Darstellung und Kristallstruktur von HfOS

Synthesis and Crystal Structure of HfOS On attempts to prepare binary and ternary hafnium sulfides a small quantity of single crystals was obtained which could be identified as HfOS. The new compound is cubic, space group P2₁3 with a = 5.6824(6) Å. It is isostructural with the cubic form o ZrOS. In order to refine the structure parameters intensity measurements were carried out by means of a four-circle single crystal diffractometer.     

Metallocenylborane III. Darstellung und eigenschaften von ferrocenyl- und cymantrenylboranen

Ferrocene, cymantrene and methylcymantrene react with BI₃, BBr₃, C₆H₅BI₂ and CH₃BI₂ in boiling CS₂ or C₆H₁₂ forming air-sensitive metallocenylhaloboranes. The direct dichloroborylation is only possible with ferrocene. Starting from metallocenyliodoboranes the corresponding substituted metallocenylboranes are obtained by halogen exchange with AsF₃ or AsCl₃, by methylation with Sn(CH₃)₄, by ether cleavage of (C₂H₅)₂O, by redox reaction with (CH₃S)₂ and by reaction with R₂NH. ¹H and ¹³C NMR spectra indicate that in contrast to cymantrenylhaloboranes, in ferrocenylhaloboranes the 3,4-protons are more deshielded than the 2,5-protons. The metallocenylboranes, isoelectronic with α-metallocenylcarbenium ions, are weaker Lewis acids than phenylboranes; they form donor-acceptor compounds with pyridine and dimethylsulfane, respectively.     

Darstellung und eigenschaften von diorganogermaniumdisulfinsäureestern

Diorganogermaniumdisulfinic esters of the type R₂Ge(O₂SR′)₂ (R = CH₃, R′ = CH₃, C₆H₅, p-CH₃C₆H₄; R = C₆H₅, R′ = CH₃, p-CH₃C₆H₄) which are sensitive to hydrolysis are obtained by reaction of the corresponding diorganogermanium dichlorides with anhydrous silver sulfinates. The newly prepared compounds are thoroughly investigated on the basis of their ¹H NMR, mass, IR and Raman spectra. The methyl ester (CH₃)₂Ge(O₂SCH₃)₂ is compared with the already known sulfinato complex of tin with the same formal composition.     

Darstellung und Kristallstruktur von KSbS2

Preparation and Crystal Structure of KSbS₂ Red KSbS₂ was prepared in a aqueous solution of KHS and Sb₂S₃ under mild hydrothermal conditions. For crystallographic data see ?Inhaltsübersicht”?. There are SbS-chains, built up by ψ-trigonal bipyramids, which are connected by sharing edges. The K⁺-Ions between these chains have a nearly octaedric coordination.     

Darstellung und Kristallstruktur von CsTe4

Preparation and Crystal Structure of CsTe₄ CsTe₄ results from a melting reaction at 570°C in sealed quartztubes. The starting materials Cs and Te in the molar ratio 1:4 are produced in a first step by controlled decomposition of the CsN₃ from mixtures of CsN₃ and Te (1:4) at 350°C. CsTe₄ is monoclinic, space group P2₁/c, with a = 7.857(1) Å, b = 7.286(1) Å, c = 14.155(2) Å, β = 93.83(1)°, and Z = 4. The tellurium atoms form a two-dimensional puckered layer built of from pseudo-trigonal-bipyramidal, T-shaped units Te₄^?. The central tellurium atom of this unit may be considered as a pseudo iodine. The compound is compared with other tellurides MTe_n having some like that unexpected principles of connection.     

Darstellung und Kristallstruktur von CsBO2

Preparation and Crystal Structure of CsBO₂ Colourless single crystals of CsBO₂ have been prepared from intimate mixtures of CsO_0.57 and B₂O₃ (Cs:B = 3.2:1.0; 600°C, 38 d). The structure determination from fourcircle diffractometer data (MoK, 443 I_o (h k l), R = 3.1%, R_w = 2.0%) confirms the isotypy with NaBO₂ and KBO₂: space group R 3 c; a = 1 363.7(2) pm, c = 836.5(2) pm; Z = 18. A characteristic structure unit is the planar cyclic anion [B₃O₆]^3?. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), the Madelung Part of Lattice Energy (MAPLE) and the Charge Distribution (CHARDI) are calculated and discussed.     

