Bi12,86Ni4Br6 und Bi12,86Ni4I6: Subhalogenide mit intermetallischen und salzartigen Schichtpaketen in alternierender Abfolge

Bi_12.86Ni₄Br₆ and Bi_12.86Ni₄I₆: Subhalides with Alternating Intermetallic and Salt‐like Layers The reaction of bismuth and nickel with bromine or iodine at 730 K yields black, air insensitive, needle shaped crystals of the ternary subhalides Bi_12.86Ni₄X₆ (X = Br, I). The isotypic compounds crystallize in the orthorhombic space groups Immm with a = 405.69(6) pm, b = 874.00(8) pm, c = 3744.7(4) pm for X = Br, and a = 410.05(5) pm, b = 912.84(7) pm, c = 3826.7(3) pm for X = I. The crystal structures contain characteristic fragments of the intermetallic phase Bi₃Ni: chains consisting of face‐sharing mono‐capped trigonal prisms of bismuth atoms with a nickel atom in the center of each prism. The chains form corrugated layers which are separated by halogen atoms and oligomeric [Bi_nX_4n+2] units of varying length. The halogenobismutate(III) units consist of trans‐edge‐sharing [BiX₆] octahedra. They are disordered within the crystal structures. The non‐integer stoichiometric coefficients of Bi_12.86Ni₄X₆ are due to the metric adjustment between the ionic and intermetallic parts of the structure. Extended Hückel calculations indicate, that the partial oxidation of the intermetallic phase causes a strengthening of the chemical bonding within the Bi₃Ni chains. The subiodide Bi_12.86Ni₄I₆ is paramagnetic and shows ferromagnetic ordering below 25 K.     

Bi4RuBr2 und Bi4RuI2: Zwei Varianten einer Kolumnarstruktur mit flächenverknüpften quadratischen [RuBi8/2]-Antiprismen

Bi₄RuBr₂ and Bi₄RuI₂: Two Varieties of a Column Structure with Face-Sharing [RuBi_8/2] Square Antiprisms Reaction of the elements yields black, lustrous, air insensitive crystals of the subhalides Bi₄RuI₂ (tetragonal, I4/m, a = 1183.9(2) pm, c = 669.7(2) pm, V = 938.66 · 10⁶ pm³) and Bi₄RuBr₂ (monoclinic, I112/m, a = 1211.9(2) pm, b = 1072.6(2) pm, c = 663.9(2) pm, γ = 91.63(1)°, V = 862.64 · 10⁶ pm³). The structures of the homöotypic compounds contain [RuBi_8/2] strands of face-sharing square antiprisms. Halogen atoms lie above the edges of alternate Bi₄ squares. Thereby chemical bonding differs significantly within the two types of Bi₄ squares. Though the Ru atoms on the central axis of the strand of antiprisms form pairs, extended Hückel calculations give no evidence of Ru? Ru bonds.     

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.     

The crystal structure of Bi14I4 condensed bismuth clusters

The crystal structure of Bi₁₄I₄ — the final known member of binary bismuth halides — was determined by the single crystal X-ray diffractometer technique (P2₁/m, Z = 1, a = 13.309(3) Å, b = 11.447 (3) å, c = 4.342(1) å, γ = 92.08(3)°, R/R_w = 0.060/0.060 for 369 reflections, sinθ/λ≤ 0.593, MoKγ). The structure consists of condensed bismuth clusters and is build up from infinite one-dimensional bismuth nets running along the c-axis and limited by iodine atoms in another direction. The common structural features of bismuth subhalides containing condensed clusters are also considered based on the analysis of interatomic distances and bond angles. The influence of the lone pair of electrons of the bismuth atom on the geometry of bismuth coordination polyhedra, and the connection between bismuth atoms coordination and the formal oxidation state of these atoms is discussed.     

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.     

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.     

Crystal Structure of a New Cation-ordered Fluorite-related Phase: Bi2Te2WO10

Bi₂Te₂WO₁₀ crystallises in the monoclinic system (space group C2/c, Z = 4) with a = 12.4972(7) Å, b = 5.6414(3) Å, c = 12.2705(6) Å and β = 91.38(3)°. The structure has been solved by means of single crystal X-ray diffraction data analysis. The reliability factors are R1 = 0.030 and wR2 = 0.065 for 1258 structure factors and 70 parameters. The Bi₂Te₂WO₁₀ crystal structure can be described as a regular stacking along the Ox axis of polyhedral layers with the stereochemically active lone pairs E of the Bi^III and Te^IV atoms all located between these layers. The cohesion of the three-dimensional network is therefore only ensured between succesive layers by weak Bi? O(5) bonds.     

Eine weitere Oxovanadat-Phase mit Granatstruktur: Ca5Mg3ZnV6O24

An Additional Oxovanadate Phase with Garnet Structure: Ca₅Mg₃ZnV₆O₂₄ Single crystals of Ca₅Mg₃ZnV₆O₂₄ were prepared by solid state reactions some degree below the melting point of the reaction mixture. It crystallizes with cubic symmetry, space group T-I4 3 d with a = 12.429 Å, Z = 4. The crystal structure is nearly related to the Garnet structure showing Ca²⁺ within distorted cubes (C.N. = 8) of O^2? on a partly unfilled position. the octahedra position are occupied by Mg²⁺ and Zn²⁺ statistically.     

