Synthesis and structure of the rhodium complex [Ph3MeP][RhBr4(DMSO)2-trans]

The ionic complex, methyltriphenylphosphonium(I) trans-bis(dimethylsulfoxido)tetrabromorhodiate, was prepared by the reaction of sodium hexabromorhodiate with methyltriphenylphosphonium bromide in dimethyl sulfoxide and studied by X-ray diffraction. The phosphorus atom in the [Ph₃MeP]⁺ cation has an almost undistorted tetragonal coordination (the CPC angles are 108.3(2)°–110.5(2)°, the P-C bonds are 1.779(6)–1.798(4) Å). In the octahedral complex anion [RhBr₄(DMSO)₂-trans]^?, the dimethyl sulfoxide ligands are coordinated by the sulfur atoms (Rh-S, 2.344(1), 2.336(1); Rh-Br, 2.4839(7)–2.4934(7) Å; SRhS, 179.56(7)°; trans-BrRhBr, 179.30(3)°, 179.56(7)°) (CIF file CCDC no. 978748).     

Synthesen,Kristallstrukturen und Drillingsbildung der Cluster‐Trimere Bi2[PtBi6Br12]3 und Bi2[PtBi6I12]3

Syntheses, Crystal Structures, and Triple Twinning of the Cluster Trimers Bi₂[PtBi₆Br₁₂]₃ and Bi₂[PtBi₆I₁₂]₃ Melting reactions of Bi with Pt and BiX₃ (X = Br, I) yield shiny black, air insensitive crystals of the subhalides Bi₂[PtBi₆X₁₂]. Bi₂[PtBi₆Br₁₂]₃ crystallizes in the monoclinic space group C2/m with lattice parameters a = 1617.6(2) pm, b = 1488.5(1) pm, c = 1752.4(2) pm, and β = 110.85(4)°. Bi₂[PtBi₆I₁₂]₃ adopts the triclinic space group with pseudo‐monoclinic lattice parameters a = 1711.2(2) pm, b = 1585.1(1) pm, c = 1865.7(2) pm, and α = 90°, β = 111.15(4)°, γ = 90°. The two homoeotypic compounds consist of cuboctahedral [Pt^?IIBi^II₆X^?I₁₂]^2? clusters that are concatenated into linear trimers by Bi^III atoms. The ordered distribution of Bi^III atoms destroys the inherent threefold rotation axes in the packing of cluster anions. As a consequence of the pseudosymmetry the crystals are triple twinned along [201]. Due to different orientations of the cluster trimers there are two Bi^II···X inter‐cluster bridges per Bi^II atom in Bi₂[PtBi₆Br₁₂]₃ but only one bridge in Bi₂[PtBi₆I₁₂]₃. The structure of the iodine compound can be deduced from the NaCl structure type, leaving 37 of 96 atomic positions unoccupied. The arrangement of the cuboctahedral clusters follows the motif of a body‐centered cubic packing.     

(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids

The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.     

Palladium Complexes [Ph3PCH2CN]2[PdBr4], [Ph4P]2[PdBr4], [Ph3PC5H9-cyclo][PdBr3(Et2SO)], and [Ph4P]2[Pd2Br6]. Synthesis and Structure

Russian Journal of General Chemistry - Palladium phosphonium complexes with mononuclear anions [Ph3PCH2CN][PdBr4], [Ph4P][PdBr4], and [Ph3PC5H9-cyclo][PdBr3(Et2SO)] were synthesized by the reaction...     

Bi24Ru3Br20: Ein pseudo-tetragonales Subbromid mit [RuBi6Br12]-Clustern und [Ru2Bi17Br4]-Gruppen

Bi₂₄Ru₃Br₂₀: A Pseudo-Tetragonal Structure with [RuBi₆Br₁₂] Clusters and [Ru₂Bi₁₇Br₄] Groups The melting reaction of Ru with Bi and BiBr yields black, lustrous, air insensitive crystals of the subbromide Bi₂₄Ru₃Br₂₀. The orthorhombic crystal structure (space group Pc2₁n, a = b = 1377.8(1) pm, c = 3222.3(4) pm, V = 6117.0 · 10⁶ pm³) deceives pseudo-symmetry with respect to the tetragonal space group P4/ncc leading to multiply twinned crystals. The structure can formally be subdivided in [RuBi₆Br₁₂] clusters, [Ru₂Bi₁₇Br₄] stacks, and [BiBr₄] groups.     

