Ein neues cis‐[Bi3I12]3−‐Anion in Tri(n‐butyl)methylammonium Dodecaiodotribismutat

The Novel cis‐[Bi₃I₁₂]^3?‐Anion in Tri(n‐butyl)methylammoniumdodecaiodo‐tribismutate By reaction of equivalent amounts of BiI₃, KI and I₂ in [N(CH₃) (n‐C₄H₉)₃][N(SO₂CF₃)₂] as Ionic Liquid, transparent reddish crystals with the composition [N(CH₃)(n‐C₄H₉)₃]₃[Bi₃I₁₂] are formed. Concerning to X‐ray diffraction investigations based on single crystals as well as powders, [N(CH₃)(n‐C₄H₉)₃]₃[Bi₃I₁₂] crystallizes monoclinic (P2₁/c; a = 2383.0(5); b = 1241.0(3); c = 2493.0(5) pm; β = 97.50(3)°; Z = 4). The anion consists of distorted (BiI₆)‐octahedra, which are face‐shared via cis‐oriented octahedral faces. With the cis‐[Bi₃I₁₂]^3?‐anion such a connectivity is firstly described.     

A Water Sensitive Hydrate: The Bis‐Catena Complex Salt [Mn(H2O)6][BiI4]2·2H2O

Bright red crystals of [Mn(H₂O)₆][BiI₄]₂ · 2H₂O are obtained from a solution of MnI₂, BiI₃, and I₂ in absolute ethanol, which is exposed to humid air. Reversible dehydratization sets in at about 50 °C. Added water decomposes the hydrate by irreversible precipitation of BiOI. The optical bandgap is about 1.9(1) eV. X‐ray diffraction on a single‐crystal revealed a monoclinic lattice (space group P2₁/c) with a = 760.39(4) pm, b = 1315.6(1) pm, c = 1398.37(7) pm, and β = 97.438(4)°. In the crystal structure zigzag chains of edge‐sharing [BiI_2/1I_4/2]^– octahedra and linear strings of H₂O‐bridged [Mn(H₂O)₆]²⁺ octahedra run parallel [100].     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

Mixed‐Valence Thallium(I,III) Bromides The Crystal Structure of α—Tl2Br3

Thallium sesquibromide Tl₂Br₃ is dimorphic. Scarlet coloured crystals of α‐Tl₂Br₃ were obtained by reactions of aqueous solutions of TlBr₃ and Tl₂SO₄ in agarose gel. In case of rapid crystallisation of hydrous TlBr₃/TlBr solutions and from TlBr/TlBr₂ melts ß‐Tl₂Br₃ is formed as scarlet coloured, extremely thin lamellae. The crystal structures of both forms are very similar and can be described as mixed‐valence thallium(I)‐hexabromothallates(III) Tl₃[TlBr₆]. In the monoclinic unit cell of α‐Tl₃[TlBr₆] (a = 26.763(7) Å; b = 15.311(6) Å; c = 27.375(6) Å; β = 108.63(2)°, Z = 32, space gr. C2/c) the 32 Tl^III‐cations are found in strongly distorted octahedral TlBr₆ groups. The 96 Tl^I cations are surrounded either by four or six TlBr₆ groups with contacts to 8 or 9 Br neighbors. Crystals of β‐Tl₃[TlBr₆] by contrast show almost hexagonal metrics (a = 13.124(4) Å, b = 13.130(4) Å, c = 25.550(7) Å, γ = 119.91(9)°, Z = 12, P2₁/m). Refinements of the parameters revealed structural disorder of TlBr₆ units, possibly resulting from multiple twinning. Both structures are composed of Tl₂[TlBr₆]^— and Tl₄[TlBr₆]⁺ multilayers, which alternate parallel (001). The structural relationships of the complicated structures of α‐ and β‐Tl₃[TlBr₆] to the three polymorphous forms of Tl₂Cl₃ as well as to the structures of monoclinic hexachlorothallates M₃TlCl₆ (M = K, Rb) and the cubic elpasolites are discussed.     

