Untersuchungen über Zinn(IV)-alkoxide. I Kristall- und Molekülstruktur des Zinn(IV)-isopropanolat-Isopropanolsolvats,Sn(OiPr)4 · i-PrOH

Investigations into Tin(IV) Alkoxides. I. Crystal and Molecular Structure of Tin(IV)-isopropoxide-Isopropanol Solvate, Sn(OⁱPr)₄ · i-PrOH The isopropanol complex of tin(IV)-isopropoxide has been prepared by the reaction of tin tetrachloride with sodium isopropoxide. The compound forms colourless, moisture sensitive crystals, which in dry air easily release the coordinated solvent molecules. The crystal and molecular structure of Sn(OⁱPr)₄ · i-PrOH has been determinated by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2₁/c with a = 1174.2(5), b = 1428.5(3), c = 1234.1(3) pm, β = 95.37(1)° and Z = 4. The crystal structure consists of discrete, dimeric molecules in which the two tin atoms are bridged by two alkoxide groups. The octahedral coordination sphere of each tin atom is completed by one solvent molecule which, in addition, forms one hydrogen bridge to an alkoxide group of the neighboring tin atom.     

Destruktive Komplexierung des dimeren Diorganylzinn(IV)‐hydroxids [Me2Sn(A)(μ‐OH)]2 (HA = Benzol‐1,2‐disulfonsäureimid): Bildung und Strukturen der Einkernkomplexe [Me2Sn(A)2(OPPh3)2] und [Me2Sn(phen)2]2⊕ · 2 A⊖ · MeCN

Polysulfonylamines. CXVI. Destructive Complexation of the Dimeric Diorganyltin(IV) Hydroxide [Me₂Sn(A)(μ‐OH)]₂ (HA = Benzene‐1,2‐disulfonimide): Formation and Structures of the Mononuclear Complexes [Me₂Sn(A)₂(OPPh₃)₂] and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN Destructive complexation of the dimeric hydroxide [Me₂Sn(A)(μ‐OH)]₂, where A^⊖ is deprotonated benzene‐1,2‐disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10‐phenanthroline in hot MeCN produced, along with Me₂SnO and water, the novel coordination compounds [Me₂Sn(A)₂(OPPh₃)₂] ( 3 , triclinic, space group P 1) and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN ( 4 , monoclinic, P2₁/c). In the uncharged all‐trans octahedral complex 3 , the heteroligands are unidentally O‐bonded to the tin atom, which resides on a crystallographic centre of inversion [Sn–O(S) 227.4(2), Sn–O(P) 219.6(2) pm, cis‐angles in the range 87–93°; anionic ligand partially disordered over two equally populated sites for N, two S and non‐coordinating O atoms]. The cation occurring in the crystal of 4 has a severely distorted cis‐octahedral C₂N₄ coordination geometry around tin and represents the first authenticated example of a dicationic tin(IV) dichelate [R₂Sn(L–L′)₂]^2⊕ to adopt a cis‐structure [C–Sn–C 108.44(11)°]. The five‐membered chelate rings are nearly planar, with similar bite angles of the bidentate ligands, but unsymmetric Sn–N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N–Sn–N 71.24(7)°, Sn–N 226.81(19) and 237.5(2) pm; ring 2: 71.63(7)°, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively C_S symmetric A^⊖ ions have their five‐membered rings distorted into an envelope conformation, with N atoms displaced by 28–43 pm from the corresponding C₆S₂ mean plane.     

Sn3N4, ein Zinn(IV)-nitrid – Synthese und erste Strukturbestimmung einer binären Zinn–Stickstoff-Verbindung

Sn₃N₄, a Tin(IV) Nitride – Syntheses and the First Crystal Structure Determination of a Binary Tin-Nitrogen Compound By reaction of SnI₄ with KNH₂ in liquid ammonia at 243 K a white product mixture was obtained. After evaporation of ammonia the solid residue was annealed in vacuum for 2–5 d at 573 K. Subsequently collected x-ray powder diffraction patterns exhibited reflections of KI and a new compound Sn₃N₄. Analogous reactions of SnBr₂ and KNH₂ led to KBr and dark brown microcrystalline Sn₃N₄ but also to metallic tin. The structure of tin(IV)-nitride was determined from X-ray and neutron powder diffraction data: Space group Fd 3 m, Z = 8, a = 9.037(3) Å. Sn₃N₄ crystallizes in a spinel type structure. Both metal atom positions are occupied by tin atoms of oxidation state plus four.     

