Metallkomplexe des Hexamethyl-trisila-tetraphospha-nortricyclen P4 (Sime2)3

Transition Metal Complexes of the Hexamethyl-trisila-tetraphospha-nortricyclene P₄ (Sime ₂) ₃ P₄(Sime₂)₃ 1 reacts with Mo(CO)₆, Cr(CO)₅THF, and Mn(η-C₅H₅)(CO)₂THF to give crystalline complexes in which 1 functions as a monodentate ligand. In each compound one phophorus atom of the cyclotriphosphane ring coordinates to the metal atom. Using Mn(η-C₅H₅)(CO)₂THF, two different P atoms of the P₃ Cr(CO)₄ norbornadiene and 1 react, yielding the dimeric, red, crystalline compound (CO) ₄Cr[μ-P₄(Sime₂)₃]₂Cr(CO)₄. In this complex the two molecules of 1 are both bonded by two P atoms of the P ₃ ring to the two Cr(CO)₄ Units, forming a six-memered (CrP₂)₂ring.     

Die Strukturen der Heptahetero-Nortricyclene P7(Sime3)3 und P4(Sime2)3

The Structures of the Heptahetero-Nortricyclenes P₇(Sime₃)₃ and P₄(Sime₂)₃ Tris(trimethylsilyl)heptaphospha-nortricyclene P₇(Sime₃)₃ 1 and Hexamethyl-trisila-tetraphospha-nortricyclene P₄Si₃me₆ 2 are structural analogons to the hetero-nortricyclenes P and P₄S₃. 1 crystallizes in the space group P2₁ with a = 965.7 pm, b = 1746.5 pm, c = 693.3 pm, β = 99.61° and Z = 2 formula units. In the P₇ system tge P? P bond lengths differ functionally, namely 221.4 pm in the three-membered ring, 219.2 pm at the ring atoms and 217.9 pm at the bridgehead atom. The P? Si and Si? C bond lengths are 228.8 pm and 187.8 pm respectively. 2 crystallizes in the space group R3 with a_R = 1129.3 pm, α_R = 50.01° (hexagonal axes: a = 954.7 pm, c = 2956.9 pm) and Z = 2 formula units. In the P₄Si₃ systems the bond lengths are P? P = 220.2 pm, P? Si = 228.3 pm and 224.7 pm (to the bridgehead atom). The Si? C bond lengths are 187.3 pm. The structures are discussed with related compounds.     

Untersuchungen zur Metallierung der Cyclophosphane P4(Cme3)3(Sime3), P4(Cme3)2(Sime3)2, P4(Sime3)4

Investigations Concerning the Metallation of the Cyclotetraphosphanes P₄(Cme₃)₃(Sime₃), P₄(Cme₃)₂(Sime₃)₂, and P₄(Sime₃)₄ The reaction of white phosphorus with LiCme₃ and me₃SiCl yields P₄(Sime₃)(Cme₃)₃ 1 . With n-buLi this crystalline cyclotetraphosphane forms the crystalline LiP₄(Cme₃)₃. In the same manner, n-buLi, with trans-P₄(Sime₃)₂(Cme₃)₂ 2 to yields LiP₄(Sime₃)(Cme₃)₂, which in contrast to LiP₄(Cme₃)₃ decomposes within a few hours yielding P(Sime₃)₂n-bu 6 , P(Sime₃)₃ 8 , LiP(Sime₃)₂ 9 and also the cyclic compounds P₄(Sime₃)(Cme₃)₃ 10 , LiP₄(Cme₃)₃ 11 and LiP₃(Cme₃)₂ 12 . The composition of the product mixture depends on the molar ratio of 2 to LiC₄H₉. At a molar ratio of 1:1 11 and 12 are not jet observed. At molar ratios of 1:1.5 and 1:2 P(Sime₃)₃ is not found. The amount of 11 and 12 grows with increasing concentration of n-buLi. On addition of n-buLi the solution of P₄(Sime₃)₄ immediately turns red. Li₃P₇ and Li₂P₇(Sime₃) (among others) are formed so fast that the first intermediates in the lithiation sequence so far could not be elucidated. These results demonstrate clearly that replacement of two me₃Si groups in P₄(Sime₃)₄ by two me₃C groups excludes the rearrangement of LiP₄(Sime₃)(Cme₃)₂ to a P₇-molecule.     

Die Kristallstruktur des Thallium(I)-hexaiodomercurat(II), Tl4Hgl6

Crystal Structure of Thallium(I) Hexaiodomercurate(II), Tl₄HgI₆ In the structure of the tetragonal Tl₄HgI₆ (a = 944.6 pm, c = 926.0 pm, Z = 2, space group P 4/mnc) isolated, in c-direction compressed HgI₆ octahedra are situated. The mercury atoms are disordered; they occupy statistically 4 positions in the equatorial plane of the octahedra in such a manner that strongly deformed HgI₄ tetrahedra are produced. The thallium atoms are eightfold coordinated like a bicapped trigonal prism. The relationship between the Tl₄HgI₆ structure and the cubical K₂PtCl₆ type will be discussed.     

