Crystal Structure of Bis (O,O’-diisopropyl dithiophosphate):[(C3H7O)2PS2]2

The crystal and molecular structures of [(C3H7O)2PS2]2 (CCDC No. 217201) were determined by means of X-ray crystallography. It crystallized in a triclinic system with space group P(-1) and lattice parameters a=0.82794(3) nm, b=0.84764(2) nm, c=0.85034(3) nm, α=97.78(3)°, β=110.77(3)°, γ= 94. 95 (3)°,V= 0. 54701(9) nm3, Z= 1. In this molecule, the two diisopropyl dithiophosphate groups, [(C3H7O)2PS2]2,which are parallel to each other, are linked by an S-S bond and there exist inversion centers in the molecule.In the structure, the P = S bonds in the two dithiophosphate units are trans-oriented to each other.     

Crystal Structure of Bis （0, O＇-diisopropyl dithiophosphate） ： [（C3H7O）2PS2]2

The crystal and molecular structures of [(C₃H₇O)₂PS₂]₂ (CCDC No.217201) were determined by means of X-ray crystallography. It crystallized in a triclinic system with space group P-1 and lattice parameters a=0.82794(3) nm, b=0.84764(2) nm, c=0.85034(3) nm, α=97.78(3)°, β=110.77(3)°, γ= 94. 95 (3)°,V= 0. 54701(9) nm³, Z= 1. In this molecule, the two diisopropyl dithiophosphate groups, [(C₃H₇O)₂PS₂]₂,which are parallel to each other, are linked by an S-S bond and there exist inversion centers in the molecule.In the structure, the P＝S bonds in the two dithiophosphate units are trans-oriented to each other.     

Synthese und Eigenschaften von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(halogenophthalocyaninato(2–)ferraten(IV)); Kristallstruktur von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(fluorophthalocyaninato(2–)ferrat(IV))-Trihydrat

Synthesis and Properties of Bis(tetra(n-butyl)ammonium)μ-Carbido-di(halophthalocyaninato(2–)ferrates(IV)); Crystal Structure of Bis(tetra(n-butyl)ammonium) μ-Carbido-di(fluorophthalocyaninato(2–)ferrate(IV)) Trihydrate μ-Carbido-di(pyridinephthalocyaninato(2–)iron(IV)) reacts with tetra(n-butyl)ammonium halide (ⁿBu₄N)X) in solution (X = F) or in a melt (X = Cl, Br) to yield bis(tetra(n-butyl)ammonium μ-carbido-di(halophthalo-cyaninato(2–)ferrat(IV)). The fluoro-complex salt crystallizes as a trihydrate monoclinically in the space group P12₁/n1 with the following cell parameters: a = 15.814(1) Å; b = 22.690(5) Å; c = 25.127(3) Å; β = 98.27(1)°, Z = 4. The Fe atoms are almost in the centre (Ct) of the (N_iso)₄ planes (N_iso: isoindoline-N atom) with a Fe–Ct distance of 0.053(1) Å. The average Fe–N_iso distance is 1.939(4) Å, the Fe–(μ-C) distance 1.687(4) Å and the Fe–F distance 2.033(2) Å. The Fe–(μ-C)–Fe core is linear (179.5(3)°). The pc²-ligands are staggered (φ = 42(1)°) with a convex distortion. The asymmetric Fe–(μ-C)–Fe stretch (in cm^–1) is observed in the IR spectra at 917 (X = F), 918 (Cl) and 920 (Br) and the symmetric Fe–(μ-C)–Fe stretch at 476 cm^–1 in the resonance Raman spectra. The IR active asymmetric Fe–X stretch (in cm^–1) absorbs at 336 (X = F), 203 (Cl), 182 (Br), respectively.     

Ein- und zweikernige MoII-Phthalocyaninate(2–): Darstellung und Eigenschaften von Bis(cyano)phthalocyaninato(2–)molybdat(II) und Bis(phthalocyaninato(2–)molybdän(II))

Mono- and Dinuclear Mo^II Phthalocyaninates(2–): Syntheses and Properties of Bis(cyano)phthalocyaninato(2–)molybdate(II) and Bis(phthalocyaninato(2–)molybdenum(II)) Blue diamagnetic bis(phthalocyaninato(2–)molybdenum(II)) is synthezied by reduction of oxophthalocyaninato(2–)molybdenum(IV) with boiling triphenylphosphine. The Mo–Mo stretching vibration ist observed in the resonance Raman spectrum at 374 cm^–1. It is chemically inert and dissolves in conc. sulfuric acid without decomposition. It reacts with molten tetra(n-butyl)ammonium cyanide to yield redbrown paramagnetic bis[tetra(n-butyl)ammonium] biscyanophthalocyaninato(2–)molybdate(II) (μ_eff = 3.15 μ_B; S = 1). The complex salt is very instable and demetallizes in solution. In the extraordinary UV-VIS-NIR spectrum an intense trip-triplet transition at 7780 cm^–1 together with a very structured B region between 14000 and 21000 cm^–1 of comparable absorbance is observed.     