Untersuchungen über Zinn(IV)-alkoxide. II. Isolierung und Charakterisierung der Verbindung Sn3O(OiBu)10 · 2i-BuOH. Das erste Beispiel für ein partielles Hydrolyseprodukt eines Zinn(IV)-alkoxids

Investigations into Tin(IV) Alkoxides. II. Isolation and Characterization of the Compound Sn₃O(OⁱBu)₁₀₁₀ · 2i-BuOH. The First Example of a Partially Hydrolized Tin(IV) Alkoxide The partial hydrolysis product Sn₃O(OⁱBu)₁₀ · 2i-BuOH was obtained by slow hydrolysis of the reaction product of tin tetrachloride with sodium isobutoxide. The compound forms colourless, moisture sensitive crystals, which easily release the coordinated solvent molecules in dry air. Its crystal and molecular structure has been determinated by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P1 with a = 1363.5(7), b = 1462.7(10), c = 1637.7(7) pm, α = 95.40(5)°, β = 96.79(4)°, γ = 102.12(5)° and Z = 2. The crystal structure consists of discrete, trimeric molecules with octahedrally coordinated tin atoms which are connected to each other corresponding to the formulation Sn₃(μ₃-O)(μ₂-OⁱBu)₃(O¹Bu)₇ · (i-BuOH)₂ by three isobutoxide groups bridging two metal atoms and a single threefold bridging oxygen atom     

Synthese und Kristallstruktur des Holmium(III)‐chlorid‐oxotellurats(IV) HoClTeO3

Synthesis and Crystal Structure of the Holmium(III) Chloride Oxotellurate(IV) HoClTeO₃ Orange coloured, rod—shaped single crystals of the holmium( III) chloride oxotellurate(IV) HoClTeO₃ (orthorhombic, Pnma; a = 730.25(5), b = 696.54(5), c = 905.18(7) pm; Z = 4) are obtained during attempts to synthesize holmium(III) oxochlorotellurates(IV) by reaction of holmium oxychloride (HoOCl) and tellurium dioxide (TeO₂; 1:1—2molar ratio, 800 °C, 40 d) in evacuated silica tubes. The crystal structure contains sevenfold coordinated Ho ³⁺ cations surrounded by five oxide and two chloride anions forming a pentagonal bipyramid. Interconnection of the [Ho(O1)(O2)₄Cl₂] polyhedra occurs via two edges made of four equatorial oxygen atoms (O2) under formation of {[Ho(O1)(O2)_4/2Cl_2/1]^5‐} chains running parallel [010]. These arrange as hexagonal closest packing of rods and are linked to each other by Cl^‐ anions to a three—dimensional {[Ho(O1)_1/1(O2)_4/2Cl_2/2]^4‐} network. All Te⁴⁺ cations are embedded therein and exhibit ψ¹—tetrahedral coordination figures as discrete anionic [Te(O1)(O2)₂]^2‐ pyramids due to the stereochemical activity of the non—binding electron pairs („lone pairs”︁). They stabilize the {[HoO₃Cl]^4‐} network via covalent bonds to one axial (O1) and two equatorial oxygen atoms (O2) of each [HoO₅Cl₂] polyhedron.     

Synthesis,Spectroscopic, and X‐Ray Diffraction Studies of cis‐Dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl3 H‐pyrazol‐3‐onato) Tin(IV)

Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O₂ gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C₂₆H₂₆N₄O₄)SnCl₂]. The compound has a six‐coordinated Sn^IV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and D_x = 1.575 g cm^–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, ¹H NMR and ¹¹⁹Sn Mössbauer spectral data of the compound are reported and discussed.     

