Die Molekül‐ und Kristallstruktur des Rubidium(Dibenzo‐18‐Krone‐6)‐pentaiodids [Rb(C20H24O6)]I5

Molecular and Crystal Structure of Rubidium(dibenzo‐18‐crown‐6)pentaiodide [Rb(C₂₀H₂₄O₆)]I₅ [Rb(Dibenzo‐18‐crown‐6)]₂(I₅)₂ is obtained as dark brown columns by reacting dibenzo‐18‐crown‐6, rubidium iodide, and iodine in a molar ratio of 1 : 1 : 6 in ethanole / dichlormethane (1:1). [Rb(C₂₀H₂₄O₆)]₂(I₅)₂ crystallizes with four formula units per unit cell in the orthorhombic space group Pnma with a = 1725.15(2) pm, b = 1863.76(3) pm and c = 1885.19(3) pm. The crystal structure consists of pentaiodide units I₅^—, which are linked to one another by head‐to‐tail‐contacts. The I₂ units, which stick out of the chain, are twisted against each other, in a way that neither a cis or a trans configuration is formed. By secondary bonding, the iodine atoms form nets of 18‐member planar rings with an almost rectangular form. This net‐like structural element has not been described up to now.     

An Ortho‐silicate‐hydroxide: Rb5[SiO4][OH]

Rb₅[SiO₄][OH] crystallizes in the monoclinc space group C2/m with a = 737.3(1) pm, b = 1073.7(2) pm, c = 1207.2(2) pm, β = 106.07(2)° and Z = 4 (single crystal data; R1= 0.0681 all data). Layers of edge‐connected distorted trigonal prismatic [(OH)Rb₆] entities and isolated tetrahedral [SiO₄] units present the main structural features of this unprecedented structure type.     

[Rb4Sn9] — A Low Dimensional Arrangement of Zintl Ions in [Rb(18‐crown‐6)]2Rb2[Sn9](en)1.5

The compound [Rb(18‐crown‐6)]₂Rb₂[Sn₉](en)_1.5 ( 1 ) was synthesized from an alloy of formal composition K₂Rb₂Sn₉ by dissolving in ethylenediamine (en) followed by the addition of 18‐crown‐6 and toluene. 1 crystallizes in the monoclinic space group P2₁/n with a = 10.557(2), b = 25.837(5), c = 20.855(4)Å, β = 102.39°, and Z = 4. The structure consists of [Sn₉]^4— cluster anions, which are connected via Rb atoms to infinite [Rb₄Sn₉] layers. The layers of binary composition are separated by the crown ether molecules. The crown ether molecules are bound by one side via the Rb atoms to the [Sn₉]^4— anions. The other side, which is turned away from the Rb atoms, shows only weak van der Waals interactions to the crown ether molecules of the next layer. Comparison with other compounds of similar composition shows, that the variation of the alkali metals and the complexing organic molecules leads to the low dimensional arrangement of the clusters.     

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.     

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.     

Kristallstrukturen von Verbindungen A2[MnF3(SO4)] (A = Rb,NH4, Cs): Jahn‐Teller‐Ordnung in Mangan(III)‐fluoridsulfaten. I.

Jahn‐Teller Ordering in Manganese(III) Fluoride Sulphates. I. Crystal Structures of A₂[MnF₃(SO₄)] (A = Rb, NH4, Cs) The three isostructural fluorosulphatomanganates(III) A₂[MnF₃(SO₄)] (A = Rb, NH₄, Cs) crystallize in space group P2₁/c, Z = 4. Rb₂[MnF₃(SO₄)]: a = 7.271, b = 11.091, c = 8.776Å, β = 92.26°, R = 0.033; (NH₄)₂[MnF₃(SO₄)]: a = 7.299, b = 10.157, c = 8.813Å, β = 91.51°, R = 0.025; Cs₂[MnF₃(SO₄)]: a = 7.365, b = 11.611, c = 9.211, β = 92.30°, R = 0.029. In the chain anions [MnF₃(SO₄)]^2— manganese(III) is coordinated by two trans‐terminal and two trans‐bridging fluorine ligands, and by the O‐atoms of two briding sulphate ligands in trans position. The Jahn‐Teller effect induces a variety of antiferrodistortive ordering resulting in distorted [MnF₄O₂] octahedra with alternating elongation of F—Mn—F — and O—Mn—O — axes, respectively. Thus, only asymmetrical bridges are formed.     

