The Crystal Structure of Tl2Te3 – a Reinvestigation

Crystals of the title compound were obtained by annealing a powder of Tl₂Te₃ in a vertical temperature gradient (230 °C–240 °C, 4 weeks). Tl₂Te₃ crystallizes in space group C2/c with lattice parameters of a = 13.275(1) Å, b = 6.562(1) Å, c = 7.918(1) Å, and β = 107.14°(2). The tellurium atoms form chains [Te₃^2–], consisting of interconnected linear triatomic · Te–^Te–Te · groups which are isosteric with XeF₂. The Te–Te distances of the XeF₂-like units are 3.02 Å, the connecting ones 2.83 Å.     

Structural Relations in the Family of Nonmetallic Filled β-Manganese Phases: The new members AGa6Te10 (A: Sn,Pb) and PbIn6Te10

Nonmetallic filled β-manganese phases form a new class of solids with a wide spaced (“eutactical”) partial structure of nonmetal atoms (Te, I), which is topologically equivalent to the arrangement of manganese atoms in cubic β-Mn (a = 6.315 Å, P4₁32, Z = 20), a manganese polymorph crystallizing in a tetrahedrally close packed structure. Different fractions of the 100 tetrahedral and 4 metaprismatic holes per unit cell of the β-Mn like arrangement of nonmetal atoms are occupied by metal atoms or pairs of covalently bonded metal atoms, leading to the different chemical compositions M₇Te₁₀, AM₆Te₁₀, Ag₂Ga₆Te₁₀, RbX₄I₅ (M: Al, Ga, In; A: Ca, Pb, Sn; X: Ag, Cu;). Basic structural properties and structural relations between the members of this new family of solids are discussed. In addition we present structural data for three new members of the family of filled β-Mn phases: SnGa₆Te₁₀ (single crystal data: a = 10.203 Å, α = 89.94°, space group R32, Z = 2) PbIn₆Te₁₀ (single crystal data: a = 10.619 Å, R32, Z = 2) and PbGa₆Te₁₀ (powder data: a = 10.237 Å, α = 89.93°, R32, Z = 2).     

Darstellung und Kristallstruktur von CsTe4

Preparation and Crystal Structure of CsTe₄ CsTe₄ results from a melting reaction at 570°C in sealed quartztubes. The starting materials Cs and Te in the molar ratio 1:4 are produced in a first step by controlled decomposition of the CsN₃ from mixtures of CsN₃ and Te (1:4) at 350°C. CsTe₄ is monoclinic, space group P2₁/c, with a = 7.857(1) Å, b = 7.286(1) Å, c = 14.155(2) Å, β = 93.83(1)°, and Z = 4. The tellurium atoms form a two-dimensional puckered layer built of from pseudo-trigonal-bipyramidal, T-shaped units Te₄^?. The central tellurium atom of this unit may be considered as a pseudo iodine. The compound is compared with other tellurides MTe_n having some like that unexpected principles of connection.     

The crystal structures of AuTe2Cl and AuTe2I

The structures of AuTe₂Cl and AuTe₂I have been determined. Both compounds are orthorhombic: for AuTe₂Cl, a = 4.020 Å, b = 11.867 Å, c = 8.773Å, Z = 4, space group Cmcm; for AuTe₂I, a = 4.056 Å, b = 12.579 Å, c = 4.741 Å, Z = 2, Pmmb. Intensities were measured on an automatic diffractometer, and the structures were refined, with anisotropic temperature factors, to R = 2.1% and R = 3.5%, respectively. The structures consist essentially of corrugated two-dimensional nets of gold and tellurium atoms, with interleaving halogen atoms. The tellurium atoms form pairs coordinated to four gold atoms, and each gold atom is coordinated to four tellurium atoms.     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Mono and Poly‐nuclear Silver(I) Complexes with Thiosaccharin and Triphenylphosphine. Synthesis,Spectroscopic and Structural Characterization of Thiosaccharinato‐bis(triphenylphosphine)silver(I) and Tetrakis{thiosaccharinato(triphenylphosphine)silver(I)}