Bi37InBr48: Eine polares Subhalogenid mit Bi95+‐Polykationen,komplexen Bromobismutat(III)‐Anionen [Bi3Br13]4— und [Bi7Br30]9— sowie Pentabromoindat(III)‐Anionen [InBr5]2—

Bi₃₇InBr₄₈: a Polar Subhalide with Bi₉⁵⁺ Polycations, Complex Bromobismuthate(III) Anions [Bi₃Br₁₃]^4— and [Bi₇Br₃₀]^9—, and Pentabromoindate(III) Anions [InBr₅]^2— Black crystals of Bi₃₇InBr₄₈ were synthesized from bismuth, indium and BiBr₃ by cooling stoichiometric melts from 570 K to 470 K. X‐ray diffraction on powders and single‐crystals revealed that the compound crystallizes with space group P 6₃ (a = 2262.6(4); c = 1305.6(2) pm). The Bi₉⁵⁺ polycations in the polar crystal structure have the shape of heavily distorted tri‐capped trigonal prisms with approximate C_s symmetry. The high complexity of the structure results from three coexisting types of anionic groups: Three edge‐sharing [BiBr₆] octahedra constitute the trigonal bromobismuthate(III) anion [Bi₃Br₁₃]^4—. Four [BiBr₆] and three [BiBr₅] polyhedra share common vertices to form the [Bi₇Br₃₀]^9— hemi‐sphere, in which the trigonal bipyramid of the pentabromoindat(III) ion [InBr₅]^2— is embedded.     

Über Thallium(I)-chlorooxomolybdate: Synthese und Kristallstrukturen von Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7] und Tl2[Mo4O4Cl14] und die Struktur von Tl2[MoCl6]

On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl₄(NCCH₃)], Tl[Mo₂O₂Cl₇], and Tl₂[Mo₄O₄Cl₁₄] and the Structure of Tl₂[MoCl₆] Black crystals of Tl₂[MoCl₆] are formed in the reaction of TlCl with MoOCl₃ in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl₂[MoCl₆] (cubic, Fm 3¯m, a = 986.35(7) pm) adopts the K₂[PtCl₆] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl₄(NCCH₃)] was obtained by the reaction of TlCl with MoOCl₃ in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl⁺ cations and octahedral [MoOCl₄(NCCH₃)]^– anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl₃ in dichloromethane yields Tl[Mo₂O₂Cl₇] and Tl₂[Mo₄O₄Cl₁₄] as green moisture sensitive crystals. The structure of Tl[Mo₂O₂Cl₇] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl⁺ cations and dinuclear [Mo₂O₂Cl₇]^– anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl₂[Mo₄O₄Cl₁₄] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl⁺ cations and [Mo₄O₄Cl₁₄]^2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl₅) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.     

Cs10Tl6SiO4, Cs10Tl6GeO4, and Cs10Tl6SnO3 – First Oxotetrelate Thallides,Double Salts Containing “Hypoelectronic” [Tl6]6– Clusters

Cs₁₀Tl₆TtO₄ (Tt = Si, Ge) and Cs₁₀Tl₆SnO₃ were synthesized by the reaction of appropriate starting materials at 623–673 K, followed by fast cooling or quenching to room temperature, in arc‐welded tantalum ampoules. According to single‐crystal X‐ray analyses, the compounds crystallize in new structure types (Cs₁₀Tl₆TtO₄ (Tt = Si, Ge), P2₁/c and Cs₁₀Tl₆SnO₃, Pnma), consisting of [Tl₆]^6– clusters, which can be characterized as distorted octahedra compressed along one of the fourfold axes of an originally unperturbed octahedron, and [SiO₄]^4–, [GeO₄]^4– or [SnO₃]^4– anions. The oxotetrelate thallides can be regarded as “double salts”, which consist of Cs₆Tl₆ on one side and respective oxosilicates, ‐germanates and ‐stannates on the other, showing almost not any direct interaction between the two anionic moieties, as might be expressed e.g. by the formula [Cs₆Tl₆][Cs₄SiO₄]. In contrast to the silicon and germanium compounds, where the oxidation state of the tetrel atom is unambiguously 4+, for the threefold coordinated tin atom in Cs₁₀Tl₆SnO₃ an oxidation state of 2+ has to be assumed. Thus, the latter reveal further evidence that the so called “hypoelectronic” [Tl₆]^6– cluster does not require additional electrons and is intrinsically stable. The distortion of [Tl₆]^6– can be understood in terms of the Jahn–Teller theorem. According to magnetic measurements all title compounds are diamagnetic.     