Über die Darstellung der Bis(triphenylsilyl)-sulfane (C6H5)3Si?Sx?Si(C6H5)3 (x = 3, 4) und die Kristallstruktur von (C6H5)3Si?S4?Si(C6H5)3

On the Preparation of Bis(triphenylsilyl)sulfanes (C₆H₅)₃Si? S_x? Si(C₆H₅)₃ (x = 3, 4) and the Crystal Structure of (C₆H₅)₃Si? S₄? Si(C₆H₅)₃ The preparation of the bis(triphenylsilyl)sulfanes Ph₃Si? S_x? SiPh₃ (x = 3, 4) from Ph₃SiSNa and SCl₂ resp. S₂Cl₂ is reported. They are characterized by vibrational, NMR and UV-VIS spectroscopic measurements. Ph₃Si? S₄? SiPh₃ crystallizes in space group P1 with a = 943.6(6) pm, b = 945.7(5) pm, c = 1 881.7(12) pm, α = 82.11(5)°, β = 78.95(5)°, γ = 83.15(5)° and Z = 2.     

Bis(bis(triphenylphosphin)iminium)-μ-nitrido-bis(azidophthalocyaninato(2–)ferrat(IV))-Triiodid Diethylether-Disolvat: Synthese,Eigenschaften und Kristallstruktur

Bis(bis(triphenylphosphine)iminium) μ-Nitrido-bis(azidophthalocyaninato(2–)ferrate(IV)) Triiodide Diethylether Di-Solvate: Synthesis, Properties, and Crystal Structure Bis(bis(triphenylphosphine)iminium) μ-nitrido-bis(azidophthalocyaninato(2–)ferrate(IV)) triiodide is prepared as a diethylether di-solvate by substitution of μ-nitrido-bis(pyridinephthalocyaninato(2–)iron(IV)) pentaiodide with bis(triphenylphosphine)iminium azide in acetone and precipitation by slow diffusion of diethylether. The doublesalt crystallizes monoclinically in the space group C12/c1 with cell parameters: a = 34.567(9) Å, b = 20.237(9) Å, c = 21.251(5) Å, β = 119.79(2)°; Z = 4. The Fe atoms are located almost in the centre (Ct) of the (N_iso)₄ planes (d(Fe–Ct) = 0.080(1) Å; N_iso: isoindoline N atom). The average Fe–N_iso distance is 1.947(5) Å, the Fe-(μ-N) distance 1.650(1) Å. The Fe-(μ-N)–Fe skeleton is linear (177.4(4)°). Both waving pc^2– ligands are in a staggered conformation (skew angle φ = 38.5(5)°). Fe coordinates linear azide (d(Fe–N_azide) = 2.152(7) Å) with an angle of 121.2(6)°. The isolated triiodide ion is almost linear (d(I–I) = 2.936(2) Å). The PNP cation obtains an hybrid conformation (∠(P–N–P) = 157.4(2)°). The asymmetrical Fe-(μ-N)–Fe stretching vibration is observed in the IR spectrum at 997 cm^–1, the symmetrical one is selectively enhanced in the resonance Raman (RR) spectrum at 478 cm^–1. The corresponding I–I stretching vibrations of the triiodide ion are present in the actual spectra at 134 (IR) and 115 cm^–1 (RR). An IR band at 334 cm^–1 is attributed to the asymmetrical Fe–N_azide stretching vibration.     