Das Hexamethyl-trisila-tetraphospha-nortricyclen,P4(Sime2)3

Hexamethyl-trisila-tetraphospha-nortricyclene, P₄ Sime₂₃ Reaction of white phosphorus with Na/K alloy and subsequent treatment with me₂SiCl₂ (me = CH₃) yields crystalline P₄(Sime₂)₃ (m. p. 159–160°C) along with polymeric silylphosphanes. The structure is derived from ³¹P-n.m.r.and mass spectra and turns out to be analogous to P₄S₃.     

Die Kristallstruktur von Co4Hf2P3

Zusammenfassung Die Struktur einer ternären Phase mit der Idealzusammensetzung Co₄Hf₂P₃ wurde röntgenographisch mittels Einkristallmethoden bestimmt und verfeinert. Die Gitterparameter der hexagonalen Elementarzelle sinda=12,0559 undc=3,6249 Å, die Raumgruppe ist . Die Phase ist strukturell mit Fe₂P und Fe₁₂Zr₂P₇ verwandt.

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The structure of a ternary phase with the ideal composition Co₄Hf₂P₃ has been determined and refined by means of singlecrystal X-ray methods. The cell dimensions of the hexagonal unit cell are found to be:a=12,0559 andc=3,6249 Å, the space group is . The phase is structurally related to Fe₂P and Fe₁₂Zr₂P₇.

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Mit 1 Abbildung     

Die Kristallstruktur des SrHg(SCN)4 · 3 H2O

Crystal Structure of SrHg(SCN)₄ · 3 H₂O SrHg(SCN)₄ · 3 H₂O is orthorhombic, space group Pcca, with a = 19.476(7), b = 8.150(1), c = 8.991(3) Å, V = 1427.1 ų, Z = 4, d_c = 2.67 g · cm^?3, μ(AgKα) = 77.95 cm^?1. The salt consists of nearly tetrahedral Hg(SCN)₄ groups, Sr has a tricapped trigonal prismatic coordination: four N and five O atoms. The thiocyanate groups form end-to-end bridges and connect the Hg and Sr coordination polyhedra.     

Die Kristallstruktur von Cu7(OH)6(TeO3)2(SO4)2

The crystal structure of the new phase Cu₇(OH)₆(TeO₃)₂(SO₄)₂ [a=7.389 (1),b=7.638 (1),c=7.662 (2) Å, =75.17 (1), =75.90 (1), =84.19 (1)°;Z=1] was determined by direct methods andFourier summations from X-ray intensities, and was refined in space group P -C _i ¹ toR=0.039. As usual, the Cu(II) atoms are coordinated to four O atoms forming approximately a square with average Cu-O=1.96 (3) Å; one or two more distant O neighbours complete the coordination. The shape of the TeO₃ group is a rather clear-cut trigonal pyramid. A disorder was found for the SO₄ tetrahedra. The compound was synthesized under hydrothermal conditions [500 (10) K, saturation vapour pressure].

Herrn Prof. Dr.K. Komarek zum 60. Geburtstag gewidmet.     

Die Kristallstruktur von CuBr · (C2H5)4P2

The crystal structure of CuBr · (C₂H₅)₄P₂ has been determined by single crystal X-ray methods. The crystals are triclinic (space group P 1 ) with two formula units per unit cell (a) = 9,29, b = 9,92, c = 7,57 Å, α = 85,3°, β = 106,6°, γ = 109,1°. The copper atoms are tetrahedrally coordinated by two bromine and two phosphorus atoms (of different biphosphine molecules). The structure has continuous chains running parallel c, in which the copper atoms are linked together by alternating double bridges consisting of two biphosphine molecules and two bromine atoms, respectively.     

Chlorthionitrenkomplexe des Wolframs Die Kristallstruktur von [WCl4(NSCl)]2

Chlorothionitrene Complexes of Tungsten. Crystal Structure of [WCl₄(NSCl)]₂ Tungsten hexachloride reacts with trithiazyl chloride, (NSCl)₃, yielding the chlorothionitrene complex [WCl₄(NSCl)]₂, from which AsPh₄[WCl₅(NSCl)] can be obtained by reaction with AsPh₄Cl. Both complexes are characterized by their i.r. spectra. The crystal structure of [WCl₄(NSCl)]₂ was determined and refined with X-ray diffraction data (1059 reflexes, R = 0.055). It crystallizes in the monoclinic space group P2₁/n with the lattice constants a = 1523, b = 904, c = 583 pm and β = 91.35°. In the unit cell there are two centrosymmetric [WCl₄(NSCl)]₂ molecules in which the W atoms are linked via two chloro bridges; short and long W? Cl distances (244 and 265 pm) alternate in the W₂Cl₂ ring, the NSCl groups are found in the trans positions to the longer W? Cl bonds. The WNS bond angle (175°) and short bond distances correspond to a formulation .     