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)°.     

(H3O)3Sb2Br9: the first member of the M3E2X9 structure family with oxonium cations

(H₃O)₃Sb₂Br₉ [trihydroxonium enneabromidodiantimonate(III)] is the first representative of the M₃E₂X₉ family (M = cation, E = Sb and Bi, and X = Br and I) with oxonium cations. The metastable compound was obtained in trace amounts from a solution of CsBr and SbBr₃ in concentrated aqueous HBr. Single crystals were isolated from the mother liquor and investigated by single‐crystal X‐ray diffraction at 100 K. (H₃O)₃Sb₂Br₉ crystallizes with the Tl₃Bi₂I₉ structure type, which is a distorted defect variant of cubic perovskite. The crystal structure comprises characteristic ²_∞[SbBr₃Br_3/2] double layers of corner‐sharing SbBr₆ octahedra with a [001] stacking direction. Due to the small size of the H₃O⁺ cation and O—H…Br hydrogen bonding, the octahedra are tilted.     

Anionic Diversity in Iodobismuthate Chemistry

Three salts containing different iodobismuthate anions have been synthesized. [(CH₃)₂NH₂]₃[BiI₆] was prepared by oxidation of bismuth by iodine in N,N‐dimethylformamide. [(CH₃)₂NH₂]₃[BiI₆] crystallizes in the space group with a = 30.760(3) Å and c = 8.8039(5) Å and contains monomeric [BiI₆]^3? anions. The hydrate Na₄[Bi₂I₁₀] · 14H₂O was prepared by the oxidation of bismuth using iodine in acetonitrile in the presence of NaI. Na₄[Bi₂I₁₀] · 14H₂O crystallizes in the space group C2/m with a = 12.875(2) Å, b = 16.177(2) Å, c = 9.904(2) Å and β = 106.57(6)°. The structure contains dimeric [Bi₂I₁₀]^4? anions and rows of sodium ions, with bridging water molecules. The hydrate [Na{(CH₃)₂NCHO}₂(H₂O)]₃[Bi₂I₉] was prepared by dissolution of Na₄[Bi₂I₁₀] · 14H₂O in N,N‐dimethylformamide and crystallizes in the space group with a = 13.2309(13) Å, b = 13.3791(14) Å, c = 18.722(2) Å, α = 70.338(9)°, β = 72.651(9)° and γ = 62.183(5). The structure contains dimeric [Bi₂I₉]^3? anions and cationic polymers, equation/tex2gif-stack-1.gif[Na{(CH₃)₂NCHO}₂(H₂O)]⁺.     

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.     

Isolated Triiodide and Pentaiodide Anions in the Crystal Structure of [Rb(Dibenzopyridino‐18‐Crown‐6)2]2(I3)(I5)

Red shiny crystals of [Rb(dibenzopyridino‐18‐crown‐6)₂]₂(I₃)(I₅) were obtained from a dichloromethane/ethanol solution of RbI, I₂ and dibenzopyridino‐18‐crown‐6. Triclinic, , a = 1494.3(1), b = 1534.1(1), c = 2412.9(2) pm, α = 76.95(1), β = 83.58(1), γ = 68.67(1)°, V = 5016.7(7) 10⁶·pm³, Z = 2. The crystal structure consists of [Rb(dbp18c6)₂]⁺ cations leaving suitable three‐dimensional channels for the linear I₃⁻ and V‐shaped I₅⁻ anions which are isolated from each other.     

