Synthesis and crystal structures of Cd[AlCl4]2 and Cd2[AlCl4]2

Colorless single crystals of Cd[AlCl₄]₂ grow from the melt of CdCl₂ and AlCl₃ upon slow cooling from 250°C. The crystal structure [monoclinic, P1a1, Z = 2, a = 1288.7(2), b = 660.2(1), c = 705.1(1) pm, β = 92.89(1)º] may be derived from hexagonally closest packed layers of Cl^?. Octahedral and tetrahedral holes are filled with Cd²⁺ and Al³⁺ in a 1:2 ratio between all layers stacked in the [104] direction. Cd[GaCl₄]₂ and Cd[AlBr₄]₂ are isotypic. Reduction of Cd[AlCl₄]₂ with excess cadmium shot and slow cooling from 350°C yields plate-like very moisture-sensitive, colorless single crystals of Cd₂[AlCl₄]₂. The crystal structure [triclinic, C1 , Z = 2, a = 655.47(3), b = 1135.26(1), c = 935.23(6) pm, α = 89.70(2)º, β = 103.61(1)º, γ = 90.455(1)º] is built from slabs stacked in the [100] direction consisting of ethane-like [Cd₂Cl₆] units with a Cd? Cd distance of 256.1 pm sharing common vertices with [AlCl₄] tetrahedra.     

Structures and conductivities of isostructural synthetic metals (DOET)4[Hg2Cl6] and (DOET)4[Hg2Br6]

The structures of organic metals (DOET)₄[Hg₂Cl₆] (1) and (DOET)₄[Hg₂Br₆] (2), where DOET is (1,4-dioxanediyl-2,3-dithio)ethylenedithiotetrathiafulvalene, were established by X-ray diffraction analysis. Compounds 1 and 2 are isostructural, and their crystals have layered structures. The conducting layers formed by the stacked DOET^1/2+ cations alternate with the layers of the [Hg₂X₆]^2– anions (X = Cl, Br). The temperature dependence of the conductivity of salt 1 shows a metallic character in the range of 300—4 K. Compound 2 undergoes the metal—semiconductor phase transition (T_M—I) at 100 K.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Crystal-chemical functions of [Hg2]2+ and [Hg3]4+ groups in inorganic structures

About 20 structures of natural and synthetic inorganic compounds containing a [H_g2] (dumbbell) pair (Hg-Hg = 2.47?2.56 å) or a [H_g3] triangle (Hg-Hg_av = 2.7 å) are analyzed. From crystal-chemical viewpoint, it is reasonable to consider these groups as a single cation with coordinates of its geometrical center. In all cases, the coordination polvhedra are convex polxhedra with 8–14 vertices and with distances from the center to the vertex of 3.00?3.91 å, which makes the [H_g2]²⁺ and [Hg3]⁴⁺ cations analogs of Cs. Examples are given to demonstrate the advantages of the suggested analysis of structures with a [Hg_n] group. This approach extends classical crystal chemistry to compounds with nonuniform chemical bonds, in particular, to compounds with pseudocluster and cluster groups inserted in the ionic structure; therefore, it is especially useful for comparison and classification purposes and for analysis of structure-foming factors.     

Cu3AlCl6 und Cu2Al2Cl8, die Gaskomplexe im System CuCl/Al2Cl6

Cu₃AlCl₆ and Cu₂Al₂Cl₈, Gas Complexes in the System CuCl/Al₂Cl₆ Investigations by mass spectroscopy in the system CuCl_s/Al₂Cl_6,gestablished that only Cu₃AlCl₆ and Cu₂Al₂Cl₈ are observed as principal gas complexes. Results of flow measurements published by LAUGHLIN and Gregory (1976) which were attributed erroneously by these authors to the complex CuAlCl₄ may be described by the equilibria given in “Inhaltsübersicht”. The complexes cu₃AlCl₆ and Cu₂Al₂Cl₈ are supposed to have a cube type structure similar to Cu₄Cl₄.     

Aromatic superclusters from all-metal aromatic and antiaromatic monomers, [Al4]2- and [Al4]4-

Calculations on the structures of dimers of all-metal aromatic and anti-aromatic molecules such as (Al4(2-)) and (Al4(4-)) reveal that, unlike their organic counterparts such as benzene and cyclobutadiene which form pi-stacked complexes, these molecules form new clusters with no reminiscence of the original units. These clusters have a very large binding energy and can be further stabilized through charge-balance by counterions and solvents.     