Bariumstannat‐Pulver durch hydrothermale Synthese und durch Thermolyse von Bariumzinn(IV)‐glykolaten. Synthese und Struktur von [Ba(C2H6O2)4][Sn(C2H4O2)3] und [Ba(C2H6O2)2][Sn(C2H4O2)3]·CH3OH

Barium Stannate Powders from Hydrothermal Synthesis and by Thermolysis of Barium‐Tin(IV)‐Glycolates. Synthesis and Structure of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] and [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH The hydrothermal reaction as well as the microwave assisted hydrothermal reaction of SnO₂·aq with barium hydroxide gives Ba[Sn(OH)₆] ( 1 ) as powder with bar like particles. Compound 1 of the same morphology can also be isolated from a hydrothermal reaction of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ). The reaction of SnO₂·aq with Ba(OH)₂·8H₂O in ethylene glycol yields the glycolate [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ), which forms in methanol the solvate [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH ( 4 ). Compounds 1 , 3 and 4 react at different temperatures to BaSnO₃ ( 2 ) consisting of powders with different morphologies; because of the grain size of the resulting powders compounds 3 and 4 are suitable as precursor for the fabrication of corresponding ceramics.     

Synthese und Kristallstrukturen von 1,1,3,3‐Tetramethylimidazolinium‐dichlorid und 1,1,4‐Trimethylpiperazinium‐chlorid

Synthesis and Crystal Structures of 1,1,3,3‐Tetramethylimidazolinium Dichloride and 1,1,4‐Trimethylpiperazinium Chloride Single crystals of 1,1,3,3‐tetramethylimidazolinium dichloride ( 1 ) and 1,1,4‐trimethylpiperazinium chloride ( 2 ) were obtained by reaction of CH₂Cl₂ with tetramethylethylenediamine (TMEDA) and NNN′N″N″‐pentamethyldiethylenetriamine (PMDETA), respectively. Both compounds are characterized by single crystal X‐ray diffraction and by IR spectroscopy. 1: [C₇H₁₈N₂]Cl₂, space group P2₁/c, Z = 4, lattice dimensions at 193(2) K: a = 821.97(11), b = 1130.38(8), c = 1143.08(13) pm, β = 100.348(15)°, R₁ = 0.0271. The C₇N₂ heterocyclic ring has envelope conformation like other salts with this dication. 2: [C₇H₁₇N₂]Cl, space group P2₁2₁2₁, Z = 4, lattice dimensions at 100(2) K: a = 1030.37(8), b = 1036.55(6), c = 831.39(4) pm, R₁ = 0.0180. Although the heterocyclic mono‐cation is without site symmetry in the crystal, its molecular symmetry is close to C_s, forming chair conformation of the C₄N₂ six‐membered ring.     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Die Molekül‐ und Kristallstruktur des Rubidium(Dibenzo‐18‐Krone‐6)‐pentaiodids [Rb(C20H24O6)]I5

Molecular and Crystal Structure of Rubidium(dibenzo‐18‐crown‐6)pentaiodide [Rb(C₂₀H₂₄O₆)]I₅ [Rb(Dibenzo‐18‐crown‐6)]₂(I₅)₂ is obtained as dark brown columns by reacting dibenzo‐18‐crown‐6, rubidium iodide, and iodine in a molar ratio of 1 : 1 : 6 in ethanole / dichlormethane (1:1). [Rb(C₂₀H₂₄O₆)]₂(I₅)₂ crystallizes with four formula units per unit cell in the orthorhombic space group Pnma with a = 1725.15(2) pm, b = 1863.76(3) pm and c = 1885.19(3) pm. The crystal structure consists of pentaiodide units I₅^—, which are linked to one another by head‐to‐tail‐contacts. The I₂ units, which stick out of the chain, are twisted against each other, in a way that neither a cis or a trans configuration is formed. By secondary bonding, the iodine atoms form nets of 18‐member planar rings with an almost rectangular form. This net‐like structural element has not been described up to now.     