Two New Benzoate‐di(methylcyclopentadienyl)ytterbium(III) Complexes: [Yb(MeCp)2(O2CC6F5)]2 and [Yb(MeCp)2(O2C‐o‐HC6F4)]2

Transparent orange crystals of [Yb(MeCp)₂(O₂CC₆F₅)]₂ and [Yb(MeCp)₂(O₂C‐o‐HC₆F₄)]₂ were obtained by oxidation of Yb(MeCp)₂ with M(O₂CR) (M = ¹/₂ Hg, Tl; R = C₆F₅, o‐HC₆F₄) in tetrahydrofuran. They have a dimeric structure with bridging bidentate (O, O')‐benzoate groups and eight coordinated ytterbium. Both crystallise isotypic in the orthorhombic space group Pbca. Room temperature as well as low temperature single crystal X‐ray investigations show the o‐H/F positions in [Yb(MeCp)₂(O₂C‐o‐HC₆F₄)]₂ not to be ordered.     

Untersuchungen an Polyhalogeniden. XXVII. Über Tetra(n-propyl)ammoniumpolyiodide (n-Pr4N)In mit n = 3, 5, 7: Darstellung und strukturelle Charakterisierung eines Triiodids (n-Pr4N)I3, eines Pentaiodids (n-Pr4N)I5 und eines Heptaiodids (n-Pr4N)I7

Studies of Polyhalides. 27. On Tetra(n-propyl)ammonium Polyiodides (n-Pr₄N)I_n with n = 3, 5, 7: Preparation and Crystal Structures of a Triiodide (n-Pr₄N)I₃, a Pentaiodide (n-Pr₄N)I₅, and a Heptaiodide (n-Pr₄N)I₇ [(n-C₃H₇)₄N]I₃, [(n-C₃H₇)₄N]I₅ and [(n-C₃H₇)₄N]I₇ have been prepared by the reaction of tetra(n-propyl)ammoniumiodide [(n-C₃H₇)₄N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The triiodide is built up from layers of the quarternary ammonium ions n-Pr₄N⁺ and from two independent differently packed centrosymmetric triiodide ions I₃^? which alternate with each other along [100]. The pentaiodide ion forms slightly puckered almost squared nets perpendicular [001] of iodide ions which are connected with four iodine molecules by secondary bonds. The meshes from twelve iodine atoms include the cations. The centrosymmetric Z-shaped heptaiodide ion is built up from a linear symmetric triiodide ion and two iodine molecules forming twisted rope ladders along [001] which are separated by stacks of cations.     

Synthese und Kristallstrukturen von (2‐Methylpyridinium)3[TbCl6] und (2‐Methylpyridinium)2[TbCl5(1‐Butanol)]

Preparation and Structure of (2‐Methylpyridinium)₃[TbCl₆] and (2‐Methylpyridinium)₂[TbCl₅(1‐Butanol)] The complex chlorides (2‐Methylpyridinium)₃[TbCl₆] (1) and (2‐Methylpyridinium)₂[TbCl₅(1‐Butanol)] (2) have been prepared for the first time. The crystal structures have been determinated from single crystal X‐ray diffraction data. 1 crystallizes in the monoclinic space group C2/c (Z = 8) with a = 3241,2(5) pm, b = 897,41(9) pm, c = 1774,2(2) pm and β = 97,83(2)°, 2 in the monoclinic space group P2₁/n (Z = 4) with a = 1372,96(16) pm, b = 997,57(9) pm, c = 1820,5(2) pm and β = 108,75(1)°. The structures contain isolated octahedral building units [TbCl₆]^3– and [TbCl₅(1‐Butanol)]^2–, respectively.     

Synthese und Kristallstrukturen von (3‐Methylpyridinium)3[DyCl6] und (3‐Methylpyridinium)2[DyCl5(Ethanol)]

Preparation and Structure of (3‐Methylpyridinium)₃[DyCl₆] and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] The complex chlorides (3‐Methylpyridinium)₃[DyCl₆] ( 1 ) and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] ( 2 ) have been prepared for the first time. The crystal structures have been determined from single crystal X‐ray diffraction data. 1 crystallizes in the trigonal space group R3c (Z = 36) with a = 2953.3(3) pm, b = 2953.3(3) pm and c = 3252.5(4) pm, compound 2 crystallizes in the triclinic space group P1 (Z = 2) with a = 704.03(8) pm, b = 808.10(8) pm, c = 1937.0(2) pm, α = 77.94(1)°, β = 87.54(1)° and γ = 83.26(1)°. The structures contain isolated octahedral building units [DyCl₆]^3– and [DyCl₅(Ethanol)]^2–, respectively.     