Crystal structures of the organic metals (ET)2[Hg(SCN)Cl2] and (ET)2[Hg(SCN)2Br]

The compositions and structures of two new organic metals based on ET [where ET = bis(ethylenedithio)tetrathiafulvalene], viz., (ET)₂[Hg(SCN)Cl₂], with a metal-dielectric transition temperature (T_m-d) of 35°K, and (ET)₂[Hg(SCN)₂Br], with T_m-d = 140°K, were established by x-ray diffraction analysis. The crystal structures of the investigated compounds are similar to the structure of the previously studied organic metal (ET)₂[Hg(SCN)₂Cl] with T_m-d = 50°K. The principal crystallographic data for (ET)₂[Hg(SCN)Cl₂] are as follows: a = 36.64(1), b = 8.300(4), c = 11.798(1) Å, = 89.91(3)°, V = 3588.1(9) ų, space group Cc, Z = 4, d_calc = 2.05 g/cm³. The principal crystallographic data for (ET)₂[Hg(SCN)₂Br] are as follows: a = 37.088(14), b = 8.338(3), c = 11.738(5) Å, = 89.71(3)°, V = 3629.6(8) ų, space group C2/c, Z = 8, d_calc = 2.15 g/cm³. A characteristic feature of the crystal structure of the investigated compounds is alternation of the anion and cation layers along the a axis of the crystal. In the cation layer of the k type the ET are interconnected by shortened S...S intermolecular contacts (3.39–3.58 Å). The [Hg(SCN)_3–nX_n]^– anions (X = Cl, Br; n = 1, 2) form polymeric chains with one or two bridged SCN groups. A tendency for a decrease in the metal-dielectric transition temperature with a decrease in the volume of the anion is detected in the (ET)₂[Hg(SCN)_3–nX_n] salts, where X = Cl and Br, and n = 1 and 2.Institute of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2323–2331, October, 1992.     

Darstellung von trans-[Mo6Cl8]Cl4Br22−ausgehend von kristallisierten [Mo6Cl8]Cl4(H2O)2 und die Kristallstruktur von [(C6H5)4As]2[Mo6Cl8]Cl4Br2

Preparation of trans-[Mo₆Cl₈]Cl₄Br₂^2? Starting from Crystalline [Mo₆Cl₈]Cl₄(H₂O)₂ and Crystal Structure of [(C₆H₅)₄As]₂[Mo₆Cl₈]Cl₄Br₂ The synthesis of the title compound is successful if the crystallized [(Mo₆Cl₈)Cl₄(H₂O)₂] containing the H₂O molecules in trans-position reacts with HBr + [(C₆H₅)₄As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo₆Cl₈)Cl₄Br₂]^2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C₆H₅)₄As]₂[(Mo₆Cl₈)Cl₄Br₂] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R₁ = 0.026). The [(Mo₆Cl₈)Cl₄Br₂]^2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo₆Cl₈]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo₆ cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo₆X₈)Y₄] cluster units (X, Y ? Cl, Br).     

Halogenomercurate: Darstellung und Strukturen von [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6] und [Cu(en)2][HgBr4]

Halomercurates: Syntheses and Crystal Structures of [Cu(en)₂][Hg₂Cl₆], [Cu(en)₂][Hg₂Br₆], and [Cu(en)₂][HgBr₄] Crystals of [Cu(en)₂][Hg₂Cl₆] ( 1 ) have been obtained by layering a solution of Hg(NO₃)₂ and NaCl with a solution of [Cu(en)₂]SO₄. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)₂][HgBr₄] ( 3 ). Crystals of [Cu(en)₂][Hg₂Br₆] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl₃ units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr₃ units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr₄]^2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R₁ = 0.040. 2 : Space group P2₁/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R₁ = 0.033. 3 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R₁ = 0.092.     

On Tetrachlorophosphonium Chlorometallates of Rhenium and Molybdenum: Syntheses,Crystal Structures,and Magnetism of [PCl4]2[Re2Cl10] and [PCl4]3[ReCl6]2, and the Magnetic Properties of [PCl4]2[Mo2Cl10]

MoCl₄, ReCl₄, and ReCl₅ react with PCl₅ in sealed glass ampoules at temperatures between 220° and 320° to [PCl₄]₂[Mo₂Cl₁₀] ( 1 ) [PCl₄]₂[Re₂Cl₁₀] ( 2 ), and [PCl₄]₃[ReCl₆]₂ ( 3 ). 2 crystallizes isotypically to the previously reported 1 and the respective titanium and tin containing analogues. The structure (triclinic, P1, Z = 1, a = 897.3(2), b = 946.0(2), c = 687.13(9) pm, α = 95.59(2)°, β = 95.80(2)°, γ = 101.07(2)°, V = 565.4(2) 10⁶ pm³) is built of tetrahedral [PCl₄]⁺ and edge sharing double octahedral [Re₂Cl₁₀]^2– ions and can be derived from a hexagonal closest packing of Cl^– ions with tetrahedral and octahedral holes partially filled by P(V) and Re(IV), respectively. 3 crystallizes isotypically to [PCl₄]₃[PCl₆][MCl₆] (M = Ti, Sn) (tetragonal, P 4₂/mbc, Z = 4, a = 1496.2(1), c = 1363.2(2) pm). Because no evidence was found for the presence of [PCl₆]^– ions, Re in 3 has to be of mixed valency with Re^IV and Re^V sharing the same crystallographic site. The structure can be derived from a cubic closest packing or alternatively from an only sparsely distorted body centered cubic arrangement of Cl^– ions which is rarely found for anion arrays. The tetrahedral and octahedral holes are partially filled by P^V and M^IV/V, respectively. Magnetic measurements show all three compounds to be paramagnetic and confirm the oxidation state IV for Mo and Re in 1 and 2 and the mixed valence (IV/V) for Re in 3 .     

