PrSeTe2, ein geordnetes ternäres Polychalkogenid mit NdTe3‐Struktur

PrSeTe₂, an Ordered Ternary Polychalcogenid with NdTe₃ Structure Single crystals of PrSeTe₂ have been obtained by reaction of the elements in a LiCl/RbCl flux at 970 K during 7 days. PrSeTe₂ crystallizes in space group Cmcm (No. 63), with four formula units per unit cell. The lattice constants are a = 426.1(1) pm, b = 2506.0(5) pm, and c = 426.0(1) pm. The crystal structure is an ordered ternary variant of the NdTe₃ type. It consists of a puckered double layer of praseodymium and selenium atoms [PrSe] sand wiched by two square planar layers of tellurium atoms [Te] yielding a stacking —[Te]—[Te]—[PrSe]— along [010]. The Te atoms build regular 4⁴ nets with Te—Te distances of 301, 3(1) pm. DFT calculations propose that this compounds should be metallic mainly due to contributions of the Pr f‐electrons. The band structure shows no significance for a distortion in the [Te]—nets.     

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.     

Die Kristallstrukturen von trans‐[NiBr2(Pyridin)4] und [Ni(HNPEt3)4]I2

Crystal Structures of trans ‐[NiBr₂(pyridine)₄] and [Ni(HNPEt₃)₄]I₂ Turquoise single crystals of trans‐[NiBr₂(pyridine)₄] have been obtained by the reaction of excess pyridine with nickel(II) bromide/diacetonealcohol. According to the crystal structure determination the nickel atom is octahedrally coordinated by the two bromine atoms in trans‐position and by the nitrogen atoms of the pyridine molecules. Space group Pna2₁, Z = 4, lattice dimensions at 20 °C: a = 1592.9(2), b = 943.8(1), c = 1413.0(2) pm, R₁ = 0.0492. Dark blue single crystals of the phosphoraneimine complex [Ni(HNPEt₃)₄]I₂ have been obtained from NiI₂/H₂O with excess Me₃SiNPEt₃ and subsequent recrystallization from acetonitrile. According to the crystal structure determination the nickel atom is tetrahedrally coordinated by the nitrogen atoms of the HNPEt₃ molecules. The iodide ions are connected via N–H…I contacts with the cation to form an ion triple. Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1934.9(2), b = 1078.3(1), c = 1966.3(2) pm, β = 111.040(8)°; R₁ = 0.043.     

Die trikline Kristallstruktur von Ag2Bi2S3Cl2: Pseudosymmetrie und Zwillingsbildung

Ruby‐red crystals of Ag₂Bi₂S₃Cl₂ were synthesized from AgCl and Bi₂S₃ by cooling a melt from 770 K to room temperature. X‐ray diffraction on powders and single‐crystals revealed a triclinic crystal structure with special lattice constants (P &1macr; (No. 2), a = 1085.0(2), b = 717.2(1), c = 1137.6(1) pm, α = 89.80(1)?, β = 74.80(1)?, γ = 87.81(1)?). In the structure [Bi^IIIS₃Cl₄] polyhedra form 2[BiS_3/2Cl_4/4]^‐ double‐layers by sharing common faces and edges. The silver(I) cations between the layers are coordinated either octahedrally by sulfide ions or tetrahedrally by sulfide and chloride ions. The deviations from the monoclinic space group P 1 2₁/c 1 are small and induce twinning along [010]. Further pseudosymmetry is based on the stacking of layer packages with the symmetry of the layer group P (2/c) 2₁/c 2/b.     

Crystal Structure and Vibrational Spectrum of Thallium(I) Europium(II) Tetrathiophosphate(V), TIEu[PS4]