The reaction of Ag₆(tsac)₆ ( 1 ) (tsac = thiosaccharinate anion) with triphenylphosphine gives rise to the already reported [Ag(tsac)(PPh₃)₃] complex ( 2 ) and to two new silver‐thiosaccharinate‐phosphine complexes, [Ag(tsac)(PPh₃)₂] ( 3 ) and [Ag₄(tsac)₄(PPh₃)₄] ( 4 ) (PPh₃= triphenylphosphine). Spectroscopic characterization was carried out using IR, UV‐Visible and NMR techniques and confirmed by single crystal X‐ray diffraction. In each complex a singular coordination mode for the thiosaccharinate ligand is observed. The most important features of the different coordination modes of the thionates are discussed. Compound 3 crystallizes in monoclinic system, space group Pn, with a = 11.2293(3) Å, b = 12.7282(3) Å, c = 13.6056(4) Å, β = 94.985(2)°, Z = 2; while crystals of compound 4 are monoclinic, space group P2₁/n, a = 15.024(3) Å, b = 14.681(3) Å, c = 21.914(4) Å, β = 95.31(3)°, Z = 2. The coordination around the silver atoms in both complexes consists of almost trigonal‐planar arrangements, AgP₂S in 3 and AgS₂P in 4 .     

New Silver Tellurates – The Crystal Structures of a Third Modification of Ag2Te2O6 and of Ag4TeO5

Single crystals of a third modification of Ag₂Te₂O₆ (denoted as Ag₂Te₂O₆–III) and of Ag₄TeO₅ have been obtained as minor by‐products during hydrothermal phase formation experiments in the system Ag‐Hg‐Te‐O. The crystal structure of Ag₂Te₂O₆–III (P2₁/c, Z = 4, a = 6.4255(10), b = 6.9852(11), c = 13.204(2) Å, β = 90.090(3)°, 1885 independent reflections, R[F² > 2σ(F²)] = 0.0334, wR2(F² all) = 0.0817) comprises tellurium in oxidation states +IV and +VI and is topologically related to the structure of the Ag₂Te₂O₆–I modification, which consists of similar layers and interjacent layers of Ag⁺ cations. Ag₄TeO₅ (C2/c, Z = 8, a = 16.271(2), b = 6.0874(10), c = 11.4373(16) Å, β = 106.730(10)°, 2372 independent reflections, R[F² > 2σ(F²)] = 0.0288, wR2(F² all) = 0.0737) is made up of a layer‐like arrangement of isolated [Te^VI₂O₁₀] double octahedra and of Ag⁺ cations situated both in layers parallel and inside the layers of the anionic moieties.     

CuClS0.94Te1.06 und CuBrS0.92Te1.08, zwei neue Kupfer(I)-chalkogenhalogenide mit neutralen [STe]-Schrauben

CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08, Two New Copper(I) Chalcogen Halides Containing Neutral [STe] Screws CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P2₁/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) ų (CuClS_0.94Te_1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) ų (CuBrS_0.92Te_1.08), both with Z = 4. The crystal structures are dominated by ordered [STe^±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS_0.94Te_1.06) and 336 °C (CuBrS_0.92Te_1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.     

Silver(I) Complexes of Schiff Bases Derived from Thiophene-2,5-dicarboxaldehyde and Furan-2,5-dicarboxaldehyde

The reactions of Schiff bases, derived by the condensation of thiophene-2,5-dicarbaldehyde and furan-2,5-dicarbaldehyde with 2-thienylmethylamine or 2-furanmethylamine, with silver nitrate have been studied in refluxing anhydrous methanol under nitrogen atmosphere. Complexes thus formed have been isolated and characterized by elemental analysis, electrical conductance, cyclic voltammetry, and ¹H NMR, ¹³C NMR, IR, LTV-Vis, and mass spectroscopic studies. The experimental results reveal that the complexes are primarily ionic in nature, consisting of (L)₃Ag₂ dication and Ag(NO₃)₃ negatively charged dianions. The molecular structure of one of the complexes, [((C₄H₃O)CH₂N? CH(C₄H₂S)CH? NCH₂(C₄H₃O))₃Ag₂] [Ag(NO₃)₃] has been studied in the solid state. The complex is crystallized in the triclinic space group $ {\rm P}\bar 1 $ with a = 12.889(7) Å, b = 14.884(5) Å, c = 15.084(6) Å, α = 92.18(4)°, β = 79.78(4)°, γ = 110.92(4)°. The structure is disordered. Each Ag in dication is tri-coordinated by three azomethine N atoms from three ligands, and each ligand employs two azomethine N atoms to coordinate to two Ag ions such that the geometry around the Ag ?Ag axis conforms to a propeller-shape. The two Ag ions are between the two N₃ planes with Ag ? Ag distance ca. 4.8.1 Å. There is no bonding between any Ag ion and any thiophene of the three ligands. However, two Ag ions and three thiophene S atoms form a trigonal bipyramidal geometry.     

