Bi53+‐Polykationen in geordneten und plastischen Kristallen von Bi5[AlI4]3 und Bi5[AlBr4]3

Bi₅³⁺ Polycations in Ordered and Plastic Crystals of Bi₅[AlI₄]₃ and Bi₅[AlBr₄]₃ Dark‐red air‐sensitive crystals of pentabismuth‐tris(tetrabromoaluminate) Bi₅[AlBr₄]₃ and black crystals of Bi₅[AlI₄]₃ have been crystallized from melts of Bi, BiX₃ and AlX₃ (X = Br, I). X‐ray diffraction on a single crystal of Bi₅[AlI₄]₃ (T = 293(2) K; space group Pnma; a = 2143.6(3) pm, b = 1889.1(1) pm, c = 811.74(5) pm) revealed an ordered packing of Bi₅³⁺ trigonal bipyramids and [AlI₄]^? tetrahedra that corresponds to the PuBr₃ structure type. Contrary to the so far known Bi₅³⁺ polycations with accurate D_3h symmetry, the bismuth cluster found in Bi₅[AlI₄]₃ holds only C_s symmetry. The room temperature structure of the tetrabromoaluminate Bi₅[AlBr₄]₃, which is related to the AuCu₃ type, shows a dynamic disorder of the Bi₅³⁺ polycations (T = 293(2) K; space group ; a = 1766.2(3) pm). Slight cooling induces the transition into an ordered rhombohedral phase isostructural to Bi₅[AlCl₄]₃ (T = 260(2) K; space group a = 1241.5(8) pm, c = 3041(2) pm).     

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.     

The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis,Crystal Structures,and Chemical Bonding

The intermetalloid clusters [M₂Bi₁₂]⁴⁺ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl₂ in [BMIm]Cl · 5AlCl₃ (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1 ) crystals of [Ni₂Bi₁₂][AlCl₄]₃[Al₂Cl₇]. Black, monoclinic (P2₁/m) crystals of [Rh₂Bi₁₂][AlBr₄]₄ precipitated after dissolving the cluster salt Bi_12–xRhX_13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr₃ at 140 °C. In the cationic cluster [Ni₂Bi₁₂]⁴⁺, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D_4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi₄ rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D_2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster.     

Ag3Bi14Br21: ein Subbromid mit Bi24+‐Hanteln und Bi95+‐Polyedern – Synthese,Kristallstruktur und Chemische Bindung

Ag₃Bi₁₄Br₂₁: a Subbromide with Bi₂⁴⁺ Dumbbells and Bi₉⁵⁺ Polyhedra – Synthesis, Crystal Structure and Chemical Bonding Black crystals of Ag₃Bi₁₄Br₂₁ = (Bi₉⁵⁺)[Ag₃Bi₃Br₁₅^3?](Bi₂Br₆^2?), the first argentiferous bismuth subhalide, were obtained from a stoichiometric melt of Ag, Bi, and BiBr₃. The compound crystallizes in the monoclinic space group P2₁/m with lattice parameters a = 1277.78(5) pm, b = 1466.87(6) pm, c = 1342.62(5) pm, and β = 108.47(1)° at 110(5) K. In contrast to all other bismuth subhalides that contain an electron‐rich transition metal, the silver atoms are not bonded to bismuth atoms. Instead they are integrated into the anionic bromometallate network, which consists of [MBr₆]‐octahedra (M = Ag, Bi) that share edges and vertices. These corrugated sheets alternate with tessellated layers formed by Bi₉⁵⁺ polycations and hitherto unknown (Bi^II₂Br₆)^2? groups. The latter anions contain Bi₂⁴⁺ dumbbells (299 pm) and can be represented by the structured formula [Br₂Bi^II(μ–Br)₂Bi^IIBr₂]^2?. The multi‐center bonding within the Bi₉⁵⁺ cluster and the bent single‐bond in the Bi₂ dumbbell can be visualized using the electron localization indicator (ELI‐D).     