TlEu[PS₄] was synthesized from the elements in a sealed quartz ampoule at 1 150 K. The compound forms transparent orange needles, stable in air and moisture. It crystallizes in the orthorhombic system, space group Pnma (No. 62), with cell dimensions a = 12.157(2), b = 6.581(1), c = 8.802(2) Å, Z = 4. The crystal structure consists of discrete [PS₄]^3? anions interconnected by Tl⁺ and Eu²⁺. The tetrahedral [PS₄]^3? groups are slightly distorted with P? S bond lengths in the range 2.028 to 2.043 Å. These tetrahedral anions are arranged in such a way that the sulfur atoms form columns of distorted trigonal S₆ prisms along [0 0 1]. The columns are condensed via common edges to puckered layers parallel to (1 0 0). The interlayer region consists of empty distorted half-cubes and tetrahedral holes, half of them filled by P atoms. The trigonal prisms in the columns are centered alternately by Tl⁺ and Eu²⁺. In this way, the structure can be regarded as an ordered superstructure of the InNi₂ type, where half of the tetrahedral holes are filled by phosphorus atoms: InInNi₄□ ? TlEuS₄P□. TlEu[PS₄] is a centrosymmetric variant of the TlSn[PS₄] structure type (space group Pna2₁). The vibrational spectrum is in accordance with the X-ray crystal structure, the Raman and infrared vibrations are assigned on the basis of [PS₄]^3? units with C_2v symmetry.     

[WNCl3 · 0,5 HN3]4; Kristallstruktur und IR-Spektrum

[WNCl₃ · 0.5 HN₃]₄: Crystal Structure and I.R. Spectrum [WNCl₃ · 0.5 HN₃]₄ is formed from tungsten hexachloride and iodine azide in dichloro methane solution yielding dark red and needleshaped crystals. The crystal structure was determined by aid of X-ray diffraction data. The compound crystallises in the triclinic space group P1 with one formula unit per unit cell (R = 0.08, 2 811 independent reflexions). The four metal atoms are arranged in a square, the edges being formed by almost linear W?N? W bridge bonds of alternating length (168 and 210 pm). Two opposite tungsten atoms are coordinated by theαN atom of a HN₃ molecule and by three terminal chloro ligands. The other tungsten atoms achieve coordination number 6 by two terminal and two bridging Cl atoms, linking the tetrameric units to bands along [010]. The i.r. spectrum is reported and assigned.     

Zur Struktur der basischen Diquecksilber(I)-nitrate. II. Kristallstruktur des Hg10(OH)4(NO3)6

Crystal Structure of the Basic Dimercury(I) Nitrates. II. Crystal Structure of Hg₁₀(OH)₄(NO₃)₆ . The crystal structure of Hg₁₀(OH)₄(NO₃)₆ has been determined from single crystal x-ray diffraction data. The unit cell is triclinic, space group P1 , a = 999.4(5), b = 909.9(5), c = 765.9(2) pm, α = 85.98(4), β = 78.70(3), γ = 109.83(5)°; Z = 1, R = 6.2%, R_w = 8.2%. Finite cationic chains [(Hg₂)₅(OH)₄(NO₃)₂]⁴⁺ are joined together by weak van der Waals-type interactions between neighbouring Hg and O atoms, thus forming ribbons running along [100]. The coordination sphere of the Hg atoms is completed by further nitrate ions, which lead to the formation of a loose framework. Thereby the metal atoms are not surrounded by simple coordination polyhedra.     

Kristallzucht und Strukturverfeinerung von Quecksilber(II)‐amidchlorid – HgClNH2

Crystal Growth and Refinement of the Crystal Structure of Mercury(II) Amide Chloride – HgClNH₂ Single crystals were prepared by recrystallization of HgClNH₂ from aqueous NH₃/NH₄⁺ solution at 160 °C. They were used for a single‐crystal X‐ray structure redetermination. The previously reported [W. N. Lipscomb, Acta. Crystallogr. 1951 , 4, 266.] structural topology determined on basis of X‐ray powder diffraction data is now confirmed. However, a higher symmetry is found: Space group type Pmma (instead of Pmm2), a = 6.709(1) Å, b = 4.351(1) Å, c = 5.154(1) Å, Z = 2. The crystal structure contains zig‐zag‐chains [Hg(NH₂)_2/2]⁺. Four Cl atoms complete the coordination sphere of Hg to a distorted octahedron. These share common faces and edges in layers [HgCl_4/4(NH₂)_2/2]. These layers are connected via hydrogen bonds N–H…Cl.     

Die Kristallstruktur von wasserfreiem Melaminiumchlorid

Crystal Structure of non‐aqueous Melaminium Chloride Melaminium chloride was obtained as colorless, needle‐shaped, single crystalline material from solid state reactions between melamin and ammonium chloride. The structure of [C₃N₆H₇]Cl was refined by single crystal X‐ray diffraction: I2/m, Z = 8, a = 852.87(4), b = 1704.4(1) c = 918.44(4) pm and β = 92.165(6)°. The crystal structure contains melaminium ions stacked to columns along [100] and linked via N‐H···N bridges to form bands along [001]. Both of the two distinct chloride ions are stabilized by six hydrogen bonds through distorted trigonal prismatic arrangements of hydrogen atoms to yield a supramolecular structure.     

