Über die Kristallstruktur von In3Mo11O17 sowie über physikalische Eigenschaften oligomerer Oxomolybdate

On the Crystal Structure of In₃Mo₁₁O₁₇ and the Physical Properties of Oligomeric Oxomolybdates In₃Mo₁₁O₁₇ is characterized by its molybdate framework Mo₂₂O₃₄^8? belonging to the general series Mo_4n+2O_6n+4^x? (with n = 5). The phase grows in star-like aggregates and crystallizes within the orthorhombic system (a = 988.0(2) pm, b = 951.2(2) pm, c = 3 176.7(4) pm). There are oligomeric clusters built from five trans edge-sharing Mo₆ octahedra, surrounded by O atoms over all empty edges according to the Aufbau principle Mo₂₂OOO. In the remaining structural channel one finds an In₆⁸⁺ polycation which is geometrically equivalent with the one of In₁₁Mo₄₀O₆₂. The Mo—O and Mo—Mo distances within the cluster are the same like in In₁₁Mo₄₀O₆₂, too, but there are shorter inter cluster distances (306 pm) in In₃Mo₁₁O₁₇. Disorder in the structure may be understood in terms of the presence of constitutional isomers. While the electrical resistivity of PbMo₅O₈ resembles the one of a strongly disturbed metal (with a local minimum around 120 K), the temperature characteristic of Tl_0.8Sn_0.6Mo₇O₁₁ is typical for a semiconductor. Oxomolybdates with even longer oligomers like In₁₁Mo₄₀O₆₂ and In₃Mo₁₁O₁₇ show metallic conductivity. This course corresponds with the sizes of the clusters and their electronic intercoupling which can be estimated from the specific lengths of the inter cluster distances. The effective magnetic moment grows with increasing cluster length from 0.97 μ_B (PbMo₅O₈) to 1.40 μ_B (In₁₁Mo₄₀O₆₂) per cluster (exception: In₃Mo₁₁O₁₂), and so does the contribution of the temperature-independent paramagnetism (from 890 to 2191 × 10^?6$ \frac{{{\rm emu}}}{{{\rm mol}}} $ per cluster). Thus, a single condensed octahedron carries roughly 440 × 10^?6$ \frac{{{\rm emu}}}{{{\rm mol}}} $ as a temperature-independent paramagnetism, similar to the M₆X₁₇ halide clusters. In₁₁Mo₄₀O₆₂ shows an interesting change in the temperature dependence of its magnetic suszeptibility.     

Synthese und Kristallstruktur von PbMo5O8; ein reduziertes Oxomolybdat mit Mo10O28-Oktaederdoppeln

Synthesis and Crystal Structure of PbMo₅O₈; a reduced Oxomolybdate with Mo₁₀O₂₈ Double Octahedra The crystal structure of the new phase PbMo₅O₈ contains oligometric Mo clusters which consist of two edge-sharing Mo₆ octahedra connected according to Mo₁₀OOO. The compound is isotypic with LaMo₅O₈. Isolated, divalent Pb atoms are located in the “channels” of the monoclinic structure (a = 999.3(2) pm, b = 924.7(1) pm, c = 753.6(2) pm, β = 109.39(2)°, P2₁/a. Compared to the compound In ₁₁Mo₄₀O₆₂ the Mo? O distances (average 206 pm) and the Mo? Mo distances within the octahedral units (average 275 pm) are slightly decreased by 1 and 4 pm, respectively. The very short Mo? Mo distances (278 pm) between the cluster units which are not observed in In₁₁Mo₄₀O₆₂ (320 pm) are due to excess electrons in these inter-cluster bonds which would otherwise occupy antibonding cluster states.     

Synthese und Strukturuntersuchung von Zn3Ta2O8

Zn₃Ta₂O₈ was prepared by high temperature solid state reaction (CO₂-Lasertechnique). X-ray investigations of single crystals yield monoclinic symmetry (a=9.499;b=8.411;c=8.881 Å; =116.03°, space group C _2h ⁶ —C2/c). There is no relationship between Zn₃Ta₂O₈ and Zn₃Nb₂O₈. Zn₃Ta₂O₈ shows a characteristic structure type with octahedral coordination of Ta⁵⁺ and tetrahedral coordination of Zn²⁺.