Tl5SnF9 und Tl5TiF9: die ersten [Tl5F3]2+‐Schichten in neuartigen Thallium(I)‐fluoridfluorometallaten(IV)

Tl₅SnF₉ and Tl₅TiF₉: The First [Tl₅F₃]²⁺ Layers in Novel Thallium(I) Fluoridefluorometallates(IV) Tl₅TiF₉ and Tl₅SnF₉ were prepared via solid state reactions from mixed powders of the TlF and SnF₄ or TiF₄, respectively, in platinum crucibles under Ar (573 K). Both fluorides are colourless, transparent and extremely hygroscopic. The compounds Tl₅MF₉ (M = Sn, Ti) crystallize in a new structure type in Pbam (Nr. 55) with a = 1117.6 pm, b = 684.8 pm, c = 799.2 pm for Tl₅SnF₉ and a = 1111.4 pm, b = 674.7 pm, c = 783.2 pm for Tl₅TiF₉. Characteristic building units in the new Thallium(I) fluoridefluorometallates(IV) are [Tl₅F₃]²⁺ sheets found for the first time, which are connected via [MF₆]^2– octahedra (M = Ti, Sn) to a threedimensional network (d_Sn–F = 194–197 pm, d_Ti–F = 186–187 pm). The monovalent Tl are coordinated by 8 F with distances Tl–F between 264 and 334 pm. The chemical bonding is discussed on the basis of Extended‐Hückel band structure calculations.     

Synthese und Strukturuntersuchungen von Iodocupraten (I). XI. Die Kristallstruktur von Tl4Cu2I6

Syntheses and Structure Analyses of Iodocuprates (I). XI. Crystal Structure of Tl₄Cu₂I₆ Tl₄Cu₂I₆ was prepared by melting TlI and CuI or by hydrothermal synthesis in concentratet aqueous HI solution. The crystal structure analysis of Tl₄Cu₂I₆ (orthorhombic, Pnnm, a = 919.6(1), b = 955.2(2), c = 933.6(2) pm, Z = 2) shows that the compound contains dinuclear anions [Cu₂I₆]^4? which are built up by edge sharing CuI₄-tetrahedra. The coordination of Tl^I with I^? is analogous to the yellow TlI.     

Die Kristallstrukturen von Tl2AgI3 und NaAgI2 · 3 H2O

Crystal Structure Investigations of Tl₂AgI₃ und NaAgI₂ · 3 H₂O Tl₂AgI₃ was synthesized by the reaction of TlI with AgI in aqueous HI (25%) in a pressure vessel. The compound crystallizes in the rhombohedral space group R3 ; a = 1044,3(2); c = 1993,5(3)pm; Z = 9. The crystal structure contains trinuclear anions [Ag₃I₈]^5? and [ITl₆]⁵⁺ octahedra. The anions are composed of two AgI₄-tetrahedra which are connected to an AgI₆ octahedron via common faces. Single crystals of NaAgI₂ · 3 H₂O were formed by reaction of NaI with AgI in aqueous solution. The compound crystallizes in the orthorhombic space group Pbca with lattice parameters a = 711,2(2); b = 939,8(3); c = 2462,2(4) pm; Z = 8. The crystal structure is built up by polymeric layers [AgI_3/3I_½^1/2?] of corner sharing AgI₄ tetrahedra (GaOCl type) and [Na(H₂O)_4/2(H₂O)I_½^1/2+] octahedra chains.     

