Die Kristallstruktur von AgCu3Cu(AsO4)3 und ihre strukturellen Beziehungen zu AgCo3H2(AsO4)3 bzw. AgZn3H2(AsO4)3

Crystal Structure of AgCu₃Cu(AsO₄)₃ and its Structural Relations to AgCo₃H₂(AsO₄)₃ and AgZn₃H₂ (AsO₄)₃ The compound AgCu₃Cu(AsO₄)₃ was synthesized and investigated by X-rays. It crystallizes in the monoclinic space group C2/c with a = 1 212.7(2), b = 1 249.0(2), c = 727.8(1) pm, β = 117.94(1)°, Z = 4. The structure is closely related to the structures of AgCo₃H₂(AsO₄)₃ and AgZn₃H₂(AsO₄)₃. Only two hydrogen atoms are replaced by an additional copper atom forming a copper coordination square instead of two hydrogen bridges. The remaining copper atoms are sixfold coordinated with the generally observed Jahn-Teller distortion. Whereas in AgCo₃H₂(AsO₄)₃ and AgZn₃H₂(AsO₄)₃ silver has a (4+4) coordination, it is in this compound distinctly eightfold coordinated.     

Zur Kenntnis der ionischen Ozonide P(CH3)4O3 und As(CH3)4O3

On the Knowledge of the New Ionic Ozonides P(CH₃)₄O₃ and As(CH₃)₄O₃ P(CH₃)₄O₃ and As(CH₃)₄O₃ were prepared via ion exchange in liquid ammonia and characterized by X-ray-powder, IR, MS and DTA techniques. P(CH₃)₄O₃ and As(CH₃)₄O₃ are isotypic and have a wurtzite-like arrangement of ions with rotationally disordered O₃^?. (Powder data: P6₃mc; P(CH₃)₄O₃: a = 687.8(2), c = 964.6(3) pm; As(CH₃)₄O₃: a = 708.6(1), c = 991.0(3) pm). As(CH₃)₄O₃ shows a displacive phase transition at ?135°C. The low temperature phase is orthorhombic (a = 715.8(7), b = 1 209(1), c = 943.3(1) pm).     

PPh4[As3S3Cl4] und PPh4[As3S3Br4]

PPh₄[As₃S₃Cl₄] and PPh₄[As₃S₃Br₄] When As₂S₃ reacts with PPh₄X and HX in 1,2-C₂H₄X₂ (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh₄[As₂SX₅]. Their crystal structures were determined by X-ray diffraction. PPh₄[As₃S₃Cl₄]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh₄[As₃S₃Br₄]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh₄[As₃S₃Br₄] does not form twins as PPh₄[As₃S₃Cl₄]. The crystals consist of PPh₄⁺ and [As₃S₃X₄]^? ions. In the anions, the three As atoms of an As₃S₃ ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers.     

[(Ph3Sn)3VO4]·CH3CN und [(Ph3Sn)3VO4]·2 DMF,Triphenylzinnvanadate mit neuartigen Kettenstrukturen

[(Ph₃Sn)₃VO₄]·CH₃CN and [(Ph₃Sn)₃VO₄]·2 DMF, Triphenyltin Vanadates with Novel Chain Structures The reaction of Na₃VO₄ with Ph₃SnCl in a water/CH₂Cl₂ mixture leads to the formation of [(Ph₃Sn)₃VO₄] ( 1 ). Recrystallization of 1 from toluene/CH₃CN gives pale yellow crystals of [(Ph₃Sn)₃VO₄]·CH₃CN ( 2 ). 2 crystallizes as coordination polymer which consists of infinite chains composed of corner‐sharing VO₄ tetrahedra and Ph₃SnO₂ trigonal bipyramides. Additionally the VO₄ groups are connected to two terminal SnPh₃‐Groups containing tin atoms in a tetrahedral environment. [(Ph₃Sn)₃VO₄]·2 DMF ( 3 ) which is obtained from Na₃VO₄ and Ph₃SnCl in a water/DMF mixture contains a polymeric chain structure similar to 2 and additionally one of the terminal SnPh₃ groups is coordinated to a DMF solvent molecule.     

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.     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (Φ/Φ) in the cyclotetrasiloxanes Φ_mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of Φ_mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from Φ_mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes Φ_mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings ΦD₃, Φ₂D₂, Φ₃D, and Φ₄. The reactivity of the siloxane links rises in the sequence ～ (CH₃)₂Si-O-Si(CH₃)₂ ～<～ (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ ～<(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) ～. Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.     