Ba2[Pd(HS2O7)2(S3O10)2]: A Heteroleptic Polysulfatopalladate

The oxidation of elemental palladium with oleum (65 % SO₃) in the presence of barium carbonate in torch‐sealed glass ampoules at 180 °C leads to yellow single crystals of the heteroleptic palladate Ba₂[Pd(HS₂O₇)₂(S₃O₁₀)₂] (triclinic, P ; Z=1; a=884.18(3), b=927.68(3), c=938.77(4) pm; α=60.473(1), β=80.266(2), γ=87.746(2)°). The crystal structure shows the Pd²⁺ ions in a square‐planar coordination of oxygen atoms of two hydrogendisulfate as well as of two trisulfate anions. The compound is the first example of the rarely seen S₃O₁₀^2? and HS₂O₇^? anions acting as ligands in a complex anion and, moreover, the first heteroleptic polysulfatometallate known so far. The complex formation leads to a stabilization of the trisulfate anion relative to its uncoordinated congener. Ba₂[Pd(HS₂O₇)₂(S₃O₁₀)₂] has been further characterized by vibrational spectroscopy and quantum chemical calculations. Thermal analyses by means of thermogravimetric/differential thermal analysis (TG/DTA) measurements show that the compound decomposes to yield elemental palladium and BaSO₄.     

Bis(phthalocyaninato(2–)rhenium(II)): Synthesis,Properties, and Crystal Structure

Blue, paramagnetic bis(phthalocyaninato(2–)rhenium(II)) (μ_eff = 0,88 μ_B, per Re, at 300 K) is prepared by thermal decomposition of trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), in boiling triphenylphosphine. It crystallizes in the triclinic space group P 1 with cell parameters as follows: a = 7.799(3) Å, b = 12.563(7) Å, c = 12.69(1) Å, α = 89.97(5)°, β = 94.14(5)°, γ = 106.39(4)°; Z = 1. Two cofacial phthalocyaninates are bonded together by a Re–Re bond with a Re–Re distance of 2.285(2) Å. The Re atoms are located distinctly outside the centre of the (N_iso)₄ planes by 0.426(3) Å. The Re–N_iso distance varies from 1.99(1) to 2.04(1) Å (average 2.02 Å). The pc^2– ligands are in an eclipsed conformation and concavely distorted. In the UV-VIS-NIR spectrum the B region is split into two bands of comparable intensity due to strong excitonic coupling. The Re–Re stretching vibration at 240 cm^–1 is selectively enhanced in the resonance Raman spectrum (λ_exc = 488 nm).     

Formation and structural characterization of mercury complexes from Te(R)CH2SiMe3 (R = Ph, CH2SiMe3) and HgCl2

The reaction of HgCl₂ and Te(R)CH₂SiMe₃ [R = CH₂SiMe₃ (1), Ph (2)] in ethanol yielded a mononuclear complex [HgCl₂{Te(R)CH₂SiMe₃}₂] (R = Ph, 3a; R = CH₂SiMe₃, 3b). The recrystallization of 3a or 3b from CH₂Cl₂ produced a dinuclear complex [Hg₂Cl₂(μ-Cl)₂{Te(R)CH₂SiMe₃}₂] (R = Ph, 4a; R = CH₂SiMe₃, 4b). When 3a was dissolved in CH₂Cl₂, the solvent quickly removed, and the solid recrystallized from EtOH, a stable ionic [HgCl{Te(Ph)CH₂SiMe₃}₃]Cl·2EtOH (5a·2EtOH) was obtained. Crystals of [HgCl₂{Te(CH₂SiMe)₂}]·2HgCl₂·CH₂Cl₂ (6b·2HgCl₂·CH₂Cl₂) were obtained from the CH₂Cl₂ solution of 3b upon prolonged standing. The complex formation was monitored by ¹²⁵Te-, and ¹⁹⁹Hg NMR spectroscopy, and the crystal structures of the complexes were determined by single crystal X-ray crystallography.     

Synthesis,Characterization and X-ray Crystal Structure of 2-Methylpropan-2-aminium Methyl ((4-Fluorobenzamido)(4-fluorophenyl)methyl) phosphonate·H_2O

A new crystal of 2-methylpropan-2-aminium methyl((4-fluorobenzamido)(4-fluorophenyl)methyl)phosphonate has been prepared at room temperature and characterized by 1HNMR, 13 C NMR, IR, MS, elemental analysis and X-ray single-crystal determination. The compound crystallizes in monoclinic space group C2/c with a = 20.719(2), b = 11.8559(13), c = 18.176(2) A, β = 94.434(2)°, V = 4451.4(9) A3, Dc = 1.317 Mg/m3, Z = 8, F(000) = 1864 and μ = 0.174 mm-1. The crystal packing is stabilized by intermolecular N–H···O and O–H···O hydrogen bonds, as well as by weak π-π stacking interactions.     

