Darstellung und Kristallstruktur von Rubidiumtrijodoplumbat(II)

Preparation and Crystal Structure of Rubidium Triiodoplumbate(II) RbPbJ₃ crystallizes in the orthorhombic space group Pnam(D) (lattice parameters see above); it is isomorphous with CsPbJ₃. The crystal structure has been determined from 1452 independent reflexes by Patterson- and Fourier-syntheses and refined three dimensionally by least-squares-methods. 6 I surround Pb nearly octahedrally. The octahedra are arranged in the form of double chains along the c-axis, which are held together by Rb. (Pb? I bond distances see above). The “inert 6s-pair” at Pb is stereochemically inactive.     

Darstellung und Kristallstruktur von Blei(II)-monoglycerat

Preparation and Crystal Structure of Lead(II) Monoglycerolate Crystals of lead(II) monoglycerolate, of a quality suitable for diffraction studies, have been prepared from an alkaline plumbate solution and an excess of glycerol. The compound crystallizes in the monoclinic space group P2₁/c with a = 5.617(6) Å, b = 9.471(8) Å, c = 9.726(7) Å, β = 102.65(11)°. The structure was refined by full matrix least-squares techniques to an R value (1026 F₀) of 0.078. The compound to which the formula Pb(C₃H₆O₃) could be assigned, is polymeric in one direction. The lead and a part of the oxygen atoms built up a zig-zag chain parallel to the aaxis. The oxygen form a distorted tetragonal pyramid with lead at the apex. A decomposition temperature of 235°C has been determined.     

Darstellung und Kristallstruktur der Hexaselenodiphosphate(IV) von Antimon und Bismut

Preparation and Crystal Structure of the Hexaselenodiphosphates(IV) of Antimony and Bismuth Sb₄(P₂Se₆)₃ and Bi₄(P₂Se₆)₃ are synthesized from the elements via chemical transport reactions with iodine. The isotypic compounds crystallize in the monoclinic space group P2₁/n (No. 14) with lattice parameters a = 2 077.7(4) pm, b = 749.35(5) pm, c = 949.49(8) pm, β = 91.25(1)° for Sb₄(P₂Se₆)₃ and a = 2 086.9(3) pm, b = 747.45(6) pm, c = 959.23(6) pm, β = 91.73(1)° for Bi₄(P₂Se₆)₃, respectively. This new structure type is closely related to the structure of Pb₂P₂Se₆ showing an ordered cation distribution combined with a reorientation of the ethane like [P₂Se₆]^4? units. From the interatomic distances in the coordination spheres a smaller lone pair effect of Bi^III compared to Sb^III may be deduced. For both compounds UV/VIS spectra and temperature dependence of the electrical resistivity are reported.     

Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

Darstellung und Kristallstruktur von Cadmiumazid Cd(N3)2

Preparation and Crystal Structure of Cadmium Azide Cd(N₃)₂ Solvent free, binary cadmium azide was synthesized by the reaction of cadmium carbonate and a 24 weight% solution of HN₃ in water. Cadmium azide is a colorless, crystalline powder which is highly sensitive to percussion and heat. Caution, the manipulation of Cd(N₃)₂ is very dangerous! The crystal structure was solved by single‐crystal methods and the phase purity was verified by a Rietveld refinement (Cd(N₃)₂, Pbca, no. 61; a = 7.820(2), b = 6.440(2), c = 16.073(3) Å; Z = 8, 1174 independent reflections, 64 parameters, R1 = 0.022). Cadmium azide crystallizes in a new structure type. In the crystal there are edge‐sharing Cd₂(N₃)₁₀ double octahedrons which are further connected to other units by azide bridges. Vibrational spectroscopic investigations (Raman an IR) are discussed with respect to the crystal structure data.     

Darstellung,Kristallstruktur und Normalkoordinatenanalyse der bindungsisomeren Pentachlororhodanoosmate(IV)

Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl₅I]^2? with (SCN)₂ in dichloromethane the linkage isomers [OsCl₅(NCS)]^2? and [OsCl₅(SCN)]^2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph₄As)₂[OsCl₅(NCS)] (monoclinic, space group P2₁/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph₄As)₂[OsCl₅(SCN)] (monoclinic, space group P2₁/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved.     

Darstellung und Kristallstruktur von Tetrakis(pentafluorphenylamino)silan

Synthesis and Crystal Structure of Tetrakis(pentafluorophenylamino)silane Colourless single-crystals of Tetrakis(pentafluorophenylamino) silane were obtained from the reaction of SiCl₄ with monolithiated pentafluoroaniline at low temperatures. The aminosilane has been characterized by various spectroscopic methods and its crystal structure has been determined by x-ray diffraction (for details see “Inhaltsübersicht”). Thermal condensation has not been achieved. However, reaction of silicon(IV)-chloride with pentafluoroaniline in the presence of triethylamine yielded the respective tricyclosilazane.     

Darstellung und Kristallstruktur von K3La(NH2)6

Preparation and Crystal Structure of K₃La(NH₂)₆. Single crystals of K₃La(NH₂)₆ were obtained by the reaction of the metals (3 K + 1 La) during five days at 200°C and 4000 atm NH₃ pressure. The compound crystallizes monoclinic with a = 6.74, b = 11.67, c = 7.23 Å and β = 108.1°; the space group is C2/m (No. 12). The lattice contains 2 formula units. The amide ions are arranged in a strongly distorted cubic closepacking. All cations occupy edging anion-octahedra.     