Die Kristallstruktur von Ag2TeO2(OH)4

Zusammenfassung Die Kristallstruktur von Ag₂TeO₂(OH)₄ wurde mit Hilfe von Einkristallmethoden bestimmt und nach der Methode der kleinsten Quadrate verfeinert. Die Gitterparameter der Elementarzelle (Fdd 2–C _2v ¹⁹ ) betragen:a=18,72;b=6,48;c=8,94 Å. Mit allen beobachteten Reflexen wurde einR-Wert von 8,50%, unter Einschluß derHamilton-Reflexe einR-Wert von 9,41% erhalten. Die Telluratome sind oktaedrisch von 6 Sauerstoffen umgeben, während die Silberatome stark verzerrt tetraedrisch von 4 Sauerstoffen umgeben sind. Zwei dieser Tetraeder bilden mit einem dazwischenliegenden Oktaeder eine geometrische Einheit. Diese Einheiten sind über Sauerstoffe, die zu zwei verschiedenen Tetraedern gehören, und über Wasserstoffbrücken zu einem dreidimensionalen Gerüst verknüpft.

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The crystal structure of Ag₂TeO₂(OH)₄

The crystal structure of Ag₂TeO₂(OH)₄ has been determined by single crystal X-ray methods and refined by the least squares method. The lattice parameters of the cell (Fdd 2–C _2v ¹⁹ ) are:a=18.72;b=6.48;c=8.94 Å. With all observed reflections anR-Value of 8.50% was obtained; if allHamilton-reflections are includedR=9.41%. The Te atoms are surrounded octahedrally by 6 oxygens, the 4 oxygens around the silver atoms form a distorted tetrahedron. Two of these tetrahedra form with an intermediate octahedron a geometric unit. These units are linked together to a three-dimensional structure by oxygens belonging to two different tetrahedra and by hydrogen bondings.

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Mit 5 Abbildungen     

Die Kristallstruktur des Hexakaliumdigermanats,K6Ge2O7

The title compound is monoclinic, space group Pc (No. 7),a=6.549 (1),b=9.094 (1),c=11.426 (2) Å, =126.78 (1)° andZ=2. Its crystal structure has been refined from 1 323 single crystal X-ray reflections toR=0.131. The structure of K₆Ge₂O₇ is very similar to that of K₆Co₂O₇ and K₆Si₂O₇ both of which have been reported to be centrosymmetric, space group P2₁/c. While the angle at the bridging oxygen atom is 180° in the latter compounds, it is 157° in K₆Ge₂O₇.

     

Die Kristallstruktur des Komplexnitrides Mo(Ta,Mo)2N2

In the ternary system Ta/Mo/N a complex nitride of formula Mo(Ta,Mo)₂N₂ was observed at a nitrogen pressure of 360 bar and a temperature of 1,600°C. The crystal structure was determined from X-ray powder diagrams. The tetragonal unit cell, space groupI4/mmm-D _4h ¹⁷ , lattice parametersa=0.3051 nm,c=1.2530 nm contains ten atoms with an arrangement of the metal atoms corresponding to the MoSi₂-Type structure.

     

Die Kristallstruktur des Bleicyclotetraphosphat-4-Hydrats,Pb2P4O12 · 4H2O

Crystal Structure of Lead Cyclotetraphosphate-4-Hydrate, Pb₂P₄O₁₂·4 H₂O Pb₂P₄O₁₂·4 H₂O is the starting product of a series of solid state reactions with the final product cyclooctaphosphate. Pb₂P₄O₁₂·4 H₂O crystallizes in the monoclinic space group P2₁/n, with a = 8.07 ± 0.02, b = 11.76 ± 0.03, c = 7.50 ± 0.02 Å and β = 108.2 ± 0.3°. The crystal structure has been solved by Patterson and Fourier methods and refined by least squares calculations to an R-index of 0.07. The structure consists of P₄0₁₂^4? ringanions, which are connected by Pb and hydrogen bonds. Lead is coordinated by eight oxygen atoms.     