Local and Permeating Disorder of Copper(I) Cations in Cu3BiS2Br2 and Cu4Bi3S5Br3–xClx (x = 1.19)

Melting reactions of Bi₂S₃, CuX (X = Cl, Br), copper, and sulfur resulted in black needles of qua‐ and quinternary copper bismuth sulfide halogenides. Cu₃BiS₂Br₂ (I) has a melting point of 638(5) K and crystallizes in the orthorhombic space group Pnma with a = 804.50(6) pm, b = 393.27(3) pm, and c = 2253.2(2) pm at T = 293(2) K. Cu₄Bi₃S₅Br_3–xCl_x (x = 1.19(2)) (II) crystallizes in the monoclinic space group I2/m with lattice parameters a = 1573.7(2) pm, b = 397.52(3) pm, c = 2164.9(3) pm, and β = 95.66(1) °. Both compounds exhibit networks of thio‐halogenido‐bismuthate(III) polyhedra that join corners, edges, and faces. The copper(I) cations are spread over numerous contiguous trigonal or tetrahedral voids. In case of (II) a continuous pathway for copper ion transport along [010] is formed. The pseudo‐potential barrier for hopping of copper ions was calculated as 30 meV only.     

Bi5,6Ni5I: Eine partiell oxidierte intermetallische Phase mit Kanalstruktur

Bi_5,6Ni₅I: A Partly Oxidized Intermetallic Phase with Channel Structure Bi_5,6Ni₅I was prepared from the elements by chemical vapour deposition. Single-crystal investigations (space group I2/m, a = 1 852.1(3), b = 418.45(6), c = 1 373.8(3) pm, β = 90.42(2)°, V = 1 064.7(3) · 10⁶ pm³) revealed parallel doublewalled channels of nickel and bismuth atoms. The central pseudo 5 axis of each channel is occupied by 6/5 disordered bismuth atoms per lattice translation along [010]. Double rows of iodine atoms fill the distorted hexagonal arrangement of the channels. Bi_5,6Ni₅I is stabilized by metallic bonding in the framework metal atoms and additional heteropolar interactions between bismuth and iodine atoms as well as between bismuth and nickel atoms. Bi_5,6Ni₅I shows metallic conductivity and ferromagnetic ordering below 17 K.     

Hydrothermalsynthese und Kristallstruktur der Münzmetall‐Quecksilber‐Chalkogenidhalogenide CuHgSeBr,AgHgSBr und AgHgSI

Hydrothermal Synthesis and Crystal Structure of the Coinage Metal Mercury Chalcogenide Halides CuHgSeBr, AgHgSBr, and AgHgSI The hydrothermal reaction of CuBr and HgSe in concentrated aqueous HBr as solvent at 285 °C yields red crystals of CuHgSeBr, the hydrothermal reaction of AgX (X = Br, I) and HgS in half‐concentrated aqueous HX (X = Br, I) as solvent at 300/400 °C yields yellow crystals of AgHgSBr and AgHgSI. The compounds crystallize isotypically (orthorhombic, Pmma, a = 1020.1(3) pm, b = 431.2(1) pm, c = 925.6(3) pm for CuHgSeBr, a = 964.8(8) pm, b = 466.1(4) pm, c = 942.6(6) pm for AgHgSBr und a = 1015.9(2) pm, b = 464.77(5) pm, c = 984.9(2) pm for AgHgSI, Z = 4). The structures consist of plane folded Hg–Y chains connected by pairs of distorted Y₂X₂ terahedra sharing the X–X‐edge (M = Cu, Ag; X = Br, I; Y = S, Se). Atoms of the monovalent metals M have a strongly distorted tetrahedral coordination of two halogen and two chalcogen atoms. The new structure type shows distinct differences in the arrangement of the Hg–Y chains in comparision to the already known CuHgSeCl, but represents the superposition structure of the order‐disorder phase γ‐Hg₃S₂Cl₂.     

Lewis-Säure-Base-Reaktionen von Goldtrihalogeniden mit Bismuttrihalogeniden – Synthese und Kristallstrukturen von AuBiX6 (X  Cl,Br)