Crystal and electronic structure of Ni3Bi2S2 (parkerite)

The crystal structure of parkerite, Ni₃Bi₂S₂, was studied by single-crystal X-ray diffraction analysis and refined. The single crystal was prepared by the method of chemical transport reactions. The electronic structure of Ni₃Bi₂S₂ was calculated by the extended Hückel and DFT--LMTO--ASA methods. Substantial delocalization of electrons in the vicinity of the Fermi level and the presence of the strong Ni--S and Ni--Bi bonds were revealed. The Ni--Ni bonds are weak, which is in agreement with the X-ray diffraction data.     

Na7I2(OH)5: Ein Hydroxidiodid im System NaOH/NaI

Na₇I₂(OH)₅: A Hydroxide Iodide in the System NaOH/NaI The pseudobinary system NaOH/NaI is investigated by X-ray methods. The crystal structure of the compound Na₇I₂(OH)₅ was solved by single crystal data: Na₇I₂(OH)₅: P4/nmm, Z = 2, a = 7.748(2) Å, c = 10.260(3) Å, Z(F_o) = 443 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.044/0.059 Na₇I₂(OH)₅ crystallizes in a new type of structure which contains puckered layers of ∞²[Na₇(OH)₅²⁺] connected via iodide ions.     

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.     

Li2I(OH): Eine Verbindung mit eindimensional unendlich kantenverknüpften [Li4/2(OH)]+-Pyramiden

Li₂I(OH): A Compound with Onedimensional Infinite Edge Sharing [Li_4/2(OH)⁺] Pyramids The pseudobinary system LiOH/LiI was investigated by X-ray methods. Two compounds, Li₂I(OH) and Li₅I(OH)₄ exist. The structure of Li₂I(OH) was solved by single-crystal data. For Li₅I(OH)₄ lattice constants and space group symmetry are given: Li₂I(OH): Pnma, Z = 4, a = 10.339(4) Å, b = 5.567(1) Å, c = 6.643(2) Å, Z(F_o) mit (F_o)² ≧ 3σ(F_o)² = 439, Z (parameter) = 23, R/R_w = 0.030/0.040 Li₅I(OH)₄: Pmmn or P2₁mn(= Pmn2₁), Z = 2, a = 10.42 Å, b = 5.30 Å, c = 5.81 Å Li₂I(OH) crystallizes in a new type of structure. The motif of a distorted hexagonal close-packed arrangement of iodide ions is penetrated by chains of [Li_4/2(OH)⁺].     

[Ni(C_5H_5N)_2(C_7·H_6O_2N)_2]H_2O三元配合物的合成及晶体结构

合成了标题化合物。该化合物的分子式[Ni(C5H5N)2(C7H6O2N)2]H2O(C24H24N4NiO3),分子量475.18,采用单色的MoKα (λ = 0.71073 )射线测定,共收集7408个数据,其中独立衍射点2567个(Rint = 0.0272),I > 2s(I)可观测点数1926个,结果表明该化合物属单斜晶系, 空间群C2/c其晶胞参数为: a = 14.466(2),b = 12.193(2),c = 14.072(2) ;β = 116.229(2)°,V = 2226.6(5) 3,Z = 4,Dc = 1.418 g/cm3 ,μ = 0.905 mm-1,F(000) = 992. 2个水杨醛亚胺各提供2个配位原子参与配位,2个吡啶各提供1个配位原子参与配位,该配合物是六配位的八面体构型,同时讨论了该体系中不同配位原子的配位能力的差异。     

Pentacalciumhexaphosphahypodiphosphat,Ca5P8: Eine Verbindung mit isolierten Anionen P810− mit der gestaffelten Konformation von Ethan

Pentacalcium Hexaphosphahypodiphosphate, Ca₅P₈, a Compound with Isolated Anions P₈^10? in the Staggered Ethane Conformation Ca₅P₈ is prepared from calcium and red phosphorus in a molar ratio 5:8 in argon atmosphere in corundum crucibles inserted in quartz ampullae (3.5 d 1 000°C). It is a red-brown powder which is hydrolyzed by moisture. Single crystals are formed from powder at 1 100°C within 60 d. Ca₅P₈ crystallizes in a new structure type (mC26) with isolated anions P₈^10? in staggered conformation: C2/m (no. 12); a = 689.9(4) pm, b = 1 188,3(4) pm, c = 748.4(3) pm, β = 108.25(2)°, Z = 2; d = 2.56(1). Ca₅P₈ is the first compound containing polyphosphide anions with fourfold and single bonded phosphorus atoms (formally P⁺ and P^2?, resp.). The cations Ca²⁺ are arranged in a distorted cubic close-packing. The centers of the polyphosphide anions replace in an ordered way one third of Ca²⁺ in every second layer. The terminal P atoms occupy all octahedral interstices, so that P₈^10? is coordinated by 18 Ca²⁺ in form of a cuboctahedron with capped squaric faces.     