     

Neue Suboxid-Cluster [O5Ba18] in den Kristallstrukturen von Ba21M2O5 (M = Si,Ge)

Novel Suboxide Clusters [O₅Ba₁₈] in the Crystal Structures of Ba₂₁M₂O₅ (M = Si, Ge) The compounds Ba₂₁M₂O₅ (M = Si, Ge) crystallize in the cubic system with space group Fd3m, lattice constants 2 038.3(10) pm (Si), 2 039.8(9) pm (Ge) resp. and Z = 8. The crystal structure contains isolated Si/Ge atoms coordinated by barium atoms in an icosahedral arrangement. The oxygen atoms are situated in the centers of barium octahedra, four of which share common faces with an additional central octahedron. The novel clusters [O₅Ba₁₈] in principal are related to those in the crystal structures of the binary Cs/Rb suboxides.     

Die trikline Kristallstruktur von Ag2Bi2S3Cl2: Pseudosymmetrie und Zwillingsbildung

Ruby‐red crystals of Ag₂Bi₂S₃Cl₂ were synthesized from AgCl and Bi₂S₃ by cooling a melt from 770 K to room temperature. X‐ray diffraction on powders and single‐crystals revealed a triclinic crystal structure with special lattice constants (P &1macr; (No. 2), a = 1085.0(2), b = 717.2(1), c = 1137.6(1) pm, α = 89.80(1)?, β = 74.80(1)?, γ = 87.81(1)?). In the structure [Bi^IIIS₃Cl₄] polyhedra form 2[BiS_3/2Cl_4/4]^‐ double‐layers by sharing common faces and edges. The silver(I) cations between the layers are coordinated either octahedrally by sulfide ions or tetrahedrally by sulfide and chloride ions. The deviations from the monoclinic space group P 1 2₁/c 1 are small and induce twinning along [010]. Further pseudosymmetry is based on the stacking of layer packages with the symmetry of the layer group P (2/c) 2₁/c 2/b.     

Synthese,Charakterisierung und Kristallstrukturen von Tetraiodoferraten(III)

Preparation, Characterization, and Crystal Structures of Tetraiodoferrates(III) The extremely air and moisture sensitive tetraiodoferrates MFeI₄ with M = K, Rb and Cs have been synthesized by reaction of Fe, MI and I₂ at 300°C in closed quartz ampoules. The essentially more stable alkylammonium tetraiodoferrates NR₄FeI₄ with R = H, C₂H₅, n-C₃H₇, n-C₄H₉ and n-C₅H₁₁ can be obtained by reaction of Fe, NR₄I and I₂ in nitromethane. The Raman and UV/Vis-spectra of the black compounds show the existence of tetrahedral [FeI₄]^? ions in the structures. The crystal structure of the monoclinic CsFeI₄ (CsTlI₄ type, spgr P2₁/c; a = 7.281(1) Å; b = 17.960(3) Å; c = 8.248(2) Å; β = 107.35(15)°) is built up by tetrahedral [FeI₄]^? ions and CsI₁₁ polyhedra. The crystal structure of the orthorhombic (n-C₅H₁₁)₄NFeI₄ (spgr Pnna; a = 20.143(4) Å; b = 12.683(3) Å; c = 12.577(3) Å) contains tetrahedral [(n-C₅H₁₁)₄N]⁺ ions and [FeI₄]^? ions, respectively.     

Synthese und Kristallstruktur von Cu6Mo5O18

Synthesis and Crystal Structure of Cu₆Mo₅O₁₈ Single crystals of the hitherto unknown compound Cu₆Mo₅O₁₈ were prepared and investigated by X-ray methods (a = 18.884(19), b = 6.273(7), c = 15.259(23) Å, β = 130.40(5)°, space group C–C2/c, Z = 4). The typical features of the structure are described and compared with the crystal chemistry of oxocuprates(I). Observed and calculated powder patterns show that the correct composition of the earlier described compound Cu₆Mo₄O₁₅ is Cu₆Mo₅O₁₈.     

