ein „perforiertes”︁ Blei(II)-oxid

HgPb₂O₂Cl₂, a “Perforated” Lead(II) Oxide Single crystals of HgPb₂O₂Cl₂ were grown in a HgCl₂ flux by reaction of PbO with HgCl₂. Crystal structure analysis by single crystal X-ray methods were carried out. HgPb₂O₂Cl₂ crystallizes monoclinic with a = 11.788(2) Å, b = 3.910(1) Å, c = 7.749(2) Å, β = 122.64(3)°, space group C2/m (No. 12) and Z = 2. HgPb₂O₂Cl₂ is the first member of a new structure type, closely related to the structure of PbO.     

Ketten aus Ringen: K5{Li[Ge2O7]} — das erste „Litho-Digermanat”︁

Chains consisting of Rings: K₅{Li[Ge₂O₇]} — the First ‘Litho-Digermanate’ By heating of a well-ground mixture of the binary oxides KO_0.55, Li₂O and GeO₂ (K: Li: Ge = 6.1 : 2.2 : 2; Ni-tube; 600°C; 49 d) we obtained for the first time single crystals of K₅{Li[Ge₂O₇]}. This ‘lithodigermanate’ represents a completely new type of structure: monoclinic, space group P2₁/c, a = 624.9(2) pm, b = 1586.6(8) pm; c = 1058.3(6) pm and β = 109.38(4)°; Guinier-Simon data, Z = 4. The structure was solved by four-circle diffractometer data [Siemens AED II, Mo? Kα ; 2872 I_o(hkl); R = 4.5%, R_w = 3.3%], 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.     

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.     

Ein sauerstoffreiches Neodymcuprat: Hochdrucksynthese und Kristallstruktur von Nd12Cu6O25 („Nd2CuO4,17”︁)

An Oxygen-rich Neodymium Cuprate: High-pressure Synthesis and Crystal Structure of Nd₁₂Cu₆O₂₅ (“Nd₂CuO_4.17”) Single crystals of Nd₁₂Cu₆O₂₅ (“Nd₂CuO_4.17”) could be obtained by reaction of Nd₂O₃ und CuO with KO₂ in a modified Belt-type apparatus at 40 kbar, 1500°C. The compound crystallizes in the monoclinic space group C2/m with a = 17.128(6), b = 3.7288(6), c = 18.364(6) Å, β = 111.22(1)º and Z = 2. The structure refinement converged at R1 = 0.0302 for 1451 reflections with F_o > 4σ(F_o) and R1 = 0.0903, wR2 = 0.0767 for all 2571 data. The structure-determining feature are Cu(1,2)? O octahedral chains, interrupted by Cu(3) atoms in square-planar coordination. Each of this CuO₄ groups is connected to another one, resulting in short copper-copper distances (d_{Cu? Cu} = 3.012 Å). A comparison of the structure of “Nd₂CuO_4.17” with those of La₂CuO₄ and Nd₂CuO₄ makes the structural relations of the former with La₂CuO₄ and, hence, the aristotype K₂NiF₄ evident, in spite of the close stoichiometric similarity between Nd₂CuO₄ and “Nd₂CuO_4.17”.     

CuTb[B5O10]: Das erste „Metaborat”︁ mit einem [B5O10]5− -Anion

CuTb[B₅O₁₀]: The first “Metaborate” with a [B₅O₁₀]^5? Anion Single crystals of the new compound CuTb[B₅O₁₀] were obtained by a B₂O₃ flux-technique. They crystallize in a so far unknown structure. X-ray investigations on single crystals led to the space group C–I ba2 (Nr. 45); a = 6.294(1) Å; b = 8.406(8) Å; c = 12.733(2) Å; Z = 4. The structure contains [B₅O₁₀]^5? chains isolated from each other. These chains include twelf membered rings of boron and oxygen. Each ring consists of two tetrahedral BO₄ and two planar B₂O₅ groups and is connected with the next one via the BO₄ units. Tb³⁺ is eightfold- and Cu²⁺ elongated octahedraly coordinated by oxygen.     