Darstellung und Kristallstruktur von HgPb2O(OH)Br3

Inhaltsübersicht. Die erstmals dargestellte Verbindung HgPb₂O(OH)Br₃ kristallisiert orthorhombisch in der Raumgruppe Aba2 (Nr. 41) mit den Gitterkonstanten a = 14,652(3) Å, b = 14,6491(8) Å, c = 7,782(2) Å und Z = 8. Die Bestimmung der Kristallstruktur mit Einkristallmethoden zeigte “isolierte”, verzerrt würfelförmige Baugruppen der Zusammensetzung [Hg₂Pb₄O₂(OH)₂]. Diese Einheiten werden von Bromidionen umhüllt. HgPb₂O(OH)Br₃ stellt damit hinsichtlich des strukturellen Aufbaus ein Bindeglied zwischen den Verbindungen [Pb₄(OH)₄](ClO₄)₄ · 2H₂O [1] und Pb₉O₄Br₁₀ [2] dar. Preparation and Crystal Structure of HgPb₂O(OH)Br₃ The new compound, HgPb₂O(OH)Br₃ was prepared and investigated by X-ray crystal structure analysis. Crystals of orthorhombic symmetry show space group Aba2 (No. 41) with lattice parameters a = 14.652(3) Å, b = 14.6491(8) Å, c = 7.782(2) Å, and Z = 8. Remarcable structural units with heterocubane skeleton were found. The [Hg₂Pb₄O₂(OH)₂] group forms a new member of the structural class between [Pb₄(OH)₄] and [Pb₈O₄] units with the relating compounds [Pb₄(OH)₄)](ClO₄)₄ · 2 H₂O [1] und Pb₉O₄Br₁₀ [2].     

Darstellung und Kristallstruktur von Cs2Mn(PO3)4

Synthesis and Crystal Structure of Cs₂Mn(PO₃)₄ On heating mixtures of Cs₂CO₃, MnO and H₃PO₄ with Cs:Mn:P = 3:1:5 at 500°C Cs₂Mn(PO₃)₄ is formed. The by-product (CsPO₃)_n may be removed by leaching with water. The x-ray structure determination (P2₁/n; a = 797.62(3), b = 1324.91(6), c = 1154.62(8) pm; β = 101.97(1)°; Z = 4) proves the title compound to contain an infinite chain of corner sharing tetrahedra.     

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.     

Darstellung,Eigenschaften und Kristallstruktur von Cl3(bpy)Ta  NOCH3, einem Methoxynitrenkomplex des Tantals

Synthesis, Properties, and Crystal Structure of Cl₃(bpy)Ta≡NOCH₃, a Methoxynitrene Complex of Tantalum TaCl₅ reacts in the presence of 2,2′-bipyridine with O-methyl-hydroxylamine or bis(trimethylsilyl)-O-methyl-hydroxylamine to yield the methoxynitrene complex Cl₃(bpy)Ta≡NOCH₃. The red complex decomposes only slowly at moist air. It crystallizes in the monoclinic space group C2/c with the lattice constants a = 1588.5, b = 1515.9, c = 1414.2 pm, β = 122.78°, Z = 8. The monomeric complex exhibits a distorted octahedral coordination for the tantalum atom. The methoxynitrene ligand is coordinated by a Ta? N triple bond resulting in a linear Ta≡N? O arrangement with Ta? N? O = 174.0° and distances Ta? N = 174.4 pm and N? O = 134.8 pm. v(Ta? N) is observed in the i.r. spectrum at 950 cm^?1.     

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.     

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 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 Kristallstruktur von RbSb3Se5

Preparation and Crystal Structure of RbSb₃Se₅ RbSb₃Se₅ was prepared by methanolothermal reaction of Rb₂CO₃ with Sb₂Se₃ at a temperature of 175°C. An X-ray structural analysis demonstrated that the compound contains polyselenoantimonate(III) anions (Sb₃Se₅^?)_n. A ψ-tetrahedral coordination is observed for one of the independent Sb atoms, a ψ-trigonal bipyramidal coordination for the other two. The Sb? Se polyhedra are linked through joint edges into sheets.     

Nitrosodicyanmethanid-Komplexe von Palladium(II) und Platin(II)

Crystal and Molecular Structure of 1,8-Dihydroxy-3,6-dithiaoctan-bis-mercury(II) Chloride The crystal structure of 1,8-dihydroxy-3,6-dithiaoctane-bis-mercury(II) chloride has been determined by X-ray crystal structure analysis. The compound crystallizes monoclinic, space group C2/c with a = 15.311(2), b = 5.870(2), c = 17.479(2) Å, β = 102.76° and 4 formula units per unit cell. The structure was solved by heavy atom technique and refined to a final R value of R = 0.050. Mercury is digonally coordinated by an S and a Cl ligator. In consequence of weak interactions to an oxygen atom of the ligand as well as to three further Cl ions the coordination number is increased to six and a strongly distorted octahedron is formed. The crystal structure is built up from polymeric complex molecules.     

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.     

Darstellung und Kristallstruktur von Barium-Cadmium-Thiostannat (iv) BaCdSnS4

Preparation and Crystal Structure of Barium-Cadmium-Thiostannate (IV) BaCdSnS₄ BaCdSnS₄ was prepared for the first time and the crystal structure determined by single crystal X-ray investigations. Lattice constants: a = 2186 ± 2; b = 2169 ± 1; c = 1318 ± 0.5 pm. Space group: C–Fdd2. There are pairs of edge-sharing tetrahedrons linked together characteristically to form twodimensional endless nets. The crystal structure is described and discussed.