Darstellung und Kristallstruktur von Calciumimid,CaNH

Synthesis and Crystal Structure of Calcium Imide, CaNH Single-crystals of calcium imide were obtained for the first time by the reaction of a mixture of calcium amide with sodium amide at 850°C in an autoclave for salt melts. After cooling the autoclave to room temperature the crystals are embedded in solid Na which was extracted by liquid ammonia. The structure of calcium imide was determined from single-crystal diffractometer data: space group Fm3 m, Z = 4, a = 5.143(1) Å, R/R_w = 0.032/0.028 mit N(F ${}_{\text{º}}^{\text{2}}$ ? 3σ(F ${}_{\text{º}}^{\text{2}}$ )) = 26, N(Var.) = 5. Ca and N atoms are arranged in the motif of the NaCl structure type. The hydrogen atoms of the imide groups are disordered within the Ca octahedra, and they occupy a six fold split position.     

Darstellung und Kristallstruktur von Lithiumhydrogensulfid,LiHS

Preparation and Crystal Structure of Lithiumhydrogensulfide, LiHS Lithiumhydrogensulfide, LiHS, is prepared from lithiumamide, LiNH₂, by reaction with liquid hydrogensulfide. At 150°C the solubility of LiHS in H₂S is sufficient for the growth of single crystals in a temperature gradient within the autoclaves used. The X-ray structure determination at 295 K is characterized by the following data: Lithium occupies tetrahedral sites in a distorted cubic close-packed arrangement of S; in PtS sulfur occupies tetrahedral sites in a similar way in a distorted close packing of Pt. Hydrogen atoms of the HS^??ions are dynamically disordered in a split position linearly bound to S. At 228 K a thermal effect occurs in DSC-measurements indicating that below this temperature the HS^??ion has fixed positions.     

Darstellung,Kristallstruktur und Eigenschaften von Kaliumhydrogencyanamid

Preparation, Crystal Structure, and Properties of Potassium Hydrogen Cyanamide For the preparation of KHCN₂ melamine has been reacted with potassium amide in liquid ammonia. After evaporation of the solvent the resulting solid has been transformed at 210°C. KHCN₂ (P2₁2₁2₁, a = 708.7(2), b = 909.0(2), c = 901.4(2) pm, Z = 8, R = 0.039, wR = 0.016) is yielded as a coarse crystalline product. In the solid K⁺ and HCN ions occur. As expected two significantly differing bond-distances C? N (117.3(5) pm) and HN? C (128.7(5) pm) have been found in the anion. According to IR-spectroscopy a non linear group N? C? N (174.4(4)°) is observed.     

Cobalthydrogenarsenat-Monohydrat. Darstellung und Kristallstruktur

Cobalt(II) Hydrogenarsenate Monohydrate. Preparation and Crystal Structure Co[H₂O|HOAsO₃] was prepared by heating of As₂O₅, CoSO₄ · 7 H₂O and H₂O at 150°C in a sealed tube and investigated by X-rays. The compound crystallizes triclinic, space group P¯1 with a = 786.5, b = 1569.9, c = 671.9 pm, α = 94.25, β = 96.89, γ = 90.28° and Z = 8. The structure contains chains of edge-shared CoO₆ octahedra connected by AsO₄ tetrahedra forming sheets. Two of such somewhat different sheets built up the whole structure. Based on the charge balance derived from the geometrical data and the IR spectra the occurrence of hydrogen bridges is discussed.     

Tetramethylammonium-calcium-triazid. Darstellung und Kristallstruktur

[N(CH₃)₄]Ca(N₃)₃,M=240.29, was prepared from aqueous solutions of tetramethylammoniumazide with calciumazide at 298 K. The crystals are tetragonala=936.6(7) pm,c=694.7(5)pm, space group P4/nmm,Z=2, (x)=1.31Mgm^–3. The crystal structure was determined by single crystal x-ray diffraction (234 Mo-K-reflections, =0.469 mm^–1,R=0.064). Calcium is octahedrally coordinated to six azide groups. The octahedra are connected via azide groups to a threedimensional array with the complex ammonium ions between. The terminal nitrogen atoms of the azide groups and the methyl groups are considerably disordered.

     

Darstellung und Kristallstruktur von Ag2MnO4

Synthese and Crystal Structure of Ag₂MnO₄ Single crystals of Ag₂MnO₄ have been grown from aqueous solution. The crystal structure has been solved and refined using diffractometer data (Pnma, a = 999.8(2); b = 698.9(1); c = 547.4(2) pm). The mean bond-length Mn? O within the tetrahedral anions is 167.9 pm. In spite of similar lattice constants and identical space group, Ag₂MnO₄ is not isostructural to Olivine. The structural differences are discussed.     