Synthese monomerer Silber(I)‐Halogenid‐Komplexe mit T‐förmigem Bau – Kristallstrukturanalyse von [P(C6H4CH2NMe2‐2)3]AgBr

Synthesis of Monomeric T‐Shaped Silver(I) Halide Complexes – Crystal Structure Analysis of [P(C₆H₄CH₂NMe₂‐2)₃]AgBr Treatment of the tetrapodal phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 1 ) with equimolar amounts of the silver(I) halides AgX ( 2 a : X = Cl, 2 b : X = Br) produces in tetrahydrofuran at 25 °C the monomeric silver(I) complexes [P(C₆H₄CH₂NMe₂‐2)₃]AgX with planar coordination at the Ag atoms ( 3 a : X = Cl, 3 b : X = Br) in excellent yields. From complex 3 b a single X‐ray crystal structure analysis was carried out. Mononuclear 3 b crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 14.504(6), b = 11.034(3), c = 17.604(5) Å, β = 102.86(4)°; V = 2746.6(16) ų; Z = 4; 2953 observed unique reflections, R₁ = 0.0805. Complex 3 b consists of monomeric sub‐units with a planar T‐shaped arrangement formed by the atoms Ag1, N1, P1 as well as Br1, whereby the P1–Ag1–Br1 array is almost linear orientated.     

Transition metal complexes with bidentate ligands spanning trans-positions part XV X-ray structural and 31P-NMR solution studies of some three-coordinate silver complexes of 2,11-bis[di(tert-butyl)phosphinomethyl]benzo[c]phenathrene and related ligands

A series of three-coordinate bis(dialkylphosphinomethyl)benzo[c]phenanthrene Ag(I) complexes, alkyl= t-Bu, (1b) , and cyclohexyl, (1c) , anion = BF₄, CIO₄, CIO₄, NO₃, Cl, Br, I, have been prepared and thier ³¹ P-NMR characteristics recorded. The solid state structures of [Ag( 1b )Br], [Ag( 1b )Cl] and [Ag( 1b )CIO₄] have been determined by X-ray diffraction. The Ag atom in these complexes shows distorted trigonal geometry. Selected bond lengths and angles are as follows: Ag-P = 2.463(4) Å and 2.433(5) Å, P-Ag-P=141.6(2)° in the bromo complex, Ag-P = 2.457(2) Å and 2.427(2) Å, P-Ag-P = 142.6(1)° ion the chloro complex, and Ag-P = 2.394(2) and 2.393 (2) Å, P-AG-P = 161.5(1)° in the perchlorato complex.     

Die Tieftemperaturmodifikationen von Ag6Si2O7 und Ag6Ge2O7 – Darstellung,Kristallstruktur und Vergleich der Ag?Ag-Abstände

On the Low Temperature Modifications of Ag₆Si₂O₇ and Ag₆Ge₂O₇ – Synthesis, Crystal Structure, and Comparison of Ag? Ag Distances For the first time, single crystals of Ag₆Si₂O₇ and Ag₆Ge₂O₇ have been obtained by solid state reactions of the binary oxides at temperatures of 350°C while applying oxygen pressures of 700 bar. According to the results of X-ray crystal structure determinations both compounds crystallize isostructural in P2₁ (Ag₆Si₂O₇: a = 5.3043(5) Å, b = 9.7533(7) Å, c = 15.9283(13) Å, β = 91.165(8)°, 3881 independent reflections, R1 = 3.3%, wR2 = 7.2%; Ag₆Ge₂O₇: a = 5.3713(4) Å, b = 9.9835(8) Å, c = 16.2249(14) Å, β = 90.904(8)°, 2111 independent reflections, R1 = 4.3%, wR2 = 6.0%, Z = 4). The crystal structures contain two independent M₂O₇^6? anions, one in a staggered, and the other in an ecliptic conformation. The cationic partial structure may be described as a distorted bcc arrangement of Ag⁺ and M⁴⁺. Comparison of the structures with respect to the Ag? Ag separations reveals the latter to be probably due to intrinsic d¹⁰–d¹⁰ bonding interactions as far as the range of 2.89 Å to 3.25 Å is considered.     