Formation and Crystal Structure of the Salt (IC(PPh3)2)2I[I3]·(I2)2 with a new Polyiodide Chain

The reaction of the carbodiphosphorane Ph₃P=C=PPh₃ ( 1 ) with MeI in the presence of iodine gives the oxidation product (IC(PPh₃)₂)₂I[I₃]·(I₂)₂ ( 2 ). In the solid state dimeric units linked by indefinite ···I^?···I₂···I₃^?···I₂···I^?··· chains are found. An additional I···I contact between the cation and the I₂ molecule is formed, amounting to 359.23(5) pm. 2 crystallizes in the monoclinic space group P2/c, with the unit cell dimensions a = 2053.9(1), b = 1011.4(1), c = 1889.8(1) pm; β = 105.21(1)° and Z = 4.     

Synthese und Kristallstrukturen von (NEt4)2[TeS3], (NEt4)2[Te(S5)(S7)] und (NEt4)4[Te(S5)2][Te(S7)2]

Synthesis and Crystal Structures of (NEt₄)₂[TeS₃], (NEt₄)₂[Te(S₅)(S₇)], and (NEt₄)₄[Te(S₅)₂][Te(S₇)₂] (NEt₄)₂[TeS₃] was obtained by the reaction of NEt₄Cl, Na₂S₄ and tellurium in acetonitrile. It reacts with sulfur, yielding (NEt₄)₂[Te(S₅)(S₇)], which is transformed to (NEt₄)₄[Te(S₅)₂][Te(S₇)₂] by recrystallization from hot acetonitrile. According to the X-ray structure analysis, crystals of (NEt₄)₂[TeS₃] are monoclinic (space group P2₁/c) and form twins with the twinning plane (001); they contain pyramidal TeS₃^2– ions. (NEt₄)₂[Te(S₅)(S₇)] forms triclinic twins (space group P1) with the twinning plane (010). In the [Te(S₅)(S₇)]^2– ion an S₅ and an S₇ atom group are bonded in a chelate manner to the tellurium atom, which has square coordination. (NEt₄)₄[Te(S₅)₂][Te(S₇)₂] (monoclinic, space group P2₁/c) contains two kinds of anions, the known [Te(S₅)₂]^2– and the new [Te(S₇)₂]^2– ion which has two S₇ chelating groups.     

Über die Decamethylferroceniumpolyiodide [(Me5C5)2Fe]Ix mit x = 3, 5 und 6,5. Darstellung und strukturelle Charakterisierung eines Triiodids (DMFc)I3, eines Pentaiodids (DMFc)I5 und eines Hexacosaiodids (DMFc)4I26

Studies on Polyhalides. 30 On Decamethylferriciniumpolyiodides [(Me₅C₅)₂Fe]I_x with x = 3, 5, 6.5: Preparation and Crystal Structures of a Triiodide (DMFc)I₃, a Pentaiodide (DMFc)I₅ and a Hexacosaiodide (DMFc)₄I₂₆ Decamethylferrocene (DMFc) may be oxidized by iodine analogous to ferrocene (Fc) to the decamethylferrocenium ion (DMFc)⁺ and precipitated as the crystalline solids decamethylferrocenium triiodide (DMFc)I₃, decamethylferrocenium pentaiodide (DMFc)I₅ and tetracisdecamethylferrocenium hexacosaiodide (DMFc)₄I₂₆. The two compounds with higher iodine content are new. These are characterized by X-ray diffraction methods on single crystals. The structures are built up from complex cations of expected geometry and isolated or remarkably connected polyiodide ions. Decamethylferrocenium triiodide C₂₀H₃₀FeI₃ crystallizes monoclinically in C2/m with a = 1489.9(4) pm, b = 1133.0(2) pm, c = 765.9(3) pm, β = 111.76(3)° and Z = 2. The crystal structure follows the CsCl-type and contains isolated triiodide ions of the linear symmetric form. Decamethylferrocenium pentaiodide C₂₀H₃₀FeI₅ crystallizes monoclinically in P2₁/c with a = 1130.0(2) pm, b = 1442.6(1) pm, c = 1716.6(2) pm, β = 96.62(1)° and Z = 4. The crystal structure may be deduced from the primitiv quadratic bundle of alternating cationic and anionic rods. It contains exceptionally isolated somewhat opened out pentaiodide ions. Tetrakisdecamethylferrocenium hexacosaiodide (C₂₀H₃₀Fe)₄I₂₆ crystallises monoclinically in P2₁/n with a = 1331.3(8) pm, b = 1319.4(4) pm, c = 3564(2) pm, β = 90.84(5)° and Z = 2. The crystal structure of this compound with unusual composition may be described as an inclusion compound with channels for the cations. The outstanding anionic grating may be derived from the primitive cubic lattice of iodide ions with iodine bridges on all edges by removing systematically 1/12 of the iodine molecules.     