Darstellung und Kristallstruktur von NaBi2AuO5

Synthesis and Crystal Structure of NaBi₂AuO₅ NaBi₂AuO₅ was obtained by hydrothermal reaction of ‘Bi₂O₅’, Au₂O₃ · 2H₂O and saturated aqueous NaOH solution at temperatures from 300 to 600°C and oxygen pressure from 3 × 10⁸ to 6 × 10⁸ Pa for the first time. The crystal structure (P4 b2; a = 1 220.02(6) pm; b = 386.68(3) pm; Z = 4; R_w = 0.022) consists of bisphenoidic distorted AuO₄ groups, which are stacked in c-direction. They are connected by square pyramidal BiO₅ units. Sodium is occupying holes within the Au/Bi/O framework thus formed.     

Darstellung und Kristallstruktur von Cs4SnO3

Preparation and Crystal Structure of Cs₄SnO₃ Crystals of Cs₄SnO₃ were synthesized by reaction of SnO with elemental Cs. The compound crystallizes with the triclinic spacegroup P1 with lattice constants a = 737.61(9) pm, b = 1171.3(1) pm, c = 1199.2(1) pm, α = 66.08(3)°, β = 80.88(2)°, γ = 82.28(3)° and Z = 4. The crystal structure exhibits isolated stannate(II) ions [Sn^IIO₃]^4– of ψ-tetrahedral form. Whereas a new structure type is present, there is a close relationship with the structures of the Cs stanntates and plumbates(IV).     

Darstellung und eigenschaften von triorganogermanium-, silicium- und -kohlenstoffsulfinsäurederivaten

A number of hitherto unknown sulfinic acid derivatives of germanium, silicon and carbon, R₃MO₂SR, were prepared by reaction of anhydrous aliphatic aromatic silver sulfinates, RSO₂Ag, with triorgano IVa element halides of the type R₃MX (R  aliphatic or aromatic group; M  Ge, Si, ;; X  Cl, Br). Their ester-like structure and the trigonal pyramidal configuration of the R₃M group result unequivocally from ¹H NMR, mass, IR and Raman spectroscopic investigations. The methyl esters (CH₃)₃MO₂SCH₃ (M  Ge, Si, C) are compared with the already known sulfinato complexes of tin and lead, (CH₃)₃SnO₂SCH₃ and (CH₃)₃PbO₂SCH₃.     

Darstellung und Kristallstruktur von Cu2SrSnS4

Preparation and Crystal Structure of Cu₂SrSnS₄ Cu₂SrSnS₄ was prepared from a mixture of the three binary sulfides at 620-700° C. The structure analyses by single crystal X-ray investigations yields a trigonal C-symmetrie for the unit of the structure with a = 6.29₀ and c = 15.57₈ Å and three formula units. Space group: C–P3₁ (No. 144). Copper and tin have tetrahedral surrounding of S^2?. The neighbourhood of Sr²⁺ has the shape of a deformed archimedic antiprisma.     

Darstellung und eigenschaften neuer monosilylcyclopentasilanderivate

New SiMe₂R-substituted derivatives of decamethylcyclopentasilane were prepared by different pathways. The halogen compounds where R = F, Cl, Br or I exhibit a strong influence of the substituent on the physical properties of the silicon ring. Hydrolysis of the halides gives a hydroxy compound (R = OH) and takes place extremely slowly, whereas the formation of polysiloxanes is favoured.     

Zur Darstellung und Kristallstruktur von RbTlF4 und CsTlF4

Preparation and Crystal Structure of RbTlF₄ and CsTlF₄ RbTlF₄ and CsTlF₄ were synthesized by heating equivalent mixtures of alkaline chlorides or carbonates and Tl₂O₃ under a current of fluorine at 450–500°C. The crystal structure of RbTlF₄ has been determined by single crystal X-ray diffraction methods. The unit cell is orthorhombic with a = 8.252, b = 8.359, c = 6.244 Å (Z = 4); space group: C?Pb2₁a. CsTlF₄ and Tl^ITl^IIIF₄ (“TlF₂”) are isostructural with RbTlF₄. The structure contains layers of 2-dimensionally corner-linked distorted [TlF_4/2F₂]-octahedra, which are connected by rubidium ions.     

Darstellung und Kristallstruktur von Ag2O3

Preparation and Crystal Structure of Ag₂O₃ The novel compound Ag₂O₃ was obtained by anodic oxidation of aqueous solutions of AgBF₄, AgClO₄, and AgPF₆. According to single crystal investigations Ag₂O₃ belongs to the orthorhombic crystal system (Fdd2; a = 1286.9(1), b = 1049.0(1), c = 366.38(5) pm; Z = 8; 309 independent diffractometer data; R = 1.2%). Ag₂O₃ is isostructural to Au₂O₃ and contains silver square-planarly coordinated by oxygen. The AgO₄ groups are connected via common vertices forming a 3-d framework.