Kristallstruktur und Pseudosymmetrie einer neuen Modifikation von Kaliumhexachloroniobat(V), KNbCl6. Anmerkungen zur kubischen Phase

Crystal Structure and Pseudosymmetry of a New Modification of Potassium Hexachloroniobate(V), KNbCl₆. Comments on the Cubic Phase Long needles of KNbCl₆ – invariably twinned around [100] – are obtained if the material is crystallized from SOCl₂ solution. The structure has been determined from X-ray data collected with a single-crystal diffractometer at room temperature [space group P2₁/n, Z = 16, a = 6.894(1), b = 22.073(4), c = 23.337(3) Å, β = 91.00(1)°, R = 0.032 for 2 909 unique reflexions, 290 structural parameters]. Distorted NbCl₆^? octahedra and ?interstitial’? K⁺ ions are found to form similar arrangements, each of them corresponding to a closest packing of spheres with the layer sequence ACAB (stacking symbol hc). The resulting asymmetry in coordination by potassium is coupled with a strong off-centre displacement of the Nb atoms in any of the four independent chlorine polyhedra (0.14 Å on average). A pronounced pseudosymmetry accounts for the twinning. Since P2₁/m2₁/n2₁/b (no. 62) is already a good approximation of the real structure, only one formal step of symmetry reduction (index t2) is needed to create both, the observed twin law and the actual space group P1 2₁/n1. Above 180°C a reconstructive phase transition leads to the ‘face-centred cubic’ modification with ～ 10% lower density.     

Die Kristall- und MolekülStruktur des Bis-(cis-1-mercapto-2-p-brombenzoyl-äthylen)-nickel(II)

Crystal and Molecular Structure of Bis(cis-1-mercapto-2-p-brominebenzoylethylen)nickel(II) From a x-ray analysis of bis(cis-1-mercapto-2-p-brominebenzoyl-ethylen)-nickel(II) distances Ni? S and Ni? O of 2.14 Å and 1.88 Å, respectively, follow for the planar square nickel complex Ni[S₂O₂]. The sulfur atoms are arranged in cis-position. The C? C distance in the sulfur neighbourhood is shortened, but the difference between the two C? C bonds in the chelate ring is less than in bis(thioisobutyrylacetonato)nickel(II). This indicates a strenthening of the quasiaromatic character in the chelate system of the investigated structure.     

Ein neues Bleistrontiumferrat(III): Die Kristallstruktur der Phase Pb4Sr2Fe6O15

A New Lead Strontium Ferrate(III): The Crystal Structure of the Phase Pb₄Sr₂Fe₆O₁₅ At orthorhombic single crystals of Pb₄Sr₂Fe₆O₁₅ (a = 568.73(8), b = 392.03(4), c = 2107.5(3) pm; Z = 4/3, space group Pnma) a X-ray structure determination has been performed (R₁ = 0,036 for 488 ?observed”? resp. wR₂ = 0,073 for all 643 independent reflexions). It revealed a framework of polyhedra related to perovskite, in which chains of edgesharing pyramids [FeO₅] (average Fe1? O: 197 pm; Fe1? Fe1: 305.5 pm) are linked via apices with corner-sharing [FeO₆] octahedra (Fe2? O: 201 pm). 12–fold, strongly distorted cuboctahedrally coordinated ?perovskite positions”? show mixed occupancy by 2/3 Sr + 1/3 Pb (= Sr2; Sr2? O: 287 pm). More spacy channels, running parallel to the chains of pyramids along [010] of the structure, contain lead atoms only. The double occupancy of the corresponding cages results in short distances Pb1? Pb1 (355.9 pm) and Pb1? Fe2 (314.4 pm), as well as in a very asymmetric [PbO₆] coordination (Pb1? O: 253 pm), in the opposite hemisphere of which the lone electron pair s² is supposed to be located. Details are communicated and structural relations discussed.     