Pniktogenidostannate(IV) mit isolierten Tetraeder‐Anionen: Neue Vertreter (E1)4(E2)2[Sn(E15)4] (mit E1 = Na,K; E2 = Ca,Sr, Ba; E15 = P,As, Sb,Bi) vom Na6[ZnO4]‐Typ und die Überstrukturvariante von K4Sr2[SnAs4]

Pnictogenidostannates(IV) with Discrete Tetrahedral Anions: New Representatives (E1)₄(E2)₂[Sn(E15)₄] (with E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) of the Na₆[ZnO₄] Type and the Superstructure Variant of K₄Sr₂[SnAs₄] The silvery to dark metallic lustrous compounds (E1)₄(E2)₂[Sn(E15)₄] (E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) were prepared from melts of stoichiometric mixtures of the elements. They crystallize in the Na₆[ZnO₄]‐type structure (hexagonal, space group: P6₃mc, Z = 2; Na₄Ca₂[SnP₄]: a = 938.94(7), c = 710.09(8) pm; K₄Sr₂[SnAs₄]: a = 1045.0(2), c = 767.0(1) pm; K₄Ba₂[SnP₄]: a = 1029.1(6), c = 780.2(4) pm; K₄Ba₂[SnAs₄]: a = 1051.3(1), c = 795.79(7) pm; K₄Ba₂[SnSb₄]: a = 1116.9(2), c = 829.2(1) pm; K₄Ba₂[SnBi₄]: a = 1139.5(2), c = 832.0(2) pm). The anionic partial structure consists of tetrahedra [Sn(E15)₄]^8– orientated all in the same direction along [001]. In the cationic partial structure one of the two cation positions is occupied statistically by alkali and alkaline earth metal atoms. Up to now only for K₄Sr₂[SnAs₄] a second modification could be isolated, forming a superstructure type with three times the unit cell volume (hexagonal, space group: P6₃cm, Z = 6; a = 1801.3(2), c = 767.00(9) pm) and an ordered cationic partial structure.     

Synthese und Kristallstruktur von 2‐Azido‐4,6‐dichloro‐s‐triazin

Synthesis and Crystal Structure of 2‐Azido‐4,6‐dichloro‐s‐triazine Single crystals of 2‐azido‐4,6‐dichloro‐s‐triazine were obtained from a reaction between cyanuric chloride and sodium azide. The structure of this compound was determined by single crystal X‐ray diffraction. 2‐Azido‐4,6‐dichloro‐s‐triazine crystallizes in the orthorhombic space group Pbca (no. 61), Z = 8, a = 746.48(8) pm, b = 952.6(1) pm, c = 2001.6(2) pm. The crystal structure contains (C₃N₃)(N₃)Cl₂ molecules being arranged in a tape‐like fashion, with tapes running along a‐axis direction. The tapes are combined with each other by interlocking azide‐ligands including an angle of approximately 90°. This arrangement leads to the formation of corrugated layers in the crystal structure.     

Kristallstruktur von Caesiumtetrafluorooxotellurat(IV) Cs2TeOF4

Crystal Structure of Cesiumtetrafluorooxotellurate(IV) Cs₂TeOF₄ Solid state reaction of cesium fluoride, cesium pentafluorotellurate(IV), and tellurium dioxide in the molar ratio 3 : 1 : 1 yields colourless single crystals of cesium tetrafluorooxotellurate(IV). The compound crystallizes in a structure analogous to potassium pentafluoroantimonate(III) (Cmcm, Z = 4, a = 669.5(1), b = 1464.0(2), c = 717.09(7) pm). The characteristic feature is the presence of discrete pseudooctahedral tetrafluorooxotellurate(IV) anions. The structure of this complex anion could be determined for the first time. It contains a short Te–O_ax bond of 177.5 pm (bond order about 1.7) and long Te–F_eq bonds of 207.2 pm (bond order about 0.6). The position of the tellurium atom deviates only slightly from the equatorial plane (O_ax–Te–F_eq: 89.0°).     

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.     

