Zur Reaktion von Makrozyklen mit Lanthanoiden. II. Die Strukturen von [K(thf)3]2[(C22H28N4)2Sm2] · 4THF und [(C22H22N4)Co] · DME

On the Reaction of Macrocycles with Lanthanoids. II. The Crystal Structures of [K(thf)₃]₂[(C₂₂H₂₈N₄)₂Sm₂] · 4 THF and [(C₂₂H₂₂N₄)Co] · DME In a complicated redox reaction [(TMTAA)K₂] and [SmI₂(thf)₂] form the polynuclear metal complex [K(thf)₃]₂[(TMTAT)₂Sm₂]. This complex crystallizes with four molecules THF per formula unit and its structure was determined by single crystal X-ray investigation (spacegroup P2₁/c (No. 14), z = 4, a = 998.0(2) pm, = b = 2618.3(6) pm, c = 1619.4(3) pm, β = 96.52(2)°). In the dimeric unit [(TMTAT)₂Sm₂]^2? the Sm³⁺ ions are bonded to the four N atoms of the macrocyclic ligand and one C₆H₄ ring of the second ligand is attached η⁶ like to one metal ion. Additionally two [K(thf)₃]⁺ fragments are bonded to this central unit, and therefor coordination number seven results for the K⁺ ion. [TMTAA]^2? is not reduced by [Cp₂Co] in a similar reaction. The monomeric paramagnetic complex [(TMTAA)Co] (μ_eff = 2,76 μ_B) is formed instead. The structure reveils a square planar coordination of the Co atom by the four N atoms of the TMTAA ligand (spacegroup C2/c (No. 15), z = 4, a = 1945.1(4) pm, b = 1165.6(2) pm, c = 1144.7(2) pm, β = 116.38(1)°).     

Zur Reaktion von 2,2′-Dilithiumbiphenyl mit SmBr3 Die Struktur von [(C24H16)SmBr(thf)2]2 · [C24H14]

On the Reaction of Dilithiumbiphenyl with SmBr₃. The Crystal Structure of [(C₂₄H₁₆)SmBr(thf)₂]₂ · [C₂₄H₁₄] In THF SmBr₃ forms with [(biph)Li₂] the dimeric complex [(quaph)SmBr(thf)₂]₂ · [C₂₄H₁₄]. The structure was characterized by X-ray single crystal structure analysis (space group P1 (No. 2), Z = 1, a = 943.3(6) pm, b = 1 350.3(1) pm, c = 1 599.9(9) pm, α = 64.99(5)°, β = 89.02(5)°, γ = 73.02(6)°). The Sm iones are bridged by two Br iones. Coordination by one quaph and THF ligands leads to distorded octahedra coordination of the Sm iones. Additionally crystallizes one molecule dibenzonaphthacene.     

Zur Reaktion der Lanthanoiden mit Chelatliganden Darstellung und Struktur von [(py2CH)3Gd]

On the Reaction of the Lanthanides with Chelate Ligands Synthesis and Crystal Structure of [(py₂CH)₃Gd] GdBr₃ reacts with [(py₂CH)Li] to the mononuclear complex [(py₂CH)₃Gd] 1 . The structure of 1 was characterized by X-ray single crystal structure analysis. Space group P2₁, Z = 2, a = 951.4(10) pm, b = 1369.4(10) pm, c = 1074.5(10) pm, β = 105.69(8)°. The Gd-Ion is surrounded by the six nitrogen atoms of the three chelate ligands and shows a distorted trigonal prismatic coordination. As a difference to the lithium salt of the ligand, the six-membered metalla-cycles in 1 are not planar, but show a boat conformation.     

Neue Komplexe der Lanthanoiden mit zweizähnigen Liganden. Die Strukturen von [(C17H17N2)GdBr2(thf)2] und [(C17H17N2)3Ln] (L = Sm,Gd)

New Complexes of the Lanthanoides with Bidentate Ligands. The Crystal Structures of [(C₁₇H₁₇N₂)GdBr₂(thf)₂] and [(C₁₇H₁₇N₂)₃Ln] (L = Sm, Gd) Reaction of [(AIP)Li] with GdBr₃ leads to a new mononuclear complex [(AIP)GdBr₂(thf)₂] 1 . In contrast to this with SmI₂ the compound [(AIP)₃Sm] 2 is build up. Such complexes are also formed with Gd(OR^*)₃ (R^* = O^tBu₂C₆H₃) and [(AIP)Li] in a 1:3 ratio, [(AIP)₃Gd] 3 . The structures of 1–3 were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (No. 33), Z = 4, a = 1 972.7(9) pm, b = 984.7(5) pm, c = 1 425.0(8) pm, α = β = γ = 90°; 2 · 2 THF: space group C2/c (No. 15), Z = 8, a = 3 644.4(9) pm, b = 1 437.5(5) pm, c = 2 334.4(7) pm, β = 1 21.07(6)°; 3 : space group P2(1)/c (No. 14), Z = 4, a = 1 872.9(1) pm, b = 1 064.6(1) pm, c = 2 282.4(2) pm, β = 103.75(8)°).     