Synthese und Kristallstruktur von Ammin(μ3‐L‐glutamato)kupfer(II)

Synthesis and Crystal Structure of Ammine(μ₃‐L‐glutamato)copper(II) [Cu(L‐Glu)H₂O]·H₂O reacts with aqueous ammonia to give the ammine complex [Cu(L‐Glu)NH₃] ( 1 ). 1 forms orthorhombic crystals, space group P 2₁2₁2 with a = 1585,1(1) pm; b = 979,46(7) pm and c = 504,70(5) pm. In the crystal structure of 1 the copper atoms are linked by μ₃‐glutamate units to give a 2D layer structure. The copper atoms exhibit a square‐pyramidal coordination with two N atoms and two O atoms in the base plane and one O atom at the apex of the pyramid. The crystal structure is stabilized by a 3D network of N–H···O hydrogen bridges.     

Zr6STe2 – ein zirconiumreiches Sulfidtellurid mit einer Zr3Te‐Teilstruktur vom Re3B‐Typ

Zr₆STe₂ – a Zirconium‐rich Sulfide Telluride with a Zr₃Te Partial Structure of the Re₃B Type Zr₆STe₂ is accessible through the reduction of a mixture of ZrTe₂ and ZrS₂ with zirconium in fused tantalum tubes at 1520 K. The spatially averaged crystal structure of Zr₆STe₂ is described in the space group Cmcm, a = 377.81(4), b = 1156.4(1), c = 887.96(8), Z = 2, Pearson symbol oC18, 320 reflexions (I > 2σ(I)), 22 variables, R_w(I) = 0.088. Zr₆STe₂ crystallizes in a unique structure type, which can be seen as a filled Re₃B type structure. The tellurium atoms are surrounded by nine zirconium atoms situated at the vertices of a distorted, tricapped trigonal prism. The Zr₉Te tetrakaidecahedra are connected by common triangular prism faces parallel [100], edges approximately along [001] and common vertices along [010], thus forming a three‐dimensional tetrakaidecahedral network [Zr_9/3Te], which is decisively stabilized by homonuclear Zr–Zr‐interactions. The tetrakaidecahedra are arranged in such a way, that Zr₆ octahedra occur. The octahedra are arranged into layers by sharing edges parallel [100] and vertices along [001]. As a result of a distortion of the structure, every second octahedron is expanded to such an extent as to be able to smoothly accommodate sulfur atoms. According to the modulation of the diffraction intensities, the vacancy ordering in adjacent layers of octahedra occurs independently of each other.     

Die Kristallstruktur von [BeCl2(15‐Krone‐5)]

Crystal Structure of [BeCl₂(15‐Crown‐5)] Single crystals of [BeCl₂(15‐crown‐5)] ( 1 ) were obtained from dichloromethane solutions of BeCl₂ in the presence of the equivalent amount of 15‐crown‐5 and characterized by IR spectroscopy and X‐ray diffraction. Space group P2₁/c, Z = 4, lattice dimensions at 100 K: a = 1036.2(1), b = 1071.1(1), c = 1360.1(1) pm, β = 109.86(1)°, R₁ = 0.0225. The structure determination shows no disorder, all hydrogen positions were refined isotropically. The results are in contrast to the previously reported crystal structure determination in the space group P2₁nb. The beryllium atom of 1 forms a BeO₂C₂ five‐membered heterocycle with terminal chlorine atoms to give a distorted tetrahedral coordination with distances Be–O 166.5(2), 169.9(2) pm, and Be–Cl 195.8(2), 197.8(2) pm. The structural results are in good agreement with DFT calculations on B3LYP/6‐311+G** level.     

Kristall- und Molekülstruktur von Bis[N-(diethylaminothiocarbonyl)-N′-phenylbenzamidinato]nickel(II)

Crystal and Molecular Structure of Bis[N-(diethylaminothiocarbonyl)-N′-phenyl-benz-amidinato]nickel(II) The structure of bis[N-(diethylaminothiocarbonyl)-N′-phenyl-benzamidinato]-nickel(II) has been determined by X-ray structure analysis. The compound crystallizes in orthorhombic space group P2₁2₁2₁ with a = 16.36, b = 16.94, c = 12.96 Å and Z = 4. The solution of the structure was performed by heavy atom technique and gave a final R value of R = 0.055 for 1764 observed reflections. The coordination polyhedron has a tetrahedrally distorted shape. The ligator atoms are arranged in cis position. The chelate rings deviate clearly from planarity. Against the chelate rings the phenyl rings are appreciably twisted. The title compound is compared regarding its structure with the analogous copper chelate.     