Die Kristallstrukturen von Hexachalcogeno‐Hypodiphosphaten des Magnesiums und Zinks

Crystal Structures of Hexachalcogeno‐Hypodiphosphates of Magnesium and Zinc Five chalcogeno‐hypodiphosphates were synthesized and investigated by single crystal X‐ray methods. Mg₂P₂S₆ (C2/m; a = 6.085(1), b = 10.560(2), c = 6.835(1)Å, β = 106.97(3)°; Z = 2) crystallizes with the Fe₂P₂S₆ type structure, whereas Mg₂P₂Se₆ (a = 6.404(1), c = 20.194(4)Å) and Zn₂P₂Se₆ (a = 6.290(3), c = 19.93(2)Å) build up the Fe₂P₂Se₆ type (R3; Z = 3). The structures are characterized by closest packings of sulfur (selenium) with Mg²⁺ (Zn²⁺) ions and P₂ pairs in half the octahedra — analogous to the CdCl₂ and CdI₂ type, respectively. In Mg₂P₂S₆ half the Mg²⁺ ions can be substituted by Ag⁺ ions resulting in Ag₂MgP₂S₆ (C2/n; a = 6.364(1), b = 10.975(2), c = 13.999(3)Å, β = 108.29(3)°; Z = 4). In this compound the Ag⁺ ions are disordered and located in the octahedra originally occupied by Mg²⁺ ions. In Mg₂P₂Se₆ an analogous substitution by K⁺ ions leads to the compound K₂MgP₂Se₆ (P2₁/n; a = 6.546(1), b = 12.724(3), c = 7.599(2)Å, β = 103.02(3)°; Z = 2) with K₂FeP₂S₆ type structure. The structure is characterized by columns of alternating face‐sharing Se octahedra (centered by Mg) and trigonal antiprisms (centered by P₂ pairs) along [100]. The columns are interconnected by inserted K⁺ ions.     

Neue metallorganisch substituierte Indium–Stickstoff-Verbindungen. Synthese und Kristallstrukturen von [{Cp(CO)3Mo}2InN(SiMe3)2] und [{Cp(CO)3Mo}In{N(SiMe3)2}2]

New Organometallic Indium Nitrogen Compounds. Synthesis and Crystal Structures of [{Cp(CO)₃Mo}₂InN(SiMe₃)₂] and [{Cp(CO)₃Mo}In{N(SiMe₃)₂}₂] The reaction of [{Cp(CO)₃Mo}₂InCl] with LiN · (SiMe₃)₂ leads to the formation of [{Cp(CO)₃Mo}₂InN · (SiMe₃)₂] ( 1 ). 1 is monomeric and it contains an indium atom which is coordinated in a trigonal planar manner by two {Cp(CO)₃Mo} fragments and a N(SiMe₃)₂ group. The corresponding bis-amide [{Cp(CO)₃Mo}In{N(SiMe₃)₂}₂] ( 2 ) is prepared by the reaction of [{Cp(CO)₃Mo}InCl₂] with two equivalents of LiN(SiMe₃)₂. In analogy to 1, 2 is monomeric and it contains an indium atom in a trigonal planar coordination.     

Zur Kristallstruktur von α-TlSmW2O8

Single crystals of -TlSm(WO₄)₂ were examined by X-ray diffractometer technique (space group C _2h ⁶ -C2/c;a=10.770,b=10.597,c=7.597 Å, =130.09°,Z=4). The coordination of W⁶⁺, Sm³⁺ and Tl⁺ are discribed and discussed.-TlSm(WO₄)₂ is isotypic to -KY(WO₄)₂.