Lewis-Acid-Base-Reactions of Gold Trihalides with Bismuth Trihalides – Synthesis and Structures of AuBiX₆ (X ? CI, Br) Gold trihalides AuX₃ (X ? Cl, Br) react with bismuth trihalides in sealed glass ampoules to the 1 : 1 adducts AuBiX₆ (X ? Cl, Br). AuBiCl₆ is obtained by a chemical transport reaction at 220°C, whereas AuBiBr₆ was synthesized by solvothermal reaction in SiBr₄ at 150°C. Both compounds crystallize triclinic, space group P1 , Z = 4. AuBiCl₆; a = 698.3(4) pm; b = 1009.3(5) pm; c = 1381(1) pm; α = 104.98(5)°; β = 94.73(5)°; γ = 110.06(3)°; V = 867(1) · 10⁶ pm³. AuBiBr₆: a = 735.7(4) pm; b = 1055.7(5) pm; c = 1445(1) pm; α =104.88(5)°; β = 94.25(5)°; γ = 110.18(4)°; V =1001(1) ·10⁶pm³. The structures are build formally of square-planar [AuX₄]^? and chains of edge-connected ([BiX_4/2]⁺)_n units. Since each Bi ion is surrounded by eight halogenide ions in a square-antiprismatic form, the structure can alternatively be described as consisting of chains of edge sharing ([BiX₄X_4/2]^3?)_n antiprisms connected by Au³⁺ ions.     

Synthese,Kristallstrukturen und Magnetismus von (Hg6As4)[MoCl6]Cl, (Hg6As4)[TiCl6]Cl und (Hg6As4)[TiBr6]Br

Polycationic Hg–As Frameworks with Trapped Anions. II Synthesis, Crystal Structure, and Magnetism of (Hg₆As₄)[MoCl₆]Cl, (Hg₆As₄)[TiCl₆]Cl, and (Hg₆As₄)[TiBr₆]Br (Hg₆As₄)[MoCl₆]Cl is obtained by reaction of Hg₂Cl₂, Hg, As, and MoCl₄ in closed, evacuated glass ampoules in a temperature gradient 450 → 400 °C in form of dark red cubelike crystals. (Hg₆As₄)[TiCl₆]Cl and (Hg₆As₄)[TiBr₆]Br are also formed in closed, evacuated ampoules from Hg₂X₂ (X = Cl, Br), Hg, As, and Ti metal at 275 °C and 245 °C in form of dark green and black crystals, respectively. All three compounds are air and light sensitive. They crystallize isotypically (cubic, Pa 3, a = 1207.8(4) pm for (Hg₆As₄)[MoCl₆]Cl, a = 1209.4(3) pm for (Hg₆As₄)[TiCl₆]Cl, a = 1230.9(3) pm for (Hg₆As₄)[TiBr₆]Br, Z = 4). The structures consist of a three‐dimensionally connected Hg–As framework which is made up of As₂ groups (As–As distance averaged 242 pm) each connected via six Hg atoms to six neighbouring As₂ groups. There are two cavities of different size in the polycationic framework. The bigger cavity is filled with [MoCl₆]^3–, [TiCl₆]^3–, and [TiBr₆]^3– ions of nearly ideal octahedral shape, the smaller cavity with discrete halide ions. The magnetic properties of the two Ti containing compounds are in accordance with a d¹ paramagnetism. The temperature dependence and the magnitude of the magnetic moment can be interpreted with consideration of the spin‐orbit coupling. The so far known representatives of this structure type can be characterised by the ionic formula (Hg₆Y₄)⁴⁺[MX₆]^3–X^– (Y = As, Sb; M = Sb³⁺, Bi³⁺, Mo³⁺, Ti³⁺; X = Cl, Br).     

Die Cluster‐Salze Bi14Si2MI12 (M = Rh,Ir): [Bi8Si2]‐ und [MBi6I12]‐Baugruppen in CsCl‐analoger Anordnung