The Phase Diagram of the System [Ph4P]Br/BiBr3. Synthesis,Crystal Structure,Thermal Behaviour,and Vibrational Spectra of [Ph4P]3[Bi2Br9] · CH3COCH3 and two Modifications of [Ph4P]4[Bi6Br22]

The phase diagram of the system [Ph₄P]Br/BiBr₃ was investigated with the aid of DSC, TG and temperature dependent X‐ray powder diffraction measurements. By varying the reaction conditions, stoichiometry and crystallisation conditions of the reaction between BiBr₃ and [Ph₄P]Br four polynuclear bromobismuthates are formed. We report here the crystal structure of the solvation product [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃, which crystallises with monoclinic symmetry in the S. G. P2₁/n No. 14, a = 12.341(1), b = 32.005(3), c = 19.929(3) Å, β = 99.75(2)°, V = 7758(7) ų, Z = 4 and the crystal structures of two modifications of the compound [Ph₄P]₄[Bi₆Br₂₂]. The α‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.507(4) Å, b = 14.434(4) Å, c = 17.709(5) Å, α = 81.34(2)°, β = 72.42(2)°, γ = 72.53(2)°, V = 3132.7(1) ų, Z = 2. The high‐temperature β‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.893(4) Å, b = 14.267(3) Å, c = 16.580(3), α = 100.13(2)°, β = 96.56(2)°, γ = 110.01(2)°, V = 2985.5(1) ų, Z = 2. Lattice parameters of [Ph₄P]₄[Bi₈Br₂₈] are also given. The thermal behaviour of the compounds and in addition the vibrational spectra of [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃ are presented and discussed.     

Die Kristallstrukturen von [Et3PNAsPh3]2[Ag2Br4] und [Et3PNAsPh3]2[Pd2Br6]

Crystal Structures of [Et₃PNAsPh₃]₂[Ag₂Br₄] and [Et₃PNAsPh₃]₂[Pd₂Br₆] Colourless single crystals of [Et₃PNAsPh₃]₂[Ag₂Br₄]( 1 ) and red single crystals of [Et₃PNAsPh₃]₂[Pd₂Br₆]( 2 ) have been isolated from saturated solutions in acetonitrile of equivalent mixtures of [Et₃PNAsPh₃]Br with AgBr and PdBr₂, respectively. Both complexes were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at ‐70°C: a = 985.0(2), b = 1042.2(5), c = 1345.8(5) pm, α = 102.88(2)°, β = 105.73(2)°, γ = 94.94(2)°, R₁ = 0.0577. 2 : Space group P2₁/c, Z = 2, lattice dimension at ‐70°C: a = 1003.0(1), b = 1371.8(2), c = 1974.0(1) pm, β = 93.30(1)°, R₁ = 0.0458. The dimeric anions of 1 and 2 form planar, centrosymmetric complex units.     

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.     

Synthesis,Crystal Structure,Vibrational Spectra,and Thermal Behaviour of [Ph4P]2[Bi2(μ‐Br)2Br6 (CH3COCH3)2]

[Ph₄P]₂[Bi₂Br₈(CH₃COCH₃)₂] ( 1 ) was obtained by the reaction of [Ph₄P]Br and BiBr₃ in acetone. Single crystals were grown by allowing a layer of n‐hexane to diffuse into the acetonic solution of 1 . The crystal structure was determined by means of X‐ray diffraction. 1 crystallises with monoclinic symmetry in the space group P2₁/n, No. 14 with the lattice parameters: a = 13.358(2), b = 12.637(2), c = 18.565(3) Å, β = 102.62(1)°, V = 3058.1(8) ų and Z = 4. The structure is characterised by the anion [Bi₂Br₈(CH₃COCH₃)₂]^2– which is embedded in a matrix of [Ph₄P]⁺ cations. The anion can be described as two edge‐sharing square pyramids with the apical bromide ions in anti‐position. Acetone co‐ordinates the bismuth atoms via oxygen atoms and increases the co‐ordination number of central bismuth atoms to six which results in the formation of a distorted bi‐octahedron. The distortion is due to the difference in terminal and bridging Bi–Br bond lengths. FT‐IR and Raman spectroscopic data are presented. In addition, the thermal behaviour of the compound was studied with the aid of TG/DSC coupled with MS revealing that acetone leaves the crystal in two steps. The compound melts at 203 °C and transforms into a glass on cooling.     