Tetraazadibora[3, 3]paracyclophane

Starting from the para‐phenylenediamine derivative HN(SiMe₃)‐C₆H₄‐NH(SiMe₃), a lithiation and subsequent borylation give [(MeO)₂B]N(SiMe₃)‐C₆H₄‐N(SiMe₃)[B(OMe)₂] ( 1 ), the hydridation of which yields Li₂[(H₃B)N(SiMe₃)‐C₆H₄‐N(SiMe₃)(BH₃)] ( 2 ). Applying ZrCl₄ upon 2 initiates a condensation to give the title compound [‐N(SiMe₃)‐p‐C₆H₄‐N(SiMe₃)‐BH‐]₂, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P2₁2₁2₁.     

Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

The alkalimetal phosphoraneiminates [KNPCy₃]₄, ( 1 ) [KNPCy₃]₄·2OPCy₃ ( 2 ) and [CsNPCy₃]₄·4OPCy₃ ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy₃PI₂ or Cy₃PBr₂ in liquid ammonia, as well as the lithium derivative [Li₄(NPPh₃)(OSiMe₂NPPh₃)₃(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe₂)n into the LiN bonds of [LiNPPh₃]₆ in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc2₁, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ₃‐NPCy₃^‐) groups, whereas 4 forms a "heteroleptic" Li₄NO₃ heterocubane.     

K3BiSe3, Rb3BiSe3 und Cs3BiSe3 – Substitutionsvarianten des Th3P4-Typs

K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ – Derivatives of the Th₃P₄ Structure Type The compounds K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ were synthesized by heating mixtures of Bi₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 850°C. Thin crystals of the compounds appear red in transmitted light. They crystallize isostructural with Na₃AsS₃, space group P2₁3, lattice constants a = 9.771(5) Å, a = 10.161(3) Å, and a = 10.587(5) Å for K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃, respectively. The Na₃AsS₃ structure type is a derivative of the Th₃P₄ structure type.     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The catalytic rearrangement of the cyclopentasiloxanes Φ_mD_5-m, where Φ represents a 3, 3, 3-trifluoropropyl(methyl)siloxane link and D a dimethylsiloxane link, and m=2–5 has been studied by the method described previously [1]. The rate of rearrangement and the rate of formation of a linear polysiloxane rise with an increase in m from 2 to 4. The equilibrium concentration of the linear polysiloxane formed from Φ_mD_5-m and from Φ_mD_4-m (m=0–4) [1] is inversely proportional to the molar fraction of Φ links in the ring and rises with an increase in the total concentration of siloxane links in solution. Results have been obtained on the kinetics of the formation of the cyclosiloxanes Φ_mD_n (where m=0–5, n=0–5, and m+n=3-6) during the rearrangement of the cyclopentasiloxanes Φ_mD_5-m. It has been established that at equilibrium a mixture of cyclosiloxanes Φ_mD_n containing practically constant ratios of tetramers, pentamers, and hexamers (m+n=4, 5, and 6) is obtained, regardless of the composition and structure of the initial cyclosiloxane and of the conditions of rearrangement (polymerization). The cyclopentasiloxanes Φ_mD_5-m are less active in the process of rearrangement than the cyclotetrasiloxanes Φ_mD_4-m. The activity of the cyclosiloxanes in rearrangement in the presence of a base rises in the sequence D₄?ΦD₃ ≈ Φ₂D₃<Φ₃D₂<Φ₄D < Φ₂D₂ < Φ₃D.     

Zwei Galliumfluorid-Ammoniakate: Ga(NH3)F3 und Ga(NH3)2F3

Two Gallium Fluoride Ammine Complexes: Ga(NH₃)F₃ and Ga(NH₃)₂F₃ Two gallium trifluoride ammines, Ga(NH₃)F₃ and Ga(NH₃)₂F₃, are obtained as single crystals through oxidation of gallium metal with NH₄HF₂ (Ga : NH₄HF₂ = 1 : 1.5) and NH₄F (Ga : NH₄F = 1 : 3.5), respectively, at 450 °C and 400 °C. Ga(NH₃)F₃ crystallizes with the non-centrosymmetric space group Abm2 (a = b = 544.6(2) pm, c = 986.6(4) pm) forming two-dimensional layers of [Ga(NH₃)F₅] octahedra. The addition of another NH₃ molecule in Ga(NH₃)₂F₃ (orthorhombic, Immm, a = 700.0(3) pm, b = 724.7(2) pm, c = 393.1(1) pm) leads to one-dimensional rods of [Ga(NH₃)₂F₄] octahedra running parallel [001] which are stacked in the [010] direction. Infrared spectra suggest hydrogen bonding (N–H…F) in Ga(NH₃)F₃, for Ga(NH₃)₂F₃ an unequivocal statement is not possible.     