Li10Si2PbIIO10 = Li20[(SiO4)4(OPbO2PbO)] — Das erste „gemischte”︁ Silicat-Plumbat(II)

Li₁₀Si₂Pb^IIO₁₀ = Li₂₀[(SiO₄)₄(OPbO₂PbO)] — The first ?mixed”? Silicate-Plumbate(II) Colourless crystals of Li₁₀Si₂PbO₁₀ were obtained by heating a well-ground mixture of LiPb, Li₂O₂ and ?SiO₂”? (deriving from Duran glas) in Ag-tubes (650°C; 60 d). The crystal structure was determined (four-circle diffractometer data, Mo? K, 1 474 I_o(hkl), R = 4.2%, R_w = 2.8%, parameters see text). The silicate-plumbate crystallizes monoclinic (space group C2/m; I. T. No. 12) with a = 2985.1(4); b = 610.6(6); c = 512.8(1) pm, β = 99.70(9)° (four-circle data), Z = 4. Further the Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), the Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution (CHARDI) are being calculated.     

Korrektur zur Kristallstruktur von „Cs4PbO3”︁ und die Strukturverwandtschaft zwischen den Modifikationen von Cs4PbO4

Correction of the Crystal Structure of “Cs₄PbO₃” and the Structural Relationship between the Modifications of Cs₄PbO₄ The compound that has been described as Cs₄PbO₃ really is Cs₄PbO₄. It does not crystallize in the space group P2₁, as assumed, but in P2₁/c. The observed fictitiuous violation of the extinction law for the c glide plane is due to twinning. The structure was refined using the original data as well as new data from an untwinned crystal. The denomination β-Cs₄PbO₄ is used to distinguish this structure from another known modification (α-Cs₄PbO₄). Both structures, α-Cs₄PbO₄ and β-Cs₄PbO₄, can be derived from the sphere packing of γ-plutonium when certain voids in its packing are occupied with oxygen atoms.     

Synthese,Charakterisierung und Struktur von P7(t-Bu3Si)3 („Tris(supersilyl)heptaphosphan(3)”︁)

Synthesis, Characterization, and Structure of P₇(t-Bu₃Si)₃ (?Tris(supersilyl)heptaphosphane(3)”? Tris(tri-tert-butylsilyl)heptaphosphanortricyclane P₇(t-Bu₃Si)₃ 1 is obtained from the reaction of (t-Bu)₃Si? Si(t-Bu)₃ with white phosphorus and forms colorless to pale yellow thermostable crystals. 1 is identified by the complete analysis of its ³¹P{¹H} NMR spectrum (A[MX]₃ spin system) as well as by a single crystal structure determination (space group Pca2₁, a = 170.76(2)pm, b = 131.14(3)pm, c = 426.61(5)pm, α = β = γ= 90°, Z = 8 formula units in the elementary cell). The steric demand of the (t-Bu)₃Si-Groups causes an increase of the exocyclic bond angles at the equatorial phosphorus atoms P^e, while it does not particularly influence the P₇-skeleton. Chlorine (r.t.) and bromine (70°C) degrade the P₇-cage of 1 with formation of PX₃ and (t-Bu)₃SiX (X = Cl, Br).     

Th2F7[AuF4] – das erste „fluorobasische”︁ Tetrafluoroaurat(III) im System ThF4/AuF3

Th₂F₇[AuF₄] – the First Fluoroaurate in the System MF₄/AuF₃ We observed for the first time single crystals of Th₂F₇[AuF₄] [1] in attempts to synthesize ternary fluoroaurates with tetravalent cations. Concerning to X‐Ray‐data (Mo–Kα), the light‐yellow compound crystallizes tetragonal in the space group I4/mcm (No. 140) with a = 1130.6(1) pm, c = 631.34(7) pm and Z = 4.     

Über „Gemischt-Koordinierte”︁ einkernige Anionen. 2. Ein Oxoruthenat(VI) neuen Typs: CsK5Ru2O9 = CsK5[RuO5][RuO4]

On ?Mixed-coordinated”? isolated Anions. 2. A New Type of Oxoruthenates(VI): CsK₅Ru₂O₉ = CsK₅[RuO₅][RuO₄] By heating of intimate mixtures of the oxides [KO_1.1, CsO_1.2, RuO₂; K:Cs:Ru = 2.2:1:1; Ag-tube, 750°C, 34d] dark-green single crystals of CsK₅Ru₂O₉ = CsK₅[RuO₅][RuO₄] were obtained for the first time. Ru⁶⁺ shows two different polyhedra in this oxide (tetrahedron, trigonal bipyramid). Untill now Rb₆[TeO₅][TeO₄] [1] next to ?Mg₄GeO₆”? [3] and the isotypic high-pressure silicate [4] was the only examples known. The structure was determined by four-circle diffractometer data [Mo? Kα , 1824 from 1949 I₀(hkl), SG: Pnma, R equals; 12.6%, R_w = 4.5%], parameters see text. Guinier-Simon data gave a = 1701.6(3), b = 827.6(1), c = 905.7(1) pm, Z = 4. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, were calculated and discussed.     