Die Kristallstruktur des Trimethylzinn-methansulfinats, (CH3)3Sn02SCH3

The Crystal Structure of Trimethyltin Methanesulfinate, (CH₃)₃SnO₂SCH₃ Trimethyltin methanesulfinate, (CH₃)₃SnO₂SCH₃ crystallizes orthorhombie in the space group A2₁22. The lattice constants are: a = 7.98 ± 0.01, b = 12.59 ± 0.02 and c = 17.83 ± 0.02 Å Within the crystal structure the Sn atoms are linked together via bridging RSO₂ groups to form a helical chain along [l00]. Each Sn atom is surrounded by three C and two 0 atoms in a trigonal bipyramidal arrangement. The Sn? C distances are in the range from 2.09 to 2.18 Å the Sn? 0 distance amounts to 2.23 Å.     

Synthese,Struktur und Phasenumwandlung von Te4[AsF6]2·SO2

Synthesis, Crystal Structure, and Solid State Phase Transition of Te₄[AsF₆]₂·SO₂ The oxidation of tellurium with AsF₅ in liquid SO₂ yields Te₄²⁺[AsF₆^—]₂ which can be crystallized from the solution in form of dark red crystals as the SO₂ solvate. The crystals are very sensitive against air and easily lose SO₂, so handling under SO₂ atmosphere or cooling is required. The crystal structure was determined at ambient temperature, at 153 K, and at 98 K. Above 127 K Te₄[AsF₆]₂·SO₂ crystallizes orthorhombic (Pnma, a = 899.2(1), b = 978.79(6), c = 1871.61(1) pm, V = 1647.13(2)·10⁶pm³ at 297 K, Z = 4). The structure consists of square‐planar Te₄²⁺ ions (Te‐Te 266 pm), octahedral [AsF₆]^— ions and of SO₂ molecules which coordinate the Te₄ rings with their O atoms in bridging positions over the edges of the square. At room temperature one of the two crystallographically independent [AsF₆]^— ions shows rotational disorder which on cooling to 153 K is not completely resolved. At 127 K Te₄[AsF₆]₂·SO₂ undergoes a solid state phase transition into a monoclinic structure (P112₁/a, a = 866.17(8), b = 983.93(5), c = 1869.10(6) pm, γ = 96.36(2)°, V = 1554, 2(2)·10⁶ pm³ at 98 K, Z = 4). All [AsF₆]^— ions are ordered in the low temperature form. Despite a direct supergroup‐subgroup relationship exists between the space groups, the phase transition is of first order with discontinuous changes in the lattice parameters. The phase transition is accompanied by crystal twinning. The main difference between the two structures lies in the different coordination of the Te₄²⁺ ion by O and F atoms of neighbored SO₂ and [AsF₆]^— molecules.     

A new rhombohedral modification of EuNi5In

A rhombohedral modification of europium pentanickel indide, r‐EuNi₅In, crystallizes in the Rm space group and adopts the UCu₅In structure type. The structure is closely related to the hexagonal, h‐EuNi₅In, form (CeNi₅Sn type). Both EuNi₅In modifications are composed of CaCu₅ (EuNi₅)‐, MgCu₂ (InNi₂)‐ and NiAs (EuNi)‐type slabs in a 1:2:1 ratio. The atoms in the structure have high coordination numbers, viz. 20 and 18 for europium, 14 for indium, and 12 and 10 for nickel. The structure features a two‐dimensional network of ²_∞[Ni₈] tetrahedral clusters arranged in the ab plane.     

Die Kristallstruktur von K[F5W(≡NCl)]

Crystal Structure of K[F₅W(≡NCl)] Orange single crystals of K[F₅W(≡NCl)] have been formed as a by‐product from the reaction of tungsten nitrido chloride, WNCl₃, with Me₃SnF in the presence of potassium fluoride in toluene suspension. K[F₅W(≡NCl)] crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. Lattice dimensions at –83 °C: a = 1145.9(3), b = 770.4(2), c = 772.5(2) pm, β = 99.91(1)°, R₁ = 0.0742. The compound forms an ionic structure with octahedral [F₅W(≡NCl)]^– ions with a nearly linear arrangement of the N‐chloroimido ligand group W≡N–Cl (bond angle 173°, WN distance 174 pm). The K⁺ ions link the anions via K…F contacts and coordination number eight to form double layers along [100]. The layers itself are associated by short bounding Cl…F contacts of 279 pm.