Darstellung und Kristallstrukturen von (Ph3PNPPh3)2[Re2Br10] und (Ph4P)[Re2Br9]

Synthesis and Crystal Structures of (Ph₃PNPPh₃)₂[Re₂Br₁₀] and (Ph₄P)[Re₂Br₉] Depending on the molar ratio by reaction of [n-Bu₄N]₂[ReBr₆] with the Lewis acid BBr₃ in dichloromethane the bioctahedral complexes [n-Bu₄N]₂[Re₂Br₁₀] and [n-Bu₄N][Re₂Br₉] are formed. The X-ray structure determination on (Ph₃PNPPh₃)₂[Re₂Br₁₀] (monoclinic, space group C 2/c, a = 20.007(4), b = 15.456(5), c = 24.695(4) Å, β = 107.53(2)°, Z = 4) reveals a centrosymmetric edge-sharing complex anion with approximate D_2h symmetry and mean terminal and bridging Re–Br bond lengths of 2.453 (equatorial), 2.482 (axial) and 2.591 Å, respectively, and a Re–Re distance of 3.880 Å. (Ph₄P)[Re₂Br₉] (triclinic, space group P 1, a = 11.062(2), b = 12.430(3), c = 13.163(5) Å, α = 72.94(2), β = 68.47(2), γ = 82.09(2)°, Z = 2) contains a confacial bioctahedral anion with nearly D_3h symmetry and mean terminal and bridging Re–Br distances of 2.460 and 2.536 Å, respectively, and a Re–Re distance of 2.780 Å.     

Synthese und Kristallstrukturen von [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19] und (Ph4P)4[Bi6I22]

Synthesis and Crystal Structure of [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], and (Ph₄P)₄[Bi₆I₂₂] Solutions of BiI₃ in THF or methanol react with MI (M = Li, Na) to form polynuclear iodo complexes of bismuth. The syntheses and results of X-ray structure analyses of compounds [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], [Na(thf)₆]₄[Bi₆I₂₂] and (Ph₄P)₄[Bi₆I₂₂] are described. The anions of these compounds consist of edge-sharing BiI₆ and BiI₅(thf) octahedra. The Bi atoms lie in a plane and are coordinated by bridging and terminal I atoms and by THF ligands in a distorted octahedral fashion. [Li(thf)₄]₂[Bi₄I₁₄(thf)₂]: Space group P1 (No. 2), a = 1 159.9(6), b = 1 364.6(7), c = 1 426.5(7) pm, α = 114.05(3), β = 90.01(3), γ = 100.62(3)°. [Li(thf)₄]₄[Bi₅I₁₉]: Space group P2₁/n (No. 14), a = 1 653.0(9), b = 4 350(4), c = 1 836.3(13) pm, β = 114.70(4)°. [Na(thf)₆]₄[Bi₆I₂₂]: Space group P2₁/n (No. 14), a = 1 636.4(3), b = 2 926.7(7), c = 1 845.8(4) pm, β = 111.42(2)°. (Ph₄P)₄[Bi₆I₂₂]: Space group P1 (No. 2), a = 1 368.6(7), b = 1 508.1(9), c = 1 684.9(8) pm, α = 98.28(4), β = 95.13(4), γ = 109.48(4)°.     