Modellkomplexe mit Hydrazonchelaten von (S)- und (R)-1-Amino-2-methoxymethylpyrrolidin („SAMP”︁ und „RAMP”︁) und Dimethylhydrazin - Struktur des Pyridinaldehyd-RAMP-hydrazon-tetracarbonyl-molybdäns

Model Complexes with Hydrazone Chelates of (S)- and (R)-1-Amino-2-methoxymethylpyrrolidine (?SAMP”? and ?RAMP”?) and Dimethylhydrazine — Structure of (Pyridine-2-aldehyde-RAMP-hydrazone)tetracarbonyl-molybdenum The hydrazones of glyoxal, biacetyl, pyridine-2-aldehyde and 2-acetylpyridine with N,N-dimethylhydrazine and (R)- and (S)-1-amino-2-methoxymethylpyrrolidine are synthesized and reacted with hexacarbonylmolybdenum to give the chelate hydrazone tetracarbonylmolybdenum complexes. In contrast to the pure electronic effect of methyl groups complexes derived from biacetyl (relativ to glyoxal) or from acetylpyridine (rel to the aldehyde) show a long-wavelength shift of the characteristic MLCT absorption band in their electric spectra, indicativ of a dominant steric effect. A single crystal x-ray diffraction study on (pyridine-2-aldehyde-RAMP-hydrazone)tetracarbonylmolybdenum 12 proves the conjugative interaction of the sp²-hybridized amino nitrogen with the chelate π-system. Orthorhombic 12 crystallizes in space group P2₁2₁2 with 4 molecules in the unit cell: a = 14.689(4), b = 15.699(1) and c = 7.866(6) Å, V = 1814 ų. Complete ¹H and ¹³C nmr parameter are given for the ligands and the complexes.     

Das erste Oxogermanat mit „Stuffed Pyrgoms”︁: CsNa3Li8{Li[GeO4]}4

The First Oxogermanate with “Stuffed Pyrgoms”: CsNa₃Li₈{Li[GeO₄]}₄ By heating the binary oxides CsO_0.52, NaO_0.45, LiO_0.5 and GeO₂ in the mol. ratio 1.24:1.4:6.7:3.9 (Ni tubes; 600°C/89 resp. 65 d) we obtained for the first time CsNa₃Li₈{Li[GeO₄]}₄ in form of pale yellow prisms as well as powder: space group I4/m (I. T. No. 87) with a = 1 120.73(5); c = 651.64(5) pm; Z = 2; (four circle diffractometer data; MoKα; 5 152 I_o(hkl); R = 1.7%; R_w = 1.6%), parameters see text. The structure determination confirmes its being isotypic with CsKNaLi₉{Li[SiO₄]}₄, CsKNa₂Li₈{Li[SiO₄]}₄ and RbNa₃Li₈{Li[SiO₄]}₄. The Madelung part of lattice energy (MAPLE), effective coordination numbers (ECoN), mean fictive ionic radii (MEFIR) and the charge distribution (CHARDI) are calculated.     

Über ein neues Oxoferrat mit „Butterfly-Motiv”︁: K2Na4[Fe2O5]

A New Oxoferrate with “Butterfly-Motiv”: K₂Na₄[Fe₂O₅] Dark red-brown single-crystals of K₂Na₄[Fe₂O₅] were obtained for the first time by heating “K₃Na₃CdO₄” at 500°C in closed Fe-cylinders. Determination and refinement of the crystal structure confirms the space group P4₂/mnm (No. 136). Four-circle diffractometer data: MoKα , 373 out of 373 I_o(hkl); R = 5.3%; R_w = 4.6%; a = 645.94(5), c = 1 039.2(1) pm. In contrast to the already known oxoferrates(II) with the “Butterfly-Motiv”, Rb₆[Fe₂O₅] and K₆[Fe₂O₅] [1], we now found an isotypic structure for K₂Na₄[Fe₂O₅] with the oxocobaltates of Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] [2].