A novel cage organotellurate(IV) macrocyclic host encapsulating a bromide anion guest: [Li(THF)4][(PriTe)12O16Br4(Li(THF)Br)4)Br].2THF

The first structural report of an unprecedented organotellurate(IV) inorganic-organic hybrid macrocyclic host encapsulating a bromide anion guest is described.     

Reaction between [MgCl2(THF)2] and [MoOCl3(THF)2]. The Crystal Structures of [Mg(THF)6][MoOCl4THF]2 and [Mg2(m̈-Cl)3(THF)6][MoOCl4THF]

Two [MoOCl₃(THF)₂] molecules are used for detachment of two Cl atoms from [MgCl₂(THF)₂]. In such reaction a green crystalline salt [Mg(THF)₆][MoOCl₄THF]₂ IV is formed. Compound IV reacts further with 3 equivalents of bis(tetrahydrofuran)magnesium dichloride, yielding a green ionic [Mg₂(m?-Cl)₃(THF)₆][MoOCl₄THF] compound V . Compound IV and V vary only in a structure of cation what indicated that the tri-m?-chlorohexakis(tetrahydrofuran)dimagnesium(II) cation in V is really formed in reaction between [Mg(THF)₆]²⁺ cation and [MgCl₂(THF)₂]. The crystal structure of compounds IV and V has been solved by X-ray diffraction method. The [Mg(THF)₆]²⁺ cation forms the tetragonally distorted octahedron with the magnesium atom in the symmetry centre. In homobimetallic di-octahedral [Mg₂(m?-Cl)₃(THF)₆]⁺ cation the magnesium atoms are surrounded by three bridging chlorine atoms and three THF molecules. The structures of [MoOCl₄THF]^? in IV and V are similar. In those anions the molybdenum atom is hexacoordinated with four chlorine atoms in equatorial plane.     

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.     

Preparation and comprehensive characterization of [Hg6(alanine)4(NO3)4].H2O

A new mercury-alanine complex has been isolated from reaction mixtures of mercurous nitrate dihydrate and alanine (L and D enantiomers). The solid-state structure contains mercury(I) and mercury(II) associated by alanine ligands in a polymeric array. The disproportionation of mercury(I) to mercury(II) and mercury(0) was facilitated by alanine and is evidenced by the appearance of mercury(0) in reactions of mercury(I) with the 20 common amino acids. This complex is the first mercury(I)-amino acid complex characterized in the solid state. The compounds have been comprehensively characterized using X-ray crystallography, solid-state and solution-state nuclear magnetic resonance spectroscopy, vibrational spectroscopies, and electrospray ionization mass spectrometry.     

[Li(THF)_4][GdCl_4(THF)_2]的晶体结构

氯化钆与对-甲基苯基锂在四氢呋喃中反应得到产物之一为[Li(THF)_4][GdCl_4-(THF)_2],(M_r=738.2),在-70℃下进行X-射线衍射研究。其晶体属单斜晶系,P2/n空间群。晶体学参数为a=13.263(2),b=8.474(1),c=14.961(0);β=99.72(1)°,V=1657.23(?)~3,Z=2,D_c=1.48g/cm~3,F(000)=750,μ_c=24.2cm~(-1),最终偏离子为R=0.0614。研究结果表明,本题晶体是离子型晶体,围绕Gd~(3+)的四个Cl~-离子和两个THF分子的氧原子构成畸变的八面体。Li~+周围的四个THF分子的氧原子构成一个近似的四面体。     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

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.     

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.     

Synthese und Kristallstrukturen der Seltenerd-Komplexe [LaI2(THF)5]+I3−, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]−, [ErCl3(DME)2] und [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]−

Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI₂(THF)₅]⁺I₃^?, [SmCl₃(THF)₄], [ErCl₂(THF)₅]⁺ [ErCl₄(THF)₂]^?, [ErCl₃(DME)₂], and [Na(18-Crown-6)(THF)₂]⁺[YbBr₄(THF)₂]^? [LaI₂(THF)₅]⁺I₃^? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl₃(THF)₄] ( 2 ) originates as colourless crystals on heating SmCl₃ with excess THF in the presence of Me₃SiNPEt₃. Space group P2₁/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl₂(THF)₅]⁺[ErCl₄(THF)₂]^? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC1₃(DME)₂] ( 4 ) originates as pink single crystals from ₃ with excess boiling 1,2-dimethoxyethane. Space group P2₁/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)₂]⁺ [YbBr₄(THF)₂]^? ( 5 ) is formed as by-product by the reaction of YbBr₃ with NaN(SiMe₃)₂ in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr₄(THF)₂]^?ions, in which the THF molecules are arranged in trans-position.     