Das erste Alkali-Erdalkalimetall-Oxoniccolat(II,III): NaBa2Ni22+Ni3+O6

The First Alkalinc Alkaline Earth Oxoniccolate(II,III): NaBa₂Ni₂²⁺Ni³⁺O₆ Single crystals of NaBa₂Ni₂²⁺Ni³⁺O₆ were prepared by solid state reaction. X-ray investigations led to orthorhombic symmetry, space group D-Fmmm; a = 8.310; b = 11.220; c = 14.397 Å; Z = 8. Na⁺ is coordinated by six O^2? in form of a trigonal prism and the two Ba²⁺ point positions show different coordination numbers C.N. = 6 + 4 and 8. The Ni²⁺ /Ni³⁺ ions are in square planar polygons, six of them are forming a so far unknown closed macro polyhedra.     

Ba3P3I2 und Ba5P5I3: Stufenweise Oxidation von Bariumphosphid mit Iod

Ba₃P₃I₂ and Ba₅P₅I₃: Stepwise Oxidation of Barium Phosphide with Iodine The novel compounds Ba₃P₃I₂ and Ba₅P₅I₃ were obtained by the reaction of barium phosphide with iodine. The air and moisture sensitive compounds crystallize in new structure types: Ba₃P₃I₂ (oP32; Pnma; a = 1719.5(4) pm; b = 462.4(2) pm; c = 1427.2(4) pm; Z = 4; R(F)_N′ = 0.067 (N′(hkl) = 2667), Ba₅P₅I₃ (mC52; C2/m; a = 4266.4(13) pm; b = 456.3(2) pm; c = 943.1(3) pm; ß = 92.20(3)°; Z = 4; R(F)_N′ = 0.040 (N′(hkl) = 3909). Both can be described as double salts of a hypothetic Zintl Phase ('Ba₂P₃' or 'Ba₇P₁₀') and a halide (BaI₂). Characteristic structural features are P₃ and P₄ chains, corresponding to Ba₃[P₃]I₂ and Ba₁₀[P₃]₂[P₄]I₆, respectively. The bonding characteristics will be interpreted on the basis of the structure and the physical properties.     

Eine neue Verbindung vom M5TiB2O10-Typ mit geordneter Metallverteilung: Ni5SnB2O10

Summary The unknown compound Ni₅SnB₂O₁₀, prepared by using a flux of excess B₂O₃, was investigated by single crystal X-ray technique. It crystallizes with orthorhombic symmetry, space group D _2h ¹⁶ — Pnma witha=9.302,b=6.089,c=12.280 Å,Z=4. The mean result of this investigation is a hitherto unobserved strictly ordered metal distribution. Ni₅SnB₂O₁₀ is not isotypic but related to Ni₅TiB₂O₁₀.

     

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.     

[Hg(C5H4S5)I2]2的合成与晶体结构(C5H4S5 = 4,5-亚乙基二硫杂-1,3-二硫杂-2-硫酮)

用 HgI2 和 4,5-亚乙基二硫杂-1,3-二硫杂-2-硫酮 (C5H4S5)反应,合成一种二核汞配合物[Hg(C5H4S5)I2]2 1。X 射线衍射结果表明,晶体属于单斜晶系,C2/c 空间群,晶胞参数 a =21.6847(1),b = 8.5125(4),c = 15.6699(8),a=112.7850(1)°,V=2666.8(2) ?3。Mr = 1357.54,Z = 4,Dx = 3.381 g/cm3,ì = 16.913 cm–1,F(000) = 2400,R=0.0639,wR=0.1711,S=1.052。配合物 1 具有二聚体结构,2 个汞原子通过 2 个碘原子桥联,形成 1 个 Hg2I2菱形平面,汞原子周围的配位是四面体结构,通过分子间的硫…硫作用和碘…硫作用,形成准二维超分子网络。 S S S H g I I S S S S I I H g S     

新型氰基桥联配位聚合物[Ni(en)2]2[Ni(CN)4]2·5H2O的合成、晶体结构和磁性质

分子组装在材料科学、催化和生物化学中具有潜在的应用前景,所以分子组装引起了化学、固体物理学和生物学等领域科学家们的普遍关注犤1犦。分子组装常用的方法是使用具有配位能力的金属配合物作为建筑块与过渡金属阳离子反应。氰基桥联多核配合物由于其结构的多样性和具有特别优异的磁性质,近10年来在配位化学领域倍受关注犤2～8犦。在系列配合物犤M(en)2犦犤Ni(CN)4犦(M=Ni,Cu,Zn,Cd等)中,犤Cu(en)2犦犤Ni(CN)4犦和犤Cd(en)2犦犤Ni(CN)4犦的晶体结构已经通过单晶衍射的方法测得犤9,10犦。在犤Cu(en)2犦犤Ni(CN)4犦中,Cu原子为六配…