Structural Variety of Defect Perovskite Variants M3E2X9 (M = Rb,Tl, E = Bi,Sb, X = Br,I)

The compounds Rb₃Sb₂Br₉, Rb₃Sb₂I₉, Rb₃Bi₂Br₉, Rb₃Bi₂I₉, and Tl₃Bi₂Br₉ were synthesized and their crystal structures determined from single crystal X‐ray diffraction data. The compounds Rb₃Sb₂Br₉, Rb₃Sb₂I₉, and Rb₃Bi₂I₉ crystallize in the Tl₃Bi₂I₉ type of structure (space group P2₁/n, no. 14). Rb₃Bi₂Br₉ and Tl₃Bi₂Br₉ crystallize in a new but closely related type of structure (space group P2₁/a, no. 14). Both structure types feature characteristic double layers comprising corner‐sharing EX₆ octahedra. The space groups are set in a way that the stacking direction of the layers is the [001] direction. The group‐subgroup relations to cubic perovskite ABO₃ are discussed. Differences between M₃E₂X₉ types are attributed to distortions of the underlying MX₃ close packing. Depending on the atomic size ratio, the distortions are quantified by an order parameter.     

Crystal Structure Determination of Thallium Carbodiimide,Tl2NCN

Orange‐red single crystals of thallium carbodiimide, Tl₂NCN, have been grown from an aqueous solution of cyanamide and thallium carbonate under strongly basic conditions. Tl₂NCN crystallizes in space group with a = 5.338(1), b = 6.626(2), c = 9.645(3) Å, α = 98.765(4)°, β = 98.685(4)°, γ = 113.178(4)°, and Z = 3; the structure can be considered a strongly distorted anti‐CdI₂ type. One finds two crystallographically different and irregular [NCN]Tl₆ octahedra in which the Tl–N distances of the three‐coordinate monovalent thallium ions lie between 2.52 and 2.72Å. The two symmetry‐inequivalent NCN^2? units adopt the carbodiimide shape, and the course of its molar volume as a function of the monovalent counter cation is analyzed.     

Low‐Temperature Topochemical Transformation of Bi13Pt3I7 into the New Layered Honeycomb Metal Bi12Pt3I5

Ordered single‐crystals of the metallic subiodide Bi₁₃Pt₃I₇ were grown and treated with n‐butyllithium. At 45 °C, complete pseudomorphosis to Bi₁₂Pt₃I₅ was achieved within two days. The new compound is air‐stable and contains the same ${{{\hfill 2\atop \hfill \infty }}}$ [(PtBi_8/2)₃I]ⁿ⁺ honeycomb nets and iodide layers as the starting material Bi₁₃Pt₃I₇, but does not include ${{{\hfill 1\atop \hfill \infty }}}$ [BiI₂I_4/2]^? iodidobismuthate strands. Electron microscopy and X‐ray diffraction studies of solid intermediates visualize the process of the topochemical crystal‐to‐crystal transformation. In the electronic band structures of Bi₁₃Pt₃I₇ and Bi₁₂Pt₃I₅, the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi₁₃Pt₃I₇ into Bi₁₂Pt₃I₅, the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi₁₃Pt₃I₇ the intermetallic layers do not interact across the iodidobismuthate spacers (two‐dimensional metal), they couple in Bi₁₂Pt₃I₅ and form a three‐dimensional metal.     

Bi13Pt3I7: Ein Subiodid mit einer pseudosymmetrischen Schichtstruktur

Bi₁₃Pt₃I₇: A Subiodide with a Pseudo-Symmetric Layer Structure The reaction of PtI₂ with Bi and BiI at 630 K yields black, lustrous, air insensitive crystals of the subiodide Bi₁₃Pt₃I₇. The layered crystal structure (triclinic, C1 , a = 1581.0(2) pm, b = 912.6(1) pm, c = 2149.6(6) pm, α = 90.03(2)°, β = 96.96(2)°, γ = 90.11(1)°, V = 3078.6 · 10⁶ pm³) contains edge-sharing [PtBi_8/2] cubes, which form nets of Kagomé type. Iodine atoms fill the hexagonal-prismatic voids therein. These [(PtBi_8/2)₃I] layers are alternately separated by layers of iodine atoms or [BiI] zigzag-chains. The marked pseudo-symmetry of the structure favours stacking faults, which cause streaks of diffuse scattering in the diffraction pattern.     

(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.