含羰基有机添加剂对AlCl3-[Emim]Cl电沉积铝的影响

以[Emim]Cl/AlCl₃(33.3/66.7 mol%)离子液体为电解质, 选取了丙酮、乙酰胺、乙酸、乙酸甲酯、氨基甲酸甲酯5种含有羰基官能团的有机分子作为添加剂, 讨论其对铝沉积层的影响. 通过CV曲线、SEM、XRD、UV-Vis、NMR等分析, 进一步研究了添加剂对Al沉积层形貌、晶面取向及沉积机理的影响. 结果表明: 氨基甲酸甲酯是一种性能优异的整平添加剂, 45 mmol/L氨基甲酸甲酯的加入明显改善Al产品的光亮度, 得到细致均匀且镜面光亮的Al沉积层. 氨基甲酸甲酯为添加剂时, 在电解液体系中没有形成新的金属络合离子, 不影响电解液中活性铝离子结构; 其羰基碳原子为正电中心在阴极表面吸附, 对Al的电沉积过程产生抑制进而获得整平和光亮效果.     

X-ray structural analysis of a novel organic metal (BEDT-TTF)4[Hg2Cl6]·PhCl

X-ray structural analysis has revealed that reaction of (BEDT-TTF)[HgCl₃]^– with PhCl leads to the formation of a cation-radical salt (BEDT-TTF)₄[Hg₂Cl₆]· PhCl, which exhibits a laminar crystal structure. The cationic layer is characterized by a grid or lattice network of contracted S...S intermolecular distances (3.396(4)–3.647(5) Å), which unite the BEDT-TTF cations in ribbons or bands, parallel to the [014] direction, and which also bind the ribbons together in a direction close to the [010] axis. The presence of this type of lattice network explains the metallic nature of the conductivity of this salt (BEDT-TTF)₄Hg₂Cl₆]·PhCl in the temperature range 300.0–1.5 K, and is the basis of assigning this salt to a new class of organic, two-dimensional conductors. The [Hg₂Cl₆]^2– anions and PhCl solvent molecules are united via secondary Hg...Cl 3.176(5) Å and Cl...Cl 3.480(6) Å interaction forces to form centrosymmetric tetramers [Hg₂Cl₆PhCl]₂ ^4–, stretched out along the [014] axis direction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2062–2070, September, 1991.The authors wish to acknowledge R. N. Lyubovskaya for supplying the crystals and for helpful discussion of the results.     

A Very Strong Methylation Agent: [Me2Cl][Al(OTeF5)4]

A new chloronium‐containing salt, [Me₂Cl][Al(OTeF₅)₄], was synthesized on multigram scale by means of a simple one‐pot procedure. The isolated product can be handled at room temperature and used as a strong electrophilic methylation agent. This is demonstrated by the methylation of the very weak bases P(CF₃)₃, PF₃, MeI, and MeBr.     

Die Kristallstrukturen von [Ph3PMe]Cl·CH2Cl2, [Ph4P]NO3·CH2Cl2 und [Ph4P]2[SiF6]·CH2Cl2

Crystal Structures of [Ph₃PMe]Cl·CH₂Cl₂, [Ph₄P]NO₃·CH₂Cl₂, and [Ph₄P]₂[SiF₆]·CH₂Cl₂ The crystal structures of the title compounds are determined by X‐ray diffraction. In all cases, the included dichloromethane molecules as well as the phosphonium cations are involved to form hydrogen bridges with the anions. [Ph₃PMe]Cl·CH₂Cl₂ ( 1 ): Space group , Z = 2, lattice dimensions at 100 K: a = 890.3(1), b = 988.0(1), c = 1162.5(1) pm, α = 106.57(1)°, β = 91.79(1)°, γ = 92.60(1)°, R₁ = 0.0253. [Ph₄P]NO₃·CH₂Cl₂ ( 2 ): Space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1057.0(1), b = 1666.0(1), c = 1358.9(1) pm, β = 100.10(1)°, R₁ = 0.0359. [Ph₄P]₂[SiF₆]·CH₂Cl₂ ( 3 ): Space group , Z = 2, lattice dimensions at 193 K: a = 1063.9(1), b = 1233.1(1), c = 1782.5(2) pm, α = 76.88(1)°, β = 83.46(1)°, γ = 72.29(1)°, R₁ = 0.0332.