Mixed‐ligand Copper(II) Complexes with N‐isopropyl‐iminodiacetato(2‐) and C‐phenyl‐imidazole Ligands. Crystal Structures of H2iPIDA, [Cu(iPIDA)(H2ϕim)(H2O)]·3H2O and [Cu(iPIDA)(H5ϕim)]n

The crystal of the N‐isopropyl‐iminodiacetic acid ( 1 ) consists of a 3D H‐bonded framework where the zwitterion (H₂iPIDA^±) is intra‐stabilized by one N⁺‐H···O interaction and both carboxyl are half‐protonated and involved in linear O‐H···O inter‐molecular bridges of 2.46 Å. The mixed‐ligand complexes [Cu(iPIDA)(H2?im)(H₂O)]·3H₂O ( 2 ) and [Cu(iPIDA)(H5?im)]_n ( 3 ) have also been synthesized and studied by thermal, spectral, magnetic and X‐ray diffraction methods. Both complexes exhibit a square base pyramidal coordination, type 4+1. Compound 3 is the less steric hindered 'remote' isomer, with H5?im instead of H4?im.     

Synthesis and Characterization of New Copper(I) Complexes Containing Thione Derivatives of 1, 2, 4‐Triazine. Crystal Structure of [Cu(PPh3)2(ATTO)]NO3 (ATTO = 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one)

The reaction of 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one (ATTO, 1 ) with [Cu(PPh₃)₂]NO₃ in ethanol led to the complex [Cu(PPh₃)₂(ATTO)]NO₃ ( 2 ). 2 was characterized by elemental analyses, IR, ¹H NMR and Raman spectroscopy. A single‐crystal X‐ray diffraction of compound 2 revealed that ATTO acts as a bidentate ligand via its nitrogen and sulfur atoms. Crystal data for 2 at 20 °C: space group P2₁/n with a = 975.7(1), b = 1533.5(2), c = 2504.2(3) pm, β = 92.25(1)°, Z = 4, R₁ = 0.0632.     

Zur Struktur zweier Isothiazolium‐Polyiodide (C19H16FeNS)I5 und (C15H12NS)2I8

On the Structure of Two Isothiazolium Polyiodides (C₁₉H₁₆FeNS)I₅ and (C₁₅H₁₂NS)₂I₈ By oxidation of 3‐phenylamino thiopropenones with iodine two isothiazolium polyiodides were obtained, whose structures have been determined by X‐ray structure analysis. 2‐Phenyl‐5‐ferrocenyl‐isothiazolium pentaiodide(C₁₉H₁₆FeNS)I₅ forms a layer structure with isothiazolium cations and polyiodide anions. The polyiodide layers contain pentaiodide ions I₅^–, triiodide ions I₃^– and iodine molecules I₂. Bis(2,5‐diphenyl‐isothiazolium) octaiodide (C₁₅H₁₂NS)₂I₈ also forms a layer structure with isothiazolium cations and polyiodide anions. The polyiodide layers are built up by octaiodide ions I₈^2–, pentaiodide ions I₅^– and triiodide ions I₃^–.     