Neue Moleküle A4B3 im System P4Se3–As4Se3

Novel A₄B₃ Molecules in the System P₄Se₃–As₄Se₃ By means of ³¹P-NMR and masspectroscopic measurements in the system P₄Se₃–As₄Se₃ was shown that in the melt and vapour phase at all compositions molecules of the type P_{4 ? n}As_nSe₃ are formed. A separation was possible by liquid chromatography (RP 18-column). The concentration distribution of the different species is nearly statistical. In the solid state at ambient temperature regions of solid solubility with α-P₄Se₃, α⁺-phase, α-P₄S₃ and α-As₄Se₃ structure were observed. P₃AsSe₃ could be transformed into a plastically-crystalline phase with β-P₄S₃ structure. At higher temperatures the phase decomposes slowly. The thermal behaviour of PAs₃Se₃ is strongly influenced by the heating rate. Using low heating rates it decomposes into an amorphous phase, by fast heating a transformation into a metastable plastically-crystalline modification was achieved. During long extraction with CS₂ molecules P_{4 ? n}As_nS_{3 ? m}Se_m are formed by an exchange reaction. They can also be prepared by melting the proper amounts of the elements.     

[{Cp″Co}3(μ3-P)(μ3-PSe)], ein Dreikerncluster mit einem PSe-Liganden

[{Cp″Co}₃(μ₃-P)(μ₃-PSe)], a Trinuclear Cluster with a PSe Ligand The cothermolysis of [Cp″Co(CO)₂] ( 1 ), Cp″ = C₅H₃Bu-1.3, and P₄ gives besides [{Cp″Co}₃(μ₃-P)₂] ( 2 ) the cobalt P_n complexes [{Cp″Co}₄(μ₃-P)₄] ( 3 ) and [{Cp″Co}₂(μ, η^2:2-P₂)₂] ( 4 ). 2 can be oxidized with grey selenium forming [{Cp″Co}₃(μ₃-P)(μ₃-PSe)] ( 5 ) and [{Cp″Co}₃(μ₃-PSe)₂] ( 6 ), complexes with the hitherto unknown PSe ligand. The crystal structure of 5 reveals a trigonal-bipyramidal Co₃P₂ skeleton with one μ₃-PSe ligand.     

Etude du Systeme LiPO3-Pr(PO3)3 Donnees sur LiPr(PO3)4

The LiPO₃-Pr(PO₃)₃ system was studied by micro-differential thermal analysis. The only new compound observed in the system was LiPr(PO₃)₄, melting incongruently at 1246 K. An eutectic appears at 926 K. Crystallographic data and powder diagram of the new compound are given. LiPr(PO₃)₄ crystallizes in the C2/c monoclinic system with unit cell: a=16.428(6), b=7.054(3), c=9.747(4) Å, β=126°31′(3), V=910.2 ų, Z=4. The IR and Raman spectra of this compound are given. This revised version was published online in July 2006 with corrections to the Cover Date.     

AgCo3H2(AsO4)3 und AgZn3H2(AsO4)3 Darstellung und Kristallstruktur Ein weiterer neuer Arsenat-Strukturtyp

AgCo₃H₂(AsO₄)₃ and AgZn₃H₂(AsO₄)₃. Preparation and Crystal Structure. Another New Structure Type of an Arsenate AgCo₃H₂(AsO₄)₃ ( 1 ) and AgZn₃H₂(AsO₄)₃ ( 2 ) were prepared by heating of As₂O₅, AgNO₃, CoSO₄ · 7H₂O, ZnSO₄ · 7H₂O, respectively, and water in a sealed tube at 300°C and investigated with X-rays. Both compounds are isotypic and crystallize in the monoclinic space group C2/c with 4 formula units per cell. The lattice parameters are ( 1 ): a = 1215.9(6), b = 1243.8(7), c = 678.2(3) pm, β = 113.16(3)° ( 2 ): a = 1216.9(2), b = 1249.5(3), c = 675.5(1) pm, β = 112.77(1)°. The structure contains chains of edge-shared CoO₆ or ZnO₆ octahedra, respectively, which are connected by AsO₄ tetrahedra and silver oxygen ribbons with square planar coordinated silver forming a framework. Based on the charge balances derived from the geometrical data and the IR spectra the occurence of hydrogen bonds is discussed.     