The Cluster Salts Bi₁₄Si₂MI₁₂ (M = Rh, Ir): [Bi₈Si₂] and [MBi₆I₁₂] Building Groups in CsCl‐like Structure The reaction of bismuth and iridium with iodine in evacuated quartz ampoules at 1320 K yields black, air insensitive crystals of Bi₁₄Si₂IrI₁₂. The silicon therein is abstracted from the ampoule material whereby the oxygen is gettered in BiOI. The synthesis of Bi₁₄Si₂RhI₁₂ requires the addition of niobium, which gives NbOI₂ with the oxygen originating from the SiO₂. X‐ray diffraction on single crystals showed that the two isotypic compounds crystallize in the space groups P 4/m c c with a = 1018.3(1), c = 2020.1(4) pm for M = Ir, and a = 1019.0(1), c = 2018.7(4) pm for M = Rh. The crystal structures consist of two types of isolated clusters, which form a CsCl‐like packing. In the [MBi₆I₁₂] cuboctahedron the central transition metal atom is octahedrally surrounded by bismuth atoms, and the iodine atoms bridge the edges of the octahedron. The [Bi₈Si₂] polyhedron is a tetragonal antiprism of bismuth atoms of which square faces are capped by silicon atoms. Based on crystal chemistry and band structure calculations the compounds may be formulated as cluster salts [Bi₈Si₂]³⁺[MBi₆I₁₂]^3–. Measurements of the electrical conductivity showed that Bi₁₄Si₂IrI₁₂ is a semiconductor with a band gap of about 0.1 eV. A single unpaired electron out of 1903 electrons per formula causes paramagnetic behaviour that is superposed by strong diamagnetic contributions.     

Bismut(II)-chalkogenometallate(III) Bi2M4X8, Verbindungen mit Bi24+-Hanteln (M = Al,Ga; X = S,Se)

Bismuth(II) Chalcogenometallates(III) Bi₂M₄X₈, Compounds with Bi₂⁴⁺ Dumbbells (M = Al, Ga and X = S, Se) The ternary bismuth(II) chalcogenometallates(III) Bi₂M₄X₈ (with M = Al, Ga and X = S, Se) were synthesized from the binary chalcogenides M₂X₃ and Bi₂X₃ and elementary bismuth. All compounds are diamagnetic semiconductors with E_g (opt.) = 1.8–2.7 eV. The phases (except Bi₂Al₄Se₈) are thermodynamically stable and decompose peritectically above 965–1020 K. Bi₂Al₄Se₈ is metastable below 825 K and is obtained only by rapid quenching from T > 825 K. The isotypic compounds crystallize in a new tetragonal tP28 structure type (P4/nnc). The characteristic unit is the hitherto unknown clustercation Bi₂⁴⁺, with the mean bond length d(Bi–Bi) = 314.2 pm, the Raman frequency 102 cm^–1 ≤ ν_s ≤ 108 cm^–1, and the mean force constant of f = 0.68 N · cm^–1. The Electron Localization Function, ELF, shows the covalent Bi–Bi bond, the lone electron pairs of the ψ-octahedrally coordinated Bi(II) cations, and the polar character of the Bi–X bonds.     

Selen‐Polykationen stabilisiert durch polymere Chlorobismutat‐Anionen: Synthesen und Kristallstrukturen von Se4[Bi4Cl14] und Se10[Bi5Cl17]

Selenium Polycations Stabilized by Polymeric Chlorobismuthate Anions: Syntheses and Crystal Structures of Se₄[Bi₄Cl₁₄] and Se₁₀[Bi₅Cl₁₇] Reactions of selenium with selenium(IV) chloride and bismuth(III) chloride in sealed evacuated glass ampoules at temperatures between 110 and 155 °C yield a series of compounds which are composed of discrete selenium polycations and polymeric chlorobismutate anions. Besides the already known Se₈[Bi₄Cl₁₄] two new compounds have been identified by crystal structure analyses as Se₄[Bi₄Cl₁₄] (tetragonal, P4/n, a = 1089.1(2) pm, c = 993.7(2) pm, Z = 2) and Se₁₀[Bi₅Cl₁₇] (monoclinic, P2₁/c, a = 1079.24(8) pm, b = 2062.9(2) pm, c = 1676.1(2) pm, β = 90.87(1)°, Z = 4). Se₄[Bi₄Cl₁₄] was obtained as red transparent platelike crystals and is the first example of a compound with (chalcogen₄)²⁺ ions of exact square‐planar symmetry and molecular point group D_4h in the solid state. The cations are surrounded by layers of two‐dimensional polymeric anions [Bi₄Cl₁₄]^2–. Se₁₀[Bi₅Cl₁₇] forms dark grey crystals with a reddish luster. The structure contains the known bicyclic polycation Se₁₀²⁺ which is disordered over two positions and the first three‐dimensional polymeric chlorobismutate anion [Bi₅Cl₁₇]^2–. The different BiCl_x polyhedra are linked by sharing common vertices, edges, and faces.     