Syntheses,Structures and Spectroscopic Studies of Silver(I) Coordination Polymers Bridged by Flexible Bidentate Ligands

The reaction of Ag₂SO₄ and bpp (bpp = 1,3‐bis(4‐pyridyl)propane) in H₂O afforded the complex [Ag₂(bpp)₂(SO₄) · 6.5H₂O·CH₃OH]_n, 1. The IR and TGA have been recorded and the structure has been determined. Crystal data for 1: Space group C₂/c, a = 17.885(4), b = 25.230(6), c = 8.832(2) Å, β = 105.437(4)°. V = 3841(1) ų, Z = 8 with final residuals R1 = 0.0710 and wR2 = 0.1620. The complex shows a three‐dimensional supramoleclar structure constructed with two‐dimensional infinite [Ag₂(bpp)₂]_n sheetlike layers pillared by Ag‐Ag interactions and Ag····O (SO₄) interactions in the solid state.     

CuClSe1.53Te0.47 and CuClSe0.56Te1.44: Structural and Vibrational Spectroscopic Investigations on Copper(I) Chalcogen Chlorides

CuClSe_1.53Te_0.47 and CuClSe_0.56Te_1.44 are obtained from the reaction of CuCl, Se, and Te in stoichiometric amounts. Both copper(I) selenium tellurium chlorides are monoclinic, space group P2₁/n (no. 14) with lattice constants of a = 7.837(1) Å, b = 4.699(1) Å, c = 10.762(2) Å, β = 104.37(2)°, V = 383.9(1) ų (CuClSe_1.53Te_0.47), and a = 8.074(1) Å, b = 4.830(1) Å, c = 10.973(1) Å, β = 103.87(2)°, V = 415.5(1) ų (CuClSe_0.56Te_1.44), and Z = 4. A common feature of these isostructural compounds are heteroatomic strands [YY'] (Y, Y' = chalcogen). These strands are running along [010] and are connected to layers by chains [CuCl]. Vibrational spectra of CuClSe_1.53Te_0.47, CuClSe_0.56Te_1.44, CuXTe₂ and CuX'Se₂ (X = Cl, Br, I; X' = Cl, Br) are analysed with respect to the bonding relations of the chalcogen chains. Modes derived from IR and Raman spectra are assigned by correlation with tri gonal Se and related copper(I) chalcogen halides. Both, X‐ray structural data and an analysis of the chalcogen vibrational modes in IR and Raman spectra, lead to a detailed insight into the ordering phenomena of the chalcogen chains in this type of copper(I) chalcogen halides.     

Structures of Iodophenyltellurium(II) and Diiododi-(β-naphtyl)tellurium(IV)

The reactions between diphenyl ditelluride, (PhTe)₂, or di(β-naphtyl)ditelluride, (β-naphtylTe)₂, with equivalent amounts of iodine have been reinvestigated and the crystal and molecular structures of iodophenyltellurium(II), (PhTeI)₄, and diiododi-(β-naphtyl)tellurium(IV), (β-naphtyl)₂TeI₂, have been determined. The structure of iodophenyltellurium(II) (space group Cc, a = 13.850(5) Å, b = 13.852(3) Å, c = 16.494(6) Å and β = 101.69(2)°, Z = 4) is built up by four PhTeI units which are linked by weak Te–Te interactions with Te–Te distances between 3.152(5) Å and 3.182(4) Å. The angles between the tellurium atoms are approximately 90° giving an almost perfect square. Long range secondary bonds (Te–I: about 4.2 Å) link the tetrameric units to give an infinite two-dimensional network. Iodo(β-naphtyl)tellurium(II) is less stable than the phenyl derivative. Solutions of this compound decompose under formation of elemental tellurium and (β-naphtyl)₂TeI₂. (β-Naphtyl)₂TeI₂ crystallises in the monoclinic space group C 2/c (a = 21.198(6) Å, b = 5.8921(8) Å, c = 16.651(5) Å, β = 114.77(2)°). The tellurium atom is situated on a two-fold crystallographic axis and Te–I and Te–C bond lengths of 2.899(1) and 2.108(7) Å have been determined.     

Die Tetracyanoborate M[B(CN)4], M = [Bu4N]+, Ag+, K+

The Tetracyanoborates M[B(CN)₄], M = [Bu₄N]⁺, Ag⁺, K⁺ The tetracyanoborate anion is prepared for the first time as the tetrabutylammonium salt by the reaction of [NBu₄]BX and BX₃ (X = Br, Cl) in toluene with KCN. After purification and recrystallization of the product from CHCl₃ colorless and needle size single crystals of [Bu₄N][B(CN)₄] are formed. After metathesis with AgNO₃ the silver salt and subsequently with KBr the potassium salt is prepared. The three salts are characterized by single crystal X‐ray diffraction (Ag[B(CN)₄] P 43m, a = 5.732(1) Å, V = 188.3 ų, Z = 1, R₁ = 0.75%; K[B(CN)₄] I4₁/a, a = 6.976(1), c = 14.210(3) Å, V = 691.5 ų, Z = 4, R₁ = 1.90%; [Bu₄N][B(CN)₄] Pnna, a = 17.765(3), b = 11.650(2), c = 11.454(2) Å, V = 2370.5 ų, Z = 4, R₁ = 6.09%) and by NMR‐, IR‐, Raman‐ as well by UV‐spectroscopy.     