     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Kristallstrukturen von [TiF3(NPPh3)(HNPPh3)]2 und von HNPPh3

Crystal Structures of [TiF₃(NPPh₃)(HNPPh₃)]₂ and of HNPPh₃ The phosphoraneiminato-phosphaneimine complex [TiF₃(NPPh₃)(HNPPh₃)]₂ was obtained by the reaction of TiF₄ with Me₃SiNPPh₃ in boiling dichloromethane. It crystallizes from 1,2-dichloroethane as yellow crystals which include four molecules C₂H₄Cl₂ per dimeric formula unit. Space group P2₁/n, Z = 2, structure solution with 7270 independent reflections, R = 0.060 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1417.5, b = 1896.9, c = 1586.6 pm, β = 101.22°. The compound forms centrosymmetric dimeric molecules via μ₂-F bridges with TiF distances of 194.6 and 223.3 pm, the longer one being in trans-position to the N atom of the (NPPh₃)^? ligand. Its TiN bond length of 177.7 pm corresponds with a double bond. The TiN bond length of the HNPPh₃ donor molecule of 213.4 pm is typical for a donor acceptor bond. According to the crystal structure determination the phosphaneimine HNPPh₃ forms monomeric molecules without intermolecular hydrogen bridges with a PN bond length of 152.4 pm. Space group P2₁/c, Z = 4, structure solution with 3229 independent reflections, R = 0.062 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1460.4, b = 928.9, c = 1096.6 pm, β = 93.35°.     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

Synthese und Kristallstruktur von Calcium-Kupfer-Diarsenat CaCuAs2O7

Synthesis and Crystal Structure of the Calcium Copper Diarsenate CaCuAs₂O₇ Solid state reactions led to single crystals of CaCuAs₂O₇. X-ray investigations revealed monoclinic symmetry, space group C⁵_2h-P2₁/c, lattice constants a = 7.272(1); b = 8.946(2); c = 9.307(2) Å; β = 109.48(2)°; Z = 4. CaCuAs₂O₇ is characterized by ¹_∞[CaO₆] chains, connected by As₂O₇ double tetrahedra and elongated square CuO₅ pyramids. The hitherto unknown crystal structure shows relationships to CaCuP₂O₇ but not to CaCuV₂O₇.     

Phosphaniminato-Komplexe des Iods. Synthese und Kristallstrukturen von Ph3PNIO2 und Ph3PNSiMe3 · I2

Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph₃PNIO₂ and Ph₃PNSiMe₃ · I₂ Ph₃PNIO₂ has been prepared as yellow crystals by the reaction of Ph₃PNSiMe₃ with I₂O₅ in boiling acetonitrile, whereas the molecular complex Ph₃PNSiMe₃ · I₂ is formed as brown crystals by the reaction of Ph₃PNSiMe₃ with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations. Ph₃PNIO₂: Space group P2₁/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond. Ph₃PNSiMe₃ · I₂: Space group P1 , Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I₂ molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N? I? I axis with a bond length N? I of 243.2 pm.     

Silanolato-Komplexe von Titan und Zirconium. Die Kristallstrukturen von Cp2TiCl(OSiPh3) und Cp2ZrCl(OSiPh3)

Silanolato Complexes of Titanium and Zirconium. The Crystal Structures of Cp₂TiCl(OSiPh₃) and Cp₂ZrCl(OSiPh₃) The title compounds have been prepared by the reaction of Cp₂MCl₂ (M = Ti, Zr) with triphenylsilanole in diethylether in the presence of piperidine. They form only sparingly moisture sensitive orange (Ti) or colourless (Zr) crystal needles, which were characterized by X-ray crystallography. Cp₂TiCl(OSiPh₃): Space group P2₁/n, Z = 4, structure solution with 3961 observed unique reflections, R = 0.057. Lattice dimensions at 20°C: a = 1029.6, b = 1719.3, c = 1388.9 pm, β = 100.69°. The compound forms monomeric molecules with bond lengths TiO of 184.2 pm, SiO of 161.5 pm, and a TiOSi bonding angle of 164.5°. Cp₂ZrCl(OSiPh₃): Space group P3 , Z = 18, structure solution with 2799 observed unique reflections, R = 0.047. Lattice dimensions at ?20°C: a = b = 3518, c = 1058.3 pm. The structure consists of three symmetry-independent monomeric molecules, which differ only slightly. The bond lengths are (in average): ZrO 196.4 pm, SiO 162.1 pm, the ZrOSi bond angle is 173.7°.     