Syntheses and X‐Ray Crystal Structures of [Li(thf)4][SnCl5(thf)] and {[Li(Et2O)2]2‐(μ‐Cl2)2‐SnIVCl2}

The syntheses and single crystal X‐ray structure determinations are reported for [Li(thf)₄][SnCl₅(thf)] ( 1 ) and {[Li(Et₂O)₂]₂‐(μ‐Cl₂)₂‐Sn^IVCl₂} ( 2 ). Compound 1 is ionic with a tetrahedral coordinated lithium cation and distorted octahedral tin (IV) atom in the anion, while compound ( 2 ) is a centrosymmetric heteronuclear double salt of LiCl and SnCl₄. [Li(thf)₄][SnCl₅(thf)] is monoclinic, P2₁/n, a = 11.204(1), b = 15.599(1), c = 17.720(2) Å; β = 96.734(2)°, Z = 4, R 0.0418; {[Li(Et₂O)₂]₂‐(μ‐Cl₂)₂‐Sn^IVCl₂} is monoclinic, P2₁/n, a = 10.848(2), b = 12.764(2), c = 11.748(2) Å; β = 90.388(3)°, Z = 4, R = 0.0851.     

Darstellung und Kristallstruktur von Na2Sn2Se5 Ein neues Chalkogenostannat(IV) mit schichtförmigen Komplexanionen

Preparation and Crystal Structure of Na₂Sn₂Se₅ A Novel Chalcogenostannate(IV) with Layered Complex Anions Na₂Sn₂Se₅ was obtained from a stoichiometric mixture of Na₂Se, Sn, and Se powders through a solid state reaction at 450 °C. It crystallizes orthorhombic, space group Pbca with a = 13.952(6) Å, b = 12.602(2) Å, c = 11.524(2) Å; Z = 8 and undergoes peritectic decomposition at 471(2) °C. The crystal structure was determined at ambient temperature from diffractometer data (MoKα‐radiation) and refined to a conventional R of 0.040 (1490 F_o's, 83 variables). Na₂Sn₂Se₅ is characterized by layered complex anions running parallel to (100) which are built up by SnSe₄ tetrahedra sharing common corners. The mean Sn–Se bond length calculates as 2.252(2) Å. The Na⁺ cations are coordinated to 6 or 7 Se in irregular configurations. The crystal structure can be described as a stacking of distorted c. p. 3⁶ chalcogen layers and mixed square 4⁴ alkali‐chalcogen layers.     

Darstellung und Kristallstruktur eines Ditelluridovanadium(IV)‐Komplexes: [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2]

Synthesis and Crystal Structure of a Ditelluridovanadium(IV) Complex: [(μ‐η¹‐Te₂)(μ‐N^tBu)₂V₂Cp₂] [(μ‐η¹‐Te₂)(μ‐N^tBu)₂V₂Cp₂] ( 2 ) is formed from [^tBuN = VCp(PMe₃)₂] ( 1 ) upon reaction with elemental tellurium. 1 and 2 are characterized by spectroscopic methods (MS; ¹H, ¹³C, ⁵¹V NMR), in addition 2 by single crystal X‐ray diffraction. The crystal structure indicates a folded cyclodivanadazen ring bridged by a bidentated ditellurido ligand, the first example of this structure type.     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Synthese,Kristallstruktur und Eigenschaften von Vanadium(II)‐tetrachloroaluminat

Synthesis, Crystal Structure, and Properties of Vanadium(II) Tetrachloroaluminate The reaction of vanadium dichloride and aluminium trichloride yields vanadium(II) tetrachloroaluminate. Amber cuboid crystals can be obtained by slow cooling of the melt. V(AlCl₄)₂ crystallizes in the monoclinic space group I2/c (a = 1284.6(3), b = 776.3(2), c = 1163.5(2) pm, β = 92.376(10)°) and is therefore isotypic to Co(AlCl₄)₂. The structure contains chains build of VCl₆ octahedra and AlCl₄ tetrahedra sharing corners and edges with each other. The temperature dependence of the magnetic susceptibility follows Curie‐Weiss behaviour (μ = 3.88(2) μ_B, Θ = ?9(1) K) complying with the spin‐only paramagnetism expected of d³ ions.     

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.