Einkristall-RöntgenStrukturanalysen von Verbindungen mit einer kovalenten Metall-Metall-Bindung. VII. Die Kristall- und Molekülstruktur von dimeren Halogenobis- (pentacarbonylrhenium)indium(III), [(Re(CO)5)2In(μ-X)]2 (X = Cl,Br, I)

Single-Crystal X-Ray Analysis of Compounds with a Covalent Metal-Metal Bond. VII. Crystal and Molecular Structure of the Halogeno-Bridged Dimers of Halogenobis(pentacarbonylrhenium)indium(III), [(Re(CO)₅)₂In(μ-X)]₂ (X = Cl, Br, I) [(Re(CO)₅)₂In(μ-X)]₂ crystallizes if X = Cl and X = Br in the monoclinic system, space group P2₁/c (No. 14), with the lattice constants X = Cl: a = 10.540(6), b = 12.961(7), c = 26.071(12) Å, β = 106.3(1) Å, Z = 4, X = Br: a = 10.548(9), b = 13.108(7), c = 26.192(15) Å, β = 106.0(2)°, Z = 4 and if X = I in the triclinic system, space group P1 (No. 2), with the lattice constants a = 10.739(2), b = 7.160(1), c = 13.647(1) Å, α = 68.65(9), β = 71.89(9), γ = 65.52(9)°, Z = 1. The central molecular fragment consists of a plane In₂X₂ ring with the mean In—X distances: X = Cl: 2.624(6) Å, X = Br: 2.764(3) Å and X = I: 2.986(2) Å and the angles In—X—In/X—In—X, X = Cl: 97.2(2)°/ 82.8(2)°, X = Br: 94.8(1)°/85.2(1)° and X = I: 96.47(5)°/83.53(5)°. Two Re(CO)₅ groups are bonded to each of these In atoms to form a distorted tetrahedral coordination. The mean In—Re bond-distances are: X = Cl: 2.797(2), X = Br: 2.796(2) and X = I:2.811 (2) Å. There is a octahedral coordination around the Re atoms.     

Dimers of Ag2+ Ions – Synthesis and Characterization of the Quaternary Silver Fluoride Ag2ZnZr2F14 with [Ag2F7]3– Units

Deep blue‐violet colored powder samples of Ag₂ZnZr₂F₁₄ were synthesized by heating Zn(NO₃)₂·4H₂O, Ag and ZrOCl₂·8H₂O at 300 °C under fluorine atmosphere. The crystal structure of Ag₂ZnZr₂F₁₄ was refined from X‐ray powder diffraction data using the Rietveld method (C2/m, a = 9.0206(1) Å, b = 6.6373(1) Å, c = 9.0563(1) Å, β = 90.44(1)°, Z = 2). The structure is derived from the isotypic Ag₃Zr₂F₁₄ by replacing only one of the two crystallographically different Ag²⁺ ions with Zn²⁺ ions, thus leading to discrete Ag₂F₇ dimers. These dimers are connected via nearly linear Ag–F···F–Ag bridges with short F···F distances of 2.33 Å to form two‐legged ladders. Magnetic susceptibility measurements and density functional calculations show that the two Ag²⁺ ions in each Ag₂F₇ dimer are strongly coupled antiferromagnetically.     

NaTe3: eine Verbindung mit verbrückten Te126−-Clustern

NaTe₃ – a Compound with Cuban-like Clusters Te₁₂^6? NaTe₃ results as a greyish microcrystalline powder if stoichiometric amounts of the pure elements sodium and tellurium (molar ratio 1:3) are allowed to react in liquid ammonia at about ?50°C. After melting the crude product (500°C, 1 h, corundum crucible in sealed glass ampoule), followed by an annealing period (380°C, 5 days) NaTe₃ yields as a silvery compound with metallic lustre. NaTe₃ is trigonal, space group P3 c1, Z = 12, with a = 9.033(2) Å and c = 21.930(4) Å. It contains Te₆^2?-chains, linked together via their terminal atoms producing infinite strings. These strings may be thought to be built up of cuban-like clusters Te₁₂^6?.