Chemie polyfunktioneller Moleküle. 124. Silber(I)-Komplexe mit den Liganden Bis(diphenylphosphanyl)amin, -amid und Tris(diphenylphosphanyl)amin

Chemistry of Polyfunctional Molecules. 124. Silver(I) Complexes Containing the Ligands Bis(diphenylphosphanyl)amine, -amide and Tris(diphenylphosphanyl)amine Bis(diphenylphosphanyl)amine HN(PPh₂)₂ ( 1 ) reacts with AgCl to the complex HN(PPh₂AgCl)₂ ( 5 ) for which in the solid state the cluster structure Ag₄Cl₄[HN(PPh₂)₂]₂ is assumed. Reaction of 5 with LiN(PPh₂)₂ ( 2 ) gives the known [N(PPh₂AgPh₂P)₂N] ( 8 ) and the new complex [Ag(μ—Ph₂PNPPh₂)₂(μ—Ph₂PNHPPh₂)Ag] · dioxane ( 7 · dioxane). The compound 7 · dioxane has been characterized by X-ray diffraction. The molecules are found to contain a bicyclo[3.3.3]undecane-type structure with trigonal planar coordinated silver atoms, which are separated by 281,6(1) pm. The dioxane is bound via H-bridge bond to the NH group of the coordinated HN(PPh₂)₂. Treatment of 8 with ClPPh₂ yields N(PPh₂AgCl)₃ ( 12 ), which has also been obtained by the reaction of N(PPh₂)₃ ( 3 ) with silver chloride. All the compounds have been characterized, so far as possible, by IR, Raman, ¹H NMR, ³¹P{¹H} NMR, ¹³C{¹H} NMR and mass spectroscopy.     

Crystal and molecular structure of Dicyanotetrasulfane S4(CN)2

S₄(CN)₂ crystallizes in the monoclinic space group P2₁/c with a = 885.7 pm, b = 794.2 pm, c = 1032.6 pm, β = 109.0° (at 173 K). The molecules occupy general sites but are of approximate C₂ symmetry. The conformation of the molecules is all-trans with torsional angles CSSS = 74.6° and 81.7° and SSSS = 84.8°. The central SS bond (201.7 pm) is much shorter than the terminal SS bonds (av. 206.8 pm). There are no stronger than van-der-Waals type intermolecular interactions.     

原位X射线衍射研究VOx和MoOx在Al2O3上的分散

 采用原位X射线衍射技术考察了机械研磨法和浸渍法制备的负载型VOx(MoOx)/Al2O3催化剂在空气中升温时的晶相变化. 结果表明,采用草酸络合浸渍法制备的VOx/Al2O3催化剂上前驱体(NH4)2［VO(C2O4)2］分散均匀,在升温至200～300 ℃时前驱体开始分解, 300～400 ℃是主要分解区间,到400 ℃时分解完全; VOx物种是通过晶相HxV2O5进行分散的. 机械研磨法制备的VOx/Al2O3催化剂在升温过程中虽然VOx与Al2O3之间存在相互作用,但并没有观察到明显的自发分散现象, V2O5一直以晶体氧化物形式存在. 在空气中升温至400 ℃时,浸渍法制备的MoOx/Al2O3催化剂上(NH4)6Mo2O24·4H2O已完全分解成MoO3. 机械研磨法制备的MoOx/Al2O3在加热过程中分解生成的MoO3与浸渍法得到的MoO3不完全相同,主要体现在(040)和(060)晶面的含量不同; 机械研磨法制得的催化剂在500 ℃下焙烧1 h的分散度小于浸渍法制备的催化剂.     

Complexation of (carbamoylmethyl)diphenylphosphine sulfide with silver nitrate. The structure of the polymeric complex [Ag2{Ph2P(S)CH2C(O)NH2}2(NO3)2] n

The reaction of (carbamoylmethyl)diphenylphosphine sulfide with AgNO₃ yields the polymeric complex [Ag₂{Ph₂P(S)CH₂C(O)NH₂}₂(NO₃)₂] _n . Its structure was established by X-ray diffraction analysis. The coordination environments about both Ag⁺ cations are formed by five donor atoms, two of which are bonded to the metal atom substantially more weakly than the remaining three atoms. The compositions of the coordination polyhedra are different: ({AgSO′(C)O(N)O₂(N′)} and {AgS′ SO(C)O₂(N)}). The coordinated ligands differ in their functions: one ligand chelates the metal cation and its sulfur atom is additionally bonded to the second cation, while the second ligand acts as a bridge between the two different cations. The structure of the complex and the character of the interaction between the ligand and AgNO₃ are substantially affected by the network of hydrogen bonds. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 838–845, April, 1997.     