Die Kristallstrukturen der Monohydrate von Lithiumchlorid und Lithiumbromid

Crystal Structure of the Monohydrates of Lithium Chloride and Lithium Bromide Using single crystal analysis and powder diffraction data the crystal structures of the monohydrates of lithium chloride and lithium bromide were solved. Both compounds crystallise isotypic in the space group Cmcm (LiCl·H₂O: single crystal analysis; T = 100 K; a = 758, 35(2); b = 768, 07(2); c = 762, 35(2) pm; Z = 8; 1179 unique reflections; R₁ = 0, 0196. LiBr·H₂O: Rietveld‐refinement; T = 220 K; a = 806, 15(1); b = 799, 44(1) und c = 794, 61(1) pm; Z = 8; 157 unique reflections; R_p = 0, 0922; R_wp = 0, 0979; R_exp = 0, 0657). The structure derives from the perowskite structure according to the formula X(H₂O)Li□₂ (X = Cl, Br). The orientation of the water molecules is linked clearly to the distribution of the lithium cations and vice versa. The high level ionic conductivity in the cubic high temperature phase of LiBr·H₂O is related to the initial rotation of the water molecules during the phase transformation. This motion favours the lithium ion hopping and the melting of the lithium substructure respectively.     

Die Kristallstrukturen von Mn5O8 und Cd2Mn3O8

The crystal structures of Mn₅O₈ and Cd₂Mn₃O₈ are determined from single crystal and high resolution X-ray powder data. Both structures have very similar monoclinic unit cells, space group C–C2/m, and are isotypic: Hence, the true formula of Mn₅O₈ is MnMnO₈. The crystal structure consists of pseudohexagonal Mn^IV sheets (bc) with similar oxygen sheets on either side, giving a distorted octahedral coordination to the Mn^IV. As every fourth Mn^IV is missing in these “main layers”, their composition becomes Mn₃O₈, and chains of coordination octahedra linked by common edges become distinct. Above and below the empty Mn^IV sites are either Mn^II or Cd^II completing the composition MnMnO₈ or Cd₂Mn₃O₈ respectively. Examples of similar “double layer” structures are given.     

Neue mehrkernige Organozinn(IV)–Stickstoff‐Verbindungen. Synthese und Kristallstrukturen von [(PhSn)4(NPh)5Cl2] und [(MeSn)4(NHPh)4(NPh)4]

New Polynuclear Organotin(IV)–Nitrogen Compounds. Synthesis and Crystal Structures of [(PhSn)₄(NPh)₅Cl₂] and [(MeSn)₄(NHPh)₄(NPh)₄] The reaction of the organotin halides PhSnCl₃ and MeSnCl₃ with LiNHPh leads to the formation of two new nitrogen bridged organotin compounds, [(PhSn)₄(NPh)₅Cl₂] ( 1 ) and [(MeSn)₄(NHPh)₄(NPh)₄] ( 2 ). The crystal structures of 1 and 2 have been determined by low temperature X‐ray diffraction. 1 contains a bicyclic Sn₄N₅ framework, which consists of two six‐membered Sn₃N₃‐rings. All tin atoms are coordinated nearly tetrahedrally. Two tin atoms are bonded to a phenyl group and three nitrogen atoms, the other two tin atoms are coordinated by a phenyl group, two nitrogen atoms and a terminal chlorine atom. In 2 the tin atoms define the corners of a distorted square. Each edge of the square is bridged by a μ²‐NHPh and a μ²‐NPh group. The bridging NHPh and NPh groups are arranged at opposite sides of the Sn₄ plane. The tin atoms are coordinated square pyramidally by 4 nitrogen atoms and a methyl group.