Tetraphenylphosphonium-tetraiodotrithiotriarsenat,PPh4[As3S3I4]

Tetraphenylphosphonium tetraiodotrithiotriarsenate, PPh₄[As₃S₃I₄] PPh₄[As₃S₃I₄] is formed along with PPh₄I₃ and other unidentified compounds by the reaction of As₂S₃, PPh₄I and HI in CH₂I₂ at 80°C. PPh₄[As₃S₃I₄] was characterized by its IR spectrum and an X-ray crystal structure determination (3684 unique observed reflexions, R = 0.083). Crystal data: a = 1390.3, b = 1548.9, c = 1505.4 pm, β = 91.08°, monoclinic, P2₁/c, Z = 4. The crystals are not isotypic with the corresponding chloro and bromo compounds, although the anion constitutions are of the same type. The [As₃S₃I₄]^? ion consists of an As₃S₃ ring in the chair conformation, the three As atoms are commonly linked to a bridging I atom and each As atom is bonded to one terminal I atom. Cations and anions are packed in alternating layers.     

Bildung von NH4[Hg3(NH)2](NO3)3 und Umwandlung in [Hg2N](NO3)

Formation of NH₄[Hg₃(NH)₂](NO₃)₃ and Transformation to [Hg₂N](NO₃) NH₄[Hg₃(NH)₂](NO₃)₃ ( 1 ) and [Hg₂N](NO₃) ( 2 ) are obtained from conc. aqueous ammonia solutions of Hg(NO₃)₂ at ambient temperature and under hydrothermal conditions at 180 °C, respectively, as colourless and dark yellow to light brown single crystals. The crystal structures {NH₄[Hg₃(NH)₂](NO₃)₃: cubic, P4₁32, a = 1030.4(2) pm, Z = 4, R_all = 0.028; [Hg₂N](NO₃): tetra gonal, P4₃2₁2, a = 1540.4(1), c = 909.8(1) pm, Z = 4, R_all = 0.054} have been determined from single crystal data. Both exhibit network type structures in which [HNHg₃] and [NHg₄] tetrahedra of the partial structures of 1 and 2 are connected via three and four vertices, respectively. 1 transforms at about 270 °C in a straightforward reaction to 2 whereby the decomposition products of NH₄NO₃ are set free. 2 decomposes at about 380 °C forming yellow HgO. Most certainly, 1 is identical with a mineral previously analyzed as “Hg(NH₂)(NO₃)” with the same Hg:N:O ratio.     

Die Kristallstrukturen von (NBu4)[(Ph3Sn)3(MoO4)2] und (NBu4)[(Ph3Sn)3(MoO4)2]·CH3CN: Organozinnmolybdate mit neuartigen 3D‐Netzwerken

The Crystal Structures of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]·CH₃CN: Organotin Molybdates with Novel 3D Networks The reaction of (NBu₄)₂[Mo₆O₁₉] with Ph₃SnCl and NBu₄OH in acetonitrile as solvent leads to the formation of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] ( 5 ). 5 and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]· CH₃CN 6 have been characterized by single crystal structure analysis at 220 K. 5 crystallizes monoclinic with a = 1429.5(4) pm, b = 2292.2(3) pm, c = 2269.7(5) pm, β = 107.42(3)°, space group Cc, 6 crystallizes orthorhombic with a = 1820.5(1) pm, b = 1848.6(2) pm and c = 2143.9(1) pm, space group P2₁2₁2₁. The crystal structures of 5 and 6 consist of isolated (NBu₄)⁺ cations and anionic 3D networks of Ph₃SnO₂ trigonal bipyramides and MoO₄ tetrahedra which are linked by common oxygen atoms.     

Synthese von 3-desoxy-3-amino-vitamin D3 und 3-desoxy-3-epiamino-vitamin D3 und D2

Vitamin D₂ and D₃ are transformed with triphenylphosphane-diethylazodicarboxylate-HN₃ into the epimeric azidoderivatives 1 and 3 with inversion of the configuration at C-3. Reduction with LiAlH₄ yields 3-desoxy-3-epiamino-vitamin D₂ and D₃2 and 4, which are characterized as their acetamides 2a and 4a. Furthermore epivitamin D₃-p-nitrobenzoate 5 is produced by reaction of vitamin D₃ with triphenyl- phosphanediethylazodicarboxylate-p-nitrobenzoic acid, which yields epivitamin D₃5a after saponification. Utilizing the same method as above leads with epivitamin D₃ to 5a 3-desoxy-3-azidovitamin D₃6, which is reduced to 3-desoxy-3-amino-vitamin D₃7 by LiAlH₄ and characterized as its acetamide 7a.     

Polythermal section Sn4P3-Sn4As3

The T-x diagram of the polythermal section Sn₄P₃-Sn₄As₃ of the Sn-P-As system was constructed using the results of X-ray powder diffraction and differential thermal analyses. A continuous series of solid solutions (Sn₄P₃) _x (Sn₄As₃)_{1 ? x} was found to exist. The section is not quasi-binary; in a Sn₄As₃-rich region, this section intersects the peritectic part of the three-phase volume (L + SnAs + α) of the ternary diagram.