Zur solvensfreien Darstellung von Tetramethylammoniumsalzen: Synthese und Charakterisierung von [N(CH3)4]2[C2O4], [N(CH3)4][CO3(CH3)], [N(CH3)4][NO2], [N(CH3)4][CO2H] und [N(CH3)4][O2C(CH2)2CO2(CH3)]

Solvent-free Synthesis of Tetramethylammonium Salts: Synthesis and Characterization of [N(CH₃)₄]₂[C₂O₄], [N(CH₃)₄][CO₃CH₃], [N(CH₃)₄][NO₂], [N(CH₃)₄][CO₂H], and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] A general procedure to synthesize tetramethylammonium salts is presented. Several tetramethylammonium salts were prepared in a crystalline state by solvent-free reaction of trimethylamine and different methyl compounds at mild conditions: [N(CH₃)₄]₂[C₂O₄] (cubic; a = 1 114.8(3) pm), [N(CH₃)₄][CO₃CH₃] (P2₁/n; a = 813.64(3), b = 953.36(3), c = 1 131.3(4) pm, β = 90.03(1)°), [N(CH₃)₄][NO₂] (Pmmn; a = 821.2(4), b = 746.5(3), c = 551.5(2) pm), [N(CH₃)₄][CO₂H] (Pmmn; a = 792.8(7), b = 791.7(3), c = 563.3(4) pm) and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] (P2₁; a = 731.1(2), b = 826.4(3), c = 1 025.2(3) pm, β = 110.1(1)°). The tetramethylammonium salts were characterized by IR-spectroscopy and X-ray diffraction. The crystal structures of the methylcarbonate and the nitrite are described.     

Synthese und Kristallstruktur des tetrameren Nitridokomplexes [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2]

Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH₃CN)₄]₂[W₄N₄Cl₁₄(CH₃CN)₂] . The title compound has been prepared by the reaction of CuCl with WNCl₃ in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH₃CN)₄]⁺ ions, which are arranged to form strands, and of anions [W₄N₄Cl₁₄(CH₃CN)₂]^2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.     

ChemInform Abstract: Crystal Structures and Vibrational Spectroscopy of [NBu4][Cu(CN)X] (X: Br,I) and [NBu4][Cu3(CN)4]×CH3CN.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Die Kristallstrukturen von (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN und [ReCl4(18-Krone-6)]

The Crystal Structures of (NH₄)₂[ReCl₆], [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN and [ReCl₄(18)(Crown-6)] Brown single crystals of (NH₄)₂[ReCl₆] are formed by the reaction of NH₄Cl with ReCl₅ in a suspension of diethylether. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN crystallizes as brown crystal plates from a solution of ReCl₅ in acetonitrile. Lustrous green single crystals of [ReCl₄(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl₅ in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH₄)₂[ReCl₆]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH₄)₂[PtCl₆] type, the Re? Cl distance is 235.5(1) pm. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl₂(CH₃CN)₄]⁺ ions with trans chlorine atoms, [ReCl₆]^2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl₄(18-crown-6)]: Space group P2₁/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.     

4-Methyl-1,2,3,5-dithiadiazoliumsalze Die Kristallstrukturen von (CH3CN2S2)5[CoCl4]Cl3 und (CH3CN2S2)Cl

4-Methyl-1,2,3,5-dithiadiazolium Salts. Crystal Structures of(CH₃CN₂S₂)₅[CoCl₄]Cl₃ and (CH₃CN₂S₂)Cl 4-Methyl-1,2,3,5-dithiadiazolium tetrachlorocobaltate trichloride, (CH₃CN₂S₂)₅[CoCl₄]Cl₃, was obtained by reaction of trithiazyl chloride, (NSCl)₃, with CoCl₂ in acetonitrile; it forms brown, moisture sensitive crystals. With tetraphenylarsonium chloride in CH₂Cl₂ it yields yellow crystalline (CH₃CN₂S₂)Cl and (AsPh₄)₂CoCl₄. The IR spectra of the title compounds are reported and assigned. Theit crystal structures were determined by X-ray diffraction. Crystal data: (CH₃CN₂S₂)₅[CoCl₄]Cl₃, orthorhombic, P2₁2₁2₁, Z = 4, a = 830, b = 1603, c = 2443 pm at 180 K (structure determination with 1787 observed independent reflexions, R = 0.070); (CH₃CN₂S₂)Cl, triclinic, P2₁2₁2₁, Z = 4, a = 749, b = 819, c = 1015 pm, α = 84.9, β = 67.4, γ = 84.6° at 296 K (2653 reflexions, R = 0.040). Both compounds are ionic, having chloride and distorted tetrahedral CoCl₄^2? anions and planar 4-methyl-1,2,3,5-dithiadiazolium cations which nearly fulfill C_2v symmetry. The (CH₃CN₂S₂)₅[CoCl₄]Cl₃ structure contains five symmetry independent cations, (CH₃CN₂Cl has two symmetry independent cations, all being nearly equal. No nitrogen atom but all sulfur atoms of the cations have contact with three to five chlorine atoms, and as a rule there is one chloride ion which is coplanar with the cation and exhibits rather short distances to both S atoms (288 to 309 pm); therefore, the positive charge of the cations must be concentrated on the sulfur atoms.     