Synthesen und Schwingungsspektren der homoleptischen Acetonitrilkomplex-Kationen [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+ und des Adduktes CH3CN · SbF5. Kristallstrukturen der Salze [M(NCCH3)4][SbF6]2 · CH3CN,M = Pd,Pt

The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH₃)₂]⁺, [Pd(NCCH₃)₄]²⁺, [Pt(NCCH₃)₄]²⁺, and the Adduct CH₃CN · SbF₅. The Crystal and Molecular Structures of [M(NCCH₃)₄][SbF₆]₂ · CH₃CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)₄][Sb₂F₁₁]₂, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb₂F₁₁]^– into [SbF₆]^– and the molecular adduct CH₃CN · SbF₅ according to: [M(CO)₄][Sb₂F₁₁]₂ + 7 CH₃CN → [M(NCCH₃)₄][SbF₆]₂ · CH₃CN + 2 CH₃CN · SbF₅ + 4 CO M = Pd, Pt The monosolvated [M(NCCH₃)₄][SbF₆]₂ · CH₃CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH₃)₂][SbF₆] and the adduct CH₃CN · SbF₅ are completely characterized by vibrational spectroscopy.     

Syntheses and Crystal Structures of （PySe）2 and Bi2（PySe）6（HPySe=2-Pyridineselenol N-Oxide）

The title compounds(PySe)2 1(HPySe=2-pyridineselenol N-oxide,(PySe)2= bis(2-pyridine-N-oxide) diselenide) and Bi2(PySe)6 2 were prepared by the reaction of 2-bromine-N-oxide with NaHSe and Bi(NO3)3·5H2O with HPySe,and the crystal structure of 2 was studied.Compound 2 crystallizes in the monoclinic space group P21/n with a=9.840(2),b=10.204(2),c=18.395(2),β=102.926(2)°,V=1800.0(5)3,Dc=2.2687 g/cm3,Z=2,the final R=0.0319 and wR=0.0646.The Bi atoms are coordinated by four selenium and four oxygen atoms from four PySe ligands to form a slightly distorted four-column geometry.     

Ammonothermal Synthesis,X-Ray and Time-of-Flight Neutron Crystal-Structure Determination,and Vibrational Properties of Barium Guanidinate,Ba(CN3H4)2

We report the crystal structure of Ba(CN₃H₄)₂ as synthesized from liquid ammonia. Structure solution based on X-ray diffraction data suffers from a severe pseudo-tetragonal problem due to extreme scattering contrast, so the true monoclinic symmetry is detectable only from neutron powder diffraction patterns, and structure solution and refinement was greatly aided by density-functional theory. The symmetry lowering is due to slight deviations of the guanidinate anion from the mirror plane in space group P b2, a necessity of hydrogen bonding. At 300 K, barium guanidinate crystallizes in P2₁/c with a=6.26439(2) Å, b=16.58527(5) Å, c=6.25960(2) Å, and a monoclinic angle of β=90.000(1)°. To improve the data-to-parameter ratio, anisotropic displacement parameters from first-principles theory were incorporated in the neutron refinement. Given the correct structural model, the positional parameters of the heavy atoms were also refinable from X-ray diffraction of a twinned crystal. The two independent guanidinate anions adopt the all-trans- and the anti-shape. The Ba cation is coordinated by eight imino nitrogens in a square antiprism with Ba−N contacts between 2.81 and 3.04 Å. The IR and Raman spectra of barium guanidinate were compared with DFT-calculated phonon spectra to identify the vibrational modes.     

Br3In · NH2Si(CH3)3 – ein stabiles Addukt des instabilen Trimethylsilylamins

Br₃In · NH₂Si(CH₃)₃ – a Stable Adduct of the Unstable Trimethylsilylamine Heating a solution of indium tribromide in bis(trimethylsilyl)amine at about 55 °C for 30 to 35 hours the two adducts Br₃In · NH₂SiMe₃ and Br₃In · NH(SiMe₃)₂ are formed in a 3 : 1 molar ratio. Both compounds have been characterized by NMR, IR and Raman spectra; the X-ray structure determination of the title compound is reported.