The pentacoordinated [Cr(CO)5]2− dianion in [2,2,2‐crypt‐K]2[Cr(CO)5] ethylenediamine monosolvate

Bis[(4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane)potassium(+)] pentacarbonylchromate(2−) ethylenediamine monosolvate, [K(C₁₈H₃₆N₂O₆)]₂[Cr(CO)₅]·C₂H₈N₂, was obtained from the reaction between K₃Cd₂Sb₂ and Cr(CO)₆ in ethylenediamine in the presence of the macrocyclic 2,2,2‐crypt ligand. The structure provides the first crystallographic characterization of the pentacoordinated [Cr(CO)₅]²⁻ dianion. The central Cr^III atom is coordinated by five carbonyl ligands in a distorted trigonal–bipyramidal geometry. The distribution of the Cr—C bond lengths indicates a greater degree of back bonding from Cr^III to the equatorial carbonyl ligands compared with the axial carbonyl ligands.     

Bismuth Polyanions in Solution: Synthesis and Structural Characterization of (2, 2, 2‐crypt‐A)2Bi4 (A = K,Rb) and the Formation of the Laves Phases ABi2 (A = K,Rb, Cs) from Solution

The possibility to synthesize and isolate different types of bismuth polyanions by dissolving various intermetallic precursors (binary samples from A‐Bi or ternary samples from A‐A'‐Bi systems, A and A' = K, Rb, Cs) in ethylenediamine or dimethylform amide in the presence of sequestering agents (2, 2, 2‐crypt or 18‐crown‐6) was investigated. The crystals of (2, 2, 2‐crypt‐K)₂Bi₄ ( 1 ) and (2, 2, 2‐crypt‐Rb)₂Bi₄ ( 2 ) compound were obtained from such solutions, the latter for the first time, and their structures were determined. The two compounds are isostructural (P1, Z=1, a = 11.052(2) Å, b = 11.370(2) Å, c = 11.698(2) Å, α = 61.85(3) °, β = 82.58(3) °, γ = 81.87(3) °, R₁ = 0.058, wR² = 0.149 for 1 and a = 11.181(2) Å, b = 11.603(2) Å, c = 11.740(2) Å, α = 61.96(3) °, β = 81.45(3) °, γ = 82.26(3) °, R₁ = 0.041, wR² = 0.109) and contain Bi₄^2— square planar cluster anions and cryptated alkali metal cations. In the case of the presence of 18‐crown‐6 the Laves phases ABi₂ (A = K, Rb, Cs) could be isolated from the solutions. A mechanism for the formation of ABi₂ is proposed.     

Three Modifications of [Pr2(ClO4)2(H2I2O10)]·8 H2O — A Theme with Variations

From solutions containing praseodymium perchlorate and periodic acid, three different modifications of [Pr₂(ClO₄)₂(H₂I₂O₁₀)] · 8 H₂O could be obtained. All of them crystallize in the monoclinic system, space group P2₁/c (α: a = 1091.47(6), b = 728.24(4), c = 1388.84(8) pm, β = 101.420(3)°; β: a = 1169.93(3), b = 728.72(2), c = 1384.50(4) pm, β = 112.303(2)°; γ: a = 1209.56(4), b = 712.53(2), c = 1361.64(5) pm, β = 115.691(1)°). The structures contain Pr³⁺ cations which are coordinated by [H₂I₂O₁₀]^4— anions yielding two‐dimensional networks. These networks are separated by ClO₄^— anions yielding a layered structure.     

Synthesen und Eigenschaften von Pentafluorethylkupfer(I)‐ und ‐(III)‐Verbindungen: Cu(C2F5) · D, [Cu(C2F5)2]– und (C2F5)2CuSC(S)N(C2H5)2

Syntheses and Properties of Pentafluoroethylcopper(I) and ‐copper(III) Compounds: CuC₂F₅ · D, [Cu(C₂F₅)₂]^–, and (C₂F₅)₂CuSC(S)N(C₂H₅)₂ The reactions of Cd(C₂F₅)₂ · D and Zn(C₂F₅)₂ · D (D = 2 CH₃CN, 2 DMF), respectively, with copper(I) halides in the presence of halides quantitatively yield the CuC₂F₅ compounds CuC₂F₅ · D and [Cu(C₂F₅)₂]^–. The CuC₂F₅ complexes are identified by NMR spectroscopy, while [Cu(C₂F₅)₂]^– is isolated as PNP salt (PNP = (C₆H₅)₃PNP(C₆H₅)₃⁺). Both compounds are excellent C₂F₅ group transfer reagents, even at low temperature. Oxidation of [Cu(C₂F₅)₂]^– with [(C₂H₅)₂NC(S)S]₂ yields the crystalline Cu(III) compound (C₂F₅)₂CuSC(S)N(C₂H₅)₂ (monoclinic, C2/c).