Bi34Ir3Br37: Ein pseudosymmetrisches Subbromid aus Bi5+- und Bi62+-Polykationen sowie [IrBi6Br12]–- und [IrBi6Br13]2–-Clusteranionen

Bi₃₄Ir₃Br₃₇: A Pseudo-Symmetric Subbromide with Bi₅⁺ and Bi₆²⁺ Polycations, and [IrBi₆Br₁₂]^– and [IrBi₆Br₁₃]^2– Cluster Anions The melting reaction of Ir with Bi and BiBr₃ yields black, lustrous, air insensitive crystals of the subbromide Bi₃₄Ir₃Br₃₇. The triclinic crystal structure (space group P 1, a = b = 1303.4(2) pm, c = 1647.4(4) pm, α = β 90°, γ = 120°, V = 2423.7 × 10⁶ pm³) deceives pseudo symmetry with respect to the rhombohedral space group R 3, which results in multiply twinned crystals. The structure can formally be subdivided in four new types of ionic groups: (a) cuboctahedral [IrBi₆Br₁₂]^– clusters, (b) [IrBi₆Br₁₃]^2– clusters with an additional Br atom, (c) Bi₅⁺ square pyramids, and (d) distorted Bi₆²⁺ octahedra. The compound shows a range of homogeneity due to variable contributions of the different clusters.     

Das erste quinquinäre Oxoaurat(I) K6Na[IO6][AuO]2 = K6[NaIO6][AuO2/2]2 [1]

Inhaltsübersicht. Bei Versuchen zur Darstellung unbekannter Phasen im System A/Au/I/O (mit A = Alkalimetall) entstanden durch Erhitzen eines Gemenges (2,2 K₂O + 1,0 NaIO₄; Au-Rohr; 700°C, 59 d) farblose, transparente Einkristalle von K₆NaAu₂IO₈, das nach Einkristalldaten (Vierkreisdiffraktometerdaten, 2465 I_o(hkl), AgKα, R = 6,8% und R_w = 5,6%) monoklin in P2/c mit a = 707,4 pm; b = 977,3 pm; c = 1199,4 pm; β = 122,9°; Z = 2 kristallisiert. Charakteristisch sind die hier erstmals gefundenen, HgO-analogen Zickzackketten [AuO_2/2] längs [001]. Daneben prägen, den NaIO₆-Teil der Struktur betreffend, Ketten aus [IO₆]-Oktaeder, über Na in prismatischer Koordination verknüpft, den Aufbau. The First Quinquinary Oxoaurate(I). K₆Na[IO₆][AuO]₂ = K₆[NaIO₆][AuO_2/2]₂ Attempting to synthesize unknown phases in the system A/Au/I/O by heating a mixture of K₂O and NaIO₄ (K: Na = 2.2:1.0, sealed gold tube, 700°C) we obtained colourless, transparent single crystals of K₆NaAu₂IO₆, a new type of Oxoaurate(I). According to single crystal data K₆NaAu₂IO₈ crystallizes in a monoclinic form with a = 707.4 pm, b = 977.3 pm, c = 1199.4 pm β = 122.9° (Z = 2, space group P2/c). Essential part of the structure are chains NaIO₆ and zigzag chains AuO_2/2, both along [001]. The Madelung part of the lattice energy, MAPLE, and effective coordination numbers, ECoN, are calculated and discussed.     

Piezoelectric Energy Harvesting from a Ferroelectric Hybrid Salt [Ph3MeP]4[Ni(NCS)6] Embedded in a Polymer Matrix

Organic–inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion‐containing A₄BX₆ type organic–inorganic hybrid salt [Ph₃MeP]₄[Ni(NCS)₆] ( 1 ) is now presented. P‐E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 μC cm^?2, at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt % compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm^?3 were observed for the 15 wt % 1 ‐TPU device. The capacitor charging experiments on the 15 wt % 1 ‐TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 μJ and 600 μC, respectively.     

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.     

The preparation and structures of Ph3AsGaI3 and [Ph3AsI][GaI4]

Colourless crystals of Ph₃AsGaI₃ (1) have been prepared by reaction of triphenylarsine with GaI₃·OEt₂ in diethyl ether. The structure of 1, in which the length of the AsGa donor-acceptor bond is 2.490(2) Å, has been determined by an X-ray diffraction study. In contact with the solvent phase, 1 is transformed into yellow crystals of [Ph₃AsI][GaI₄], 2 which has been structurally characterised by Raman spectroscopy (AsI stretching at 196 cm⁻¹) and by X-ray diffraction. The salt 2 is the first arsenic(V) iodo complex to have been examined crystallographically; the AsI bond distance is 2.485(1) Å.