Synthesis, structure, and magnetic properties of [(CH3CN)5V-O-V(CH3CN)5][BF4]4

The reaction of vanadium(III) acetylacetonate with HBF4 in acetonitrile yields [(CH3CN)5V-O-V(CH3CN)5][BF4]4, a material that serves as a convenient precursor to other [V-O-V]4+ species such as [(bipy)2(CH3CN)V-O-V(CH3CN)(bipy)2][BF4]4 (bipy=2,2'-bipyridine). Single-crystal X-ray diffraction shows that the V-O-V linkage of [(CH3CN)5V-O-V(CH3CN)5]4+ is linear. An Evans method measurement of the solution-phase magnetic susceptibility indicates strong ferromagnetic coupling between the vanadium centers. Magnetic susceptibility (chi) and magnetization (M(H)) data for a powdered sample and for a single crystal oriented with its V-O-V axis parallel to the applied field were measured over 1.8-300 K. The results suggest that the V(III) centers are ferromagnetically coupled with J approximately 72 K (approximately 50 cm(-1)) yielding a ground state with a total spin Stotal=2. Theoretical fit to the M(H) plot for the single crystal yielded g||=2.01+/-0.01 and the zero-field splitting parameter D=0.60+/-0.04 K (0.42+/-0.03 cm(-1)). EPR measurements at 34 and 101.6 GHz are consistent with the Stotal=2 ground state and yield g||=1.9825, g perpendicular=1.9725 and D=0.57+/-0.03 K.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Structural organization and thermal behavior of the heteropolynuclear complex [Au2{S2CN(CH3)2}4][ZnCl4] and the heterovalent complex ([Au{S2CN(CH3)2}2][AuCl2]) n obtained in the chemisorption system [Zn2{S2CN(CH3)2}4]-Au3+/2 M HCl

Reactions of freshly precipitated binuclear zinc dimethyldithiocarbamate with [AuCl₄]^? anions in 2 M HCl were studied. The heteropolynuclear complex [Au₂{S₂CN(CH₃)₂}₄][ZnCl₄] (I) and the polymeric heterovalent complex ([Au{S₂CN(CH₃)₂}₂][AuCl₂]) _n (II) were preparatively isolated from the chemisorption system [Zn₂{S₂CN(CH₃)₂}₄]-Au³⁺/2 M HCl. The products were characterized by ¹³C MAS NMR data and by X-ray diffraction determination of crystal and molecular structures. The principal structural units of compounds I and II are the tetragonal planar complex cations [Au{S₂CN(CH₃)₂}₂]⁺ (in which the complex-forming ion coordinates two MDtc ligands in the S,S′-bidentate mode) and the anions, namely, the distorted tetrahedral anion [ZnCl₄]^2? in I and the linear [AuCl₂]^? anion in II. The further structural self-organization of complexes at the supramoleular level occurs through relatively weak secondary bonds Au?S and Au?Cl. The chemisorption capacities of zinc dimethyldithiocarbamate calculated from gold(III)-binding reactions are 644.1 and 1288.2 mg of gold per gram of the sorbent. Simultaneous thermal analysis studies of the thermal behavior of I and II were used to elucidate the conditions of gold recovery.     

Synthese und Strukturuntersuchungen von Iodocupraten(I). XV Iodocuprate(I) mit solvatisierten Kationen: [Li(CH3CN)4][Cu2I3] und [Mg{(CH3)2CO}6][Cu2I4]

Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH₃CN)₄] [Cu₂I₃] and [Mg{(CH₃)₂CO}₆][Cu₂I₄] [Li(CH₃CN)₄][Cu₂I₃] 1 and [Mg((CH₃)₂CO)₆][Cu₂I₄] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI₂ in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH₃CN)₄]⁺ cations are located between rod packings of CuI₄ tetrahedra double chains [(CuI_2/2I_2/4)₂]^? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P2₁/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH₃)₂CO)₆]²⁺ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu₂I₄]^2? occupy holes in the trigonal prismatic channels formed by the cations.     