Thionitrosylkomplexe des Osmiums. Die Kristallstruktur von AsPh4[OsCl4(NS)2Cl]

Thionitrosyl Complexes of Osmium. Crystal Structure of AsPh₄[OsCl₄(NS)₂Cl] The reaction of osmium pentachloride with trithiazyl chloride (NSCl)₃ yields the thiazylchloride complex [OsCl₄(NSCl)₂], from which the thionitrosyl complex AsPh₄[OsCl₄(NS)₂Cl] is obtained by reaction with AsPh₄Cl in CH₂Cl₂. From this, the neutral thionitrosyl complex [OsCl₄(NS)₂] forms by chloride abstraction with gallium trichloride. The crystal structure of AsPh₄[OsCl₄(NS)₂Cl] was determined and refined with the aid of X-ray diffraction data (R = 0.033, 2161 reflexions). It crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. The lattice constants are a = 1735, b = 1058, c = 1578 pm and β 95.64°. In the [OsCl₄(NS)₂Cl]^? ion the osmium is octahedrally coordinated by four Cl atoms and two NS groups in a cis arrangement. The NS groups are essentially linear with the bond lengths Os?N 184 pm and N?S 146 pm. Loosely attached to one of the S atoms there is a Cl atom (S? Cl distance 228 pm); in the crystal it statistically belongs to both S atoms with an occupation probability of one half, and it cannot be decided whether there is a dynamical fluctuation between the S atoms or a static positional disorder. However, according to the i.r. spectrum the dynamical model seems more probable.     

Die Kristallstruktur des Natriumorthogermanats,Na4GeO4

The crystal structure of the title compound has been determined from single crystal X-ray diffraction data and refined toR=0.125. The unit cell is triclinic, space group P, (No. 2),a=5.688(1),b=5.701(1),c=8.583(1) Å, =81.32(1), =71.50(1), =67.95(1)° andZ=2. The structure consists of isolated [GeO₄] tetrahedra linked together by four- and five-coordinate sodium atoms. Na₄GeO₄ is isostructural with Na₄CoO₄ (which has been described to be non-centrosymmetric and for which a centrosymmetric model is presented), K₄GeO₄, K₄SnO₄ and K₄PbO₄.

     

Die Kristallstruktur von (Ph4P)2[Be4Cl4(μ‐N3)6]

Suitable single crystals for X‐ray analysis of the recently published azido beryllate (Ph₄P)₂[Be₄Cl₄(μ‐N₃)₆] ( 1 ) [1] were obtained by a modified synthetic route, and the crystal structure of 1 was determined. The compound crystallizes isotypically with the corresponding bromo derivative [1] in the space group C2/c with 12 formula units per unit cell. Lattice dimensions at 193 K: a = 4125.5(1), b = 2001.7(1), c = 2050.4(1) pm, β = 101.05 (1)°, R₁ = 0.0359. The structure contains adamantanlike dianions [Be₄Cl₄(μ‐N₃)₆]^2? with a Be₄N₆ core forming by the bridging function of the α‐nitrogen atoms of the azido groups.     

Die Kristallstruktur des Chromarsenids Cr4As3

The crystal structure of Cr₄As₃ has been determined by single crystal photographs: $$\begin{gathered} space group Cm - C_s ^3 \hfill \\ \alpha = 13.16_8 {\AA} \hfill \\ b = 3.54_2 {\AA} \hfill \\ c = 9.30_2 {\AA} \hfill \\ \beta = 102.1_9 \circ \hfill \\ \end{gathered}$$ Cr₄As₃ crystallizes with a novel structure type, which can be derived from the MnP-structure type.     

Azidocuprate(II). Die Kristallstruktur von (PPh4)2[Cu2(N3)6]

Azidocuprates(II). Crystal Structure of (PPh₄)₂[Cu₂(N₃)₆] (PPh₄)₂[Cu(N₃)₄] and (PPh₄)₂[Cu₂(N₃)₆], which is already known, are prepared from the corresponding chloro cuprates and excess silver azide in dichloro methane suspension. The azido cuprates form nonexplosive brown crystals of low sensitivity to moisture and are characterized by i.r. spectroscopy. (PPh₄)₂[Cu₂(N₃)₆] was submitted to a X-ray crystallographic structural analysis (4284 observed, independent reflexions, R = 0.034). The compound crystallizes triclinic in the space group P1 with one formula unit per unit cell. The lattice parameters are a = 1047.4 pm; b = 1131.1 pm; c = 1179.4 pm; α = 101.26°; β = 109.31°; γ = 103.42°. The compound consists of PPh₄^⊕ cations and centrosymmetric anions [Cu₂(N₃)₆]^2?, which meet D_2h-symmetry fairly well. In the anions the copper atoms are linked to a planar Cu₂N₂ four-membered ring by the N α atoms of two azide groups. The other azido ligands are bonded terminally and complete coordination number 4 at the Cu atoms which show planar geometry.