Die Kristallstrukturen der Triarylzinkate [Mg2Br3(THF)6][ZnPh3] und [MgBr(THF)5][ZnMes3]

Crystal Structures of the Triarylzincates [Mg₂Br₃(THF)₆][ZnPh₃] and [MgBr(THF)₅][ZnMes₃] The title compounds were obtained from reactions of the phosphoraneiminato complex [ZnBr(NPMe₃)]₄ with excess Grignard reagents RMgBr (R = C₆H₅, 2,4,6-(CH₃)₃–C₆H₂) in THF solution. According to X-ray structure determinations the [ZnR₃]^– ions contain zinc atoms which are coordinated in a planar fashion with Zn–C distances of 200.7 pm (R = Ph) and 203.4 pm (R = Mes) in average.     

Zur Reaktion von WOCl4 mit Mesitylgrignardreagenz – Kristallstrukturanalysen von [ClMg(THF)4{OWCl4(THF)}], [Mg(THF)4{OWCl4(THF)}2] und WOMes3(THF)2

Mesityl Oxo Molybdenum and Tungsten Compounds. III. Reactions of WOCl₄ with Mesityl Grignard Reagent – X-Ray Crystal Structures of [ClMg(THF)₄{OWCl₄(THF)}], [Mg(THF)₄{OWCl₄(THF)}₂], and WOMes₃(THF)₂ The reaction of WOCl₄ with MesMgBr (1 : 1) in tetrahydrofuran (THF) proceeds via reduction to tungsten(V), which can be isolated as [MgX(THF)₄][WOCl₄(THF)] ( 2 ) and by elimination of MgX₂ in form of [Mg(THF)₄{OWCl₄(THF)}₂] ( 3 ). The reaction of WOCl₄ with MesMgBr in the molar ratio 1 : 4 yields after reduction [WOMes₃(THF)] · THF ( 4 ). All complexes are characterized by X-ray structure analyses. In 2 and 3 [WOCl₄(THF)]^– anions are linked via their oxo ligands to the magnesium ions. 4 has a distorted trigonal bipyramidal coordination sphere.     

Mercury(II) cyanide coordination polymer with dinuclear gold(I) amidinate. Structure of the 2-D [Au2(2,6-Me2-formamidinate)2].2Hg(CN)2.2THF complex

The dinuclear gold(I) amidinate complex [Au(2)(Me(2)-form)(2)], 1, (Me(2)-form = 2,6-Me(2)-formamidinate) reacts with Hg(CN)(2) to form a 2D structure, 1.2Hg(CN)(2).2THF. Each gold center interacts with two Hg(CN)(2) molecules. The Au...Au distance increases from 2.7 Angstroms in the starting dinuclear complex to 2.9 Angstroms in the adduct. The gold centers are connected to four nitrogen atoms with Au-N distances in the range 2.13-2.51 Angstroms. The cyanide stretch is shifted from 2192 cm(-1) in the Hg(CN)(2) to 2147 cm(-1) in the adduct.     

Synthesis and Crystal Structure of[C_6H_5CH_2C_5H_4ErCl_2(THF)_3]·THF

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Crystal structure of [p-C6H4(CH2ImMe)2][PtCl6].

The structure of the title complex consists of a [p-C6H4(CH2ImMe)2]2+ and [PtCl6](2-) pair. The platinum atom is hexacoordinated by six chloride ions in octahedral coordination geometry. The average Pt-Cl bond distance is 2.3199 A. The imidazolium cation and hexachloroplatinate anion are linked via hydrogen bonds, and the crystal packing is governed by the CH...Cl interactions.     

Die Kristallstruktur der Hexaquomagnesiumhexahalogeno-dimercurate [Mg(OH2)6][Hg2X6] (X = Br,I)

Crystal Structure of the Hexaquomagnesiumhexahalogenodimercurates [Mg(OH₂)₆][Hg₂X₆] (X = Br, I) Hexaquodimercurates [Mg(OH₂)₆][Hg₂X₆] (X = Br, I) were obtained by crystallization from aqueous solutions of HgX₂ and MgX₂. The crystal structure of the monoclinic compounds consists of binuclear Hg₂X₆ anions and octahedral Mg(OH₂)₆ cations.