配合物[Fe(OPPh3)4Cl2][FeCl4]的合成和晶体结构

亚砜（R2SO4）是四价有机硫化合物中最重要的一类化合物,它的还原产物R2S可作为配体与过渡金属离子配位,从而得到许多结构新颖的化合物。这类反应一般在金属离子Os^11、Ru^11、Pt^11和Re^Vi等存在下发生,但很少出现在Fe^Ⅲ离子上。本文首次利用FeCl3、PPh3和DMSO反应,得到标题配合物并测定了其晶体结构。     

Synthesis and Structure of Tetra(para-tolyl)antimony Dicyanodiiodoaurate [p-Tol4Sb][Au(CN)2I2] and Alkyltriphenylphosphonium Dicyanodiiodoaurates [Ph3PAlk][Au(CN)2I2], Alk = Me,CH2CN

Russian Journal of Coordination Chemistry - Red-colored crystalline gold complexes [p-Tol4Sb][Au(CN)2I2] (I), [Ph3PMe][Au(CN)2I2] (II), and [Ph3PCH2CN][Au(CN)2I2] (III) were synthesized by the...     

Attempted Abstraction of the Halogenides in (HNEt3)[Re(CH3CN)2Cl4] and Crystal Structures of cis‐[Re(CH3CN)2Cl4]·CH3CN and cis‐[Re(NHC(OCH3)CH3)2Cl4]

The abstraction of the halogenide ligands in [Re(CH₃CN)₂Cl₄]^? should result in a solvent‐only stabilized Re^III complex. The reactions of salts of [Re(CH₃CN)₂Cl₄]^? with silver(I) and thallium(I) salts were investigated and the solid‐state structures of cis‐[Re(CH₃CN)₂Cl₄]·CH₃CN and cis‐[Re(NHC(OCH₃)CH₃)₂Cl₄] are described.     

New linear tricobalt complex of di(2-pyridyl)amide (dpa), [Co3(dpa)4(CH3CN)2][PF6]2

Reaction of the linear tricobalt compound Co3(dpa)4Cl2 (1) (dpa = di(2-pyridyl)amide) with silver hexafluorophosphate in acetonitrile yields [Co3(dpa)4(CH3CN)2][PF6]2 (2). Two crystalline forms are obtained from the same solution, namely, a monoclinic (P2(1)) form 2xCH3CNx2Et2O and a triclinic (P1) form, 2x3CH3CN. The tricobalt units in both crystals are essentially symmetrical, though this is not required by crystal symmetry, with Co-Co distances in the range 2298-2304 A. Each of the two terminal Co atoms is coordinated to an acetonitrile molecule with Co-N distances in the range 2068-2111 A at 213 K. The spiral arrangement of ligands gives an overall idealized D4 point group symmetry for the cation [Co3(dpa)4(CH3CN)2]2+ . Chiral crystals of both delta and lambda configurations in the P2(1) form have been isolated. The absolute configurations were determined by X-ray crystallography and their mirror-image circular dichroism spectra measured. The D4 symmetry of the cation appears to be preserved in solution as judged by the presence of only five proton resonance signals in the 1H NMR spectrum. Magnetic susceptibility measurements in the solid state indicates that 2 has a doublet ground state and exhibits an increase of the effective moment at high temperature (approximately 160 K) due to a spin crossover process.     

1-D and 2-D homoleptic dicyanamide structures, [Ph4P]2[CoII[N(CN)2]4] and [Ph4P][M[N(CN)2]3] (M = Mn, Co)

The homoleptic complexes [Ph(4)P](2)[Co[N(CN)(2)](4)] and [Ph(4)P][M[N(CN)(2)](3)] [M = Co, Mn] have been structurally as well as magnetically characterized. The complexes containing [M[N(CN)(2)](4)](2-) form 1-D chains, which are bridged via a common dicyanamide ligand in [M[N(CN)(2)](3)](-) to form a 2-D structure. The five-atom [NCNCN](-) bridging ligands lead to weak magnetic coupling along a chain. The six [NCNCN](-) ligands lead to a (4)T(1g) ground state for Co(II) which has an unquenched spin-orbit coupling that is reflected in the magnetic properties. Long-range magnetic ordering was not observed in any of these materials.     

Tetracyanometallates with Complex Dien Cations: [Ni(dien)2][Ni(CN)4]·2H2O and [Ni(dien)2][Pd(CN)4]

The crystal structures of two square tetracyanocomplexes were determined. [Ni(dien)₂][Ni(CN)₄]·2H₂O (NDNCH) and [Ni‐(dien)₂][Pd(CN)₄] (NDPC) (dien = diethylene triamine) exhibit ionic structures consisting of mer‐[Ni(dien)₂]²⁺ cations and [Ni(CN)₄]^2‐ or [Pd(CN)₄]^2‐ anions, respectively. Moreover, the structure of NDNCH is completed by two water molecules of crystallisation. In both compounds hydrogen bonds contribute to the stabilisation of the structure. NDNCH dehydrates on air quickly yielding anhydrous [Ni(dien)₂][Ni(CN)₄] (NDNC). Its thermal decomposition proceeds in a complicated process followed by aerial oxidation of metallic nickel to NiO.