Polymere,bandförmige Tellurkationen in den Strukturen des Chloroberyllats Te7[Be2Cl6] und des Chlorobismutats (Te4)(Te10)[Bi4Cl16]

Polymeric, Band Shaped Tellurium Cations in the Structures of the Chloroberyllate Te₇[Be₂Cl₆] and the Chlorobismutate (Te₄)(Te₁₀)[Bi₄Cl₁₆] Te₇[Be₂Cl₆] is obtained at 250 °C in an eutectic Na₂[BeCl₄] / BeCl₂ melt from Te, TeCl₄ und BeCl₂ in form of black crystals, which are sensitive towards hydrolysis in moist air. (Te₄) (Te₁₀)[Bi₄Cl₁₆] is prepared from Te, TeCl₄ und BiCl₃ by chemical vapour transport in sealed evacuated glass ampoules in a temperature gradient 150 ° → 90 °Cin form of needle shaped crystals with a silver lustre. The structures of both compounds were determined based on single crystal X‐ray diffraction data (Te₇[Be₂Cl₆]: orthorhombic, Pnnm, Z = 2, a = 541.60(3), b = 974.79(6), c = 1664.4(1) pm; (Te₄)(Te₁₀)[Bi₄Cl₁₆]: triclinic, P1¯, Z = 2, a = 547.2(3), b = 1321.1(7), c = 1490(1) pm, α = 102.09(5)°, β = 95.05(5)°, γ = 96.69(4)°). The structure of Te₇[Be₂Cl₆] consists of one‐dimensional polymeric cations (Te₇²⁺)_n which form folded bands and of discrete [Be₂Cl₆]^2— anions which form double tetrahedraconnected by a common edge. By a different way of folding compared with the cations present in the structures of Te₇[MOX₄]X (M = Nb, W; X = Cl, Br) the (Te₇²⁺)_n cation in Te₇[Be₂Cl₆]represents a new, isomeric form. The structure of (Te₄)(Te₁₀)[Bi₄Cl₁₆] contains two different polymeric cations. (Te₁₀²⁺)_n consists of planar Te₁₀ groups in the form of three corner‐sharing Te₄ rings connected to folded bands. (Te₄²⁺)_n forms in contrast to the so far notoriously observed discrete, square‐planar E₄²⁺ ions a chain of rectangular planar Te₄ rings (Te—Te 274 and 281 pm) connected by Te‐Te bonds of 297 pm. [Bi₄Cl₁₆]^4— has a complex one‐dimensional structure of edge‐ and corner‐sharing BiCl₇ units.     

Room‐Temperature Synthesis of Bismuth Clusters in Ionic Liquids and Crystal Growth of Bi5(AlCl4)3

The viability of Lewis‐acid ionic liquids for the synthesis of low‐valent bismuth compounds is demonstrated. At room temperature, elemental bismuth and bismuth(III) cations synproportionate in the ionic liquid [BMIM]Cl/AlCl₃ ([BMIM]⁺: 1‐n‐butyl‐3‐methylimidazolium) within minutes. The existence of bismuth polycations in the dark colored solution was proven by Raman spectroscopy. Dark‐red crystals of Bi₅(AlCl₄)₃ were isolated from the ionic liquid and characterized by Raman spectroscopy and X‐ray crystallography (rhombohedral space‐group , a = 1187.1(2) pm, c = 3012.0(3) pm). The method allows the synthesis of bismuth cluster compounds under milder conditions than in high‐temperature melts and more conveniently and environmental friendly than in liquid SO₂ with strongly oxidizing, toxic agents like SbF₅ or AsF₅.     

A new bismuth iron oxyphosphate,Bi6(Bi0.32Fe0.68)(PO4)4O4

Iron was inserted into the known crystal structure of the bismuth phosphate oxide Bi_6.67(PO₄)₄O₄ to ascertain its location in the vacancies associated with the bismuth ion located at the origin of the unit cell. Single‐crystal X‐ray diffraction refinements converged to a model of composition Bi₆(Bi_0.32Fe_0.68)(PO₄)₄O₄ (hexabismuth iron tetraphosphate tetraoxide), in which Bi and Fe are displaced from the origin giving rise to a random distribution over the 2i sites instead of 1a, the origin of space group P. The isotropic displacement parameter for Bi/Fe has a reasonable value in this model. This structure establishes for the first time that Fe substitutes in the Bi‐deficient site in this series of materials and that Fe and Bi are disordered around the center of symmetry. These results enhance understanding of the crystal chemistry of these main group phosphates that are of interest in ion transport.     

Synthese und Einkristallröntgenstrukturanalyse von Bromdi(isopropenyl)bismutan

Synthesis and Single Crystal X‐Ray Structure Analysis of Bromodi(isopropenyl)bismuthane Tri(isopropenyl)bismuthane ( 1 ) reacts with bromine to form bromodi(isopropenyl)bismuthane ( 2 ) and dibromo(isopropenyl)bismuthane ( 3 ). The single crystal X‐ray structure determination of 2 (monoclinic, P 2₁/c; a = 1058.6(3), b = 1127.0(3), c = 1561.3(4) pm, and β = 109.26(2)°; Z = 8 molecules; d_c = 2.803 g/cm³; R = 0.059) shows two crystallographically independent molecules which are connected by Bi–Br…Bi bridges (Bi–Br 282.3(2) and 284.7(2); Br…Bi 302.9(2) and 303.6(2) pm) forming helical chains directed along the b‐axis of the unit cell. Every turn of the helix (360°) consists of four molecules and corresponds to the length of the b‐axis (1127.0(3) pm).     

Über Münzmetall‐Quecksilber‐Chalkogenidhalogenide. II Hydrothermalsynthese,Kristallstruktur und Phasenumwandlung von CuHgSCl und CuHgSBr

On Coinage Metal Mercury Chalcogenide Halides II: Hydrothermal Synthesis, Crystal Structure, and Solid State Phase Transition of CuHgSCl and CuHgSBr The hydrothermal reaction of CuCl and CuBr with HgS in concentrated aqueous HX (X = Cl, Br) as solvent at 670 K in sealed glass ampoules yields yellow‐orange crystals of CuHgSCl and CuHgSBr. Both compounds crystallize isotypically (orthorhombic, Pbam, a = 984.01(8), b = 1775.1(2), c = 409.59(3) pm for CuHgSCl and a = 1003.7(4), b = 1833.6(5), c = 412.4(2) pm for CuHgSBr, Z = 8). The structures consist of plane folded HgS chains connected by pairs of distorted CuS₂X₂ tetrahedra sharing the X—X‐edge (X = Cl, Br) in which the copper atoms occupy off‐centered positions. The large displacement factors of the Cu atoms represent thermal vibrations as shown by additional X‐ray investigations at different temperatures. The single‐crystal structure determination shows that the earlier structure model, based on powder diffraction data, is incorrect. The structure type of CuHgSCl und CuHgSBr shows distinct similarities to the structure type of the already known compounds CuHgSeBr, AgHgSBr and AgHgSI (MHgYX). At 323 K CuHgSBr undergoes a second order phase transition into a higher symmetric structure of the MHgYX type (orthorhombic, Pmam, a = 1009.2(3), b = 918.40(4), c = 413.81(2) pm) with halved b‐axis.     

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)°.     

(Bzl4P)2[Bi2I8] – ein Iodobismutat mit fünffach koordiniertem Bi3+‐Ion

(Bzl₄P)₂[Bi₂I₈] – an Iodobismuthate with Penta‐coordinated Bi³⁺ Ions (Bzl₄P)₂[Bi₂I₈] ( 1 , Bzl = –CH₂–C₆H₅) is the first iodobismuthate showing square pyramidal coordination of the Bi³⁺ ion. The anion structure of 1 is compared with that of (Ph₄P)₂[Bi₂I₈(thf)₂] ( 2 ), in which the vacant coordination sites in 1 are occupied by THF ligands. (Bzl₄P)₂[Bi₂I₈] ( 1 ): Space group P1 (No. 2), a = 1300.6(6), b = 1316.8(6), c = 2157.0(9) pm, α = 78.66(3), β = 87.17(3), γ = 60.62(3)°, V = 3151(2)_.10⁶ pm³; (Ph₄P)₂[Bi₂I₈(thf)₂] ( 2 ): Space group P1 (No. 2), a = 1146.5(1), b = 1181.2(1), c = 1249.2(1) pm, α = 92.28(1), β = 105.71(1), γ = 95.67(1)°, V = 1616.6(2)_.10⁶ pm³.