Ternäre Hydroxide. I. Synthese,Struktur und Eigenschaften von Li2[Sn(OH)6] · 2 H2O

Ternary Hydroxides. I. Synthesis, Structure, and Properties of Li₂[Sn(OH)₆] · 2 H₂O Colourless crystals of Li₂[Sn(OH)₆] · 2 H₂O were synthesized by reaction of SnCl₄ with LiOH in aqueous solution. The crystal structure was determined from single crystal data. Li₂[Sn(OH)₆] · 2 H₂O: monoclinic, P2₁/n (Nr. 14), a = 502.3(1), b = 692.3(1), c = 1020.2(3) pm, β = 99.78(1)°, V = 349.6(2) · 10⁶ pm³, Z = 2, R/Rw = 0.0192/0.0472, N(I) > 2σ(I) = 1527, N(Par.) = 54. Within the crystal structure only slightly distorted octahedrally [Sn(OH)₆]^2? ions are bonded via hydrogen bonds with water molecules forming layers, which themselve are linked by tetrahedrally coordinated Li ions; the structure is in accordance with the IR-data and the results of the ¹¹⁹Sn solid state NMR-spectroscopy; the hydrat water is eliminated at 117.1°C, the condensation reaction – forming the ternary oxide – takes place at 257.7°C.     

Darstellung und Struktur von [Cp2MoHLi(thf)]3 · Toluol

Synthesis and Crystal Structure of [Cp₂MoHLi(thf)]₃ · Toluene [Cp₂MoHLi]₄ reacts in THF/Toluene to the trimeric complex [Cp₂MoHLi(thf)]₃ · Toluene 1 . The structure of 1 was characterized by X-ray single crystal structure analysis. Space group P6₃, Z = 2, a = 1459.5(9) pm, c = 1182.3(8) pm. The central unit is represented by a Mo₃Li₃-hexagon. Each Mo-Atom is surrounded by two Cp-Ligands. One THF-Molecule is coordinated to each Li-atom. The Hydrogen-Ligand could not be located by the single crystal structure analysis.     

Synthese und Struktur eines Molybdän–Gadolinium-Heterometall-Komplexes Die Struktur von [Li(thf)4]2[Cp2MoSGdBr4(thf)]2

Synthesis and structure of a Molybdenum–Gadolinium Heterometallic Complex. The Structure of [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂ [Cp₂MoHLi] reacts in THF with S and GdBr₃ to yield the tetranuclear heterobimetallic complex [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂. The bonding situation and the structure of this compound were characterized by X-ray structure analysis (space group P1 (No. 2), Z = 1, a = 10.845(2) Å, b = 12.166(2) Å, c = 15.881(2) Å, α = 101.74(2)°, β = 97.62(2)°, γ = 103.97(2)°). Each S atom of the central Mo₂S₂-ring is coordinated by a GdBr₄(thf) fragment. Additionally each Mo atom is connected to two Cp ligands. This leads to a tetrahedral coordination of the Mo atoms and a octahedral coordination of the Gd ions.     

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)°.     

Zur Kristallstruktur von CaZn2(OH)6 · 2 H2O

Crystal Structure of CaZn₂(OH)₆ · 2 H₂O The electrochemical oxidation of zinc in a zinc/iron-pair leads in an aqueous NH₃ solution of calciumhydroxide at room temperature to colourless crystals of CaZn₂(OH)₆ · 2 H₂O. The X-ray structure determination was now successful including all hydrogen positions. P2₁/c, Z = 2, a = 6.372(1) Å, b = 10.940(2) Å, c = 5.749(2) Å, β = 101.94(2)° N(F ≥ 3σF) = 809, N(Var.) = 69, R/R_W = 0.011/0.012 The compound CaZn₂(OH)₆ · 2H₂O contains Zn²⁺ in tetrahedral coordination by OH^? and Ca²⁺ in octahedral coordination by four OH^? and two H₂O. The tetrahedra around Zn²⁺ form corner sharing chains, three-dimensionally linked by isolated polyhedra around Ca²⁺. Weak hydrogen bridge bonds result between H₂O as donor and OH^?.     

Darstellung und Kristallstruktur von [Li(DME)2I]

Synthesis and Crystal Structure of [Li(DME)₂I] . LiI can be dissolved at 50°C in toluene/DME (2:1). At - 20°C [Li(DME)₂I] ( 1 ) was isolated in 75% yield. 1 was characterized by NMR techniques as well as an X-Ray structure determination. 1 crystallizes in the space group C2/c with a = 1 356.9(2), b = 813.2(1), c = 1 259.1(2) pm, and β = 99.74(1)°.     

Über die Kristallstruktur von Barium-Acetylendicarboxylat Monohydrat – Ba[C2(COO)2] · H2O

On the Crystal Structure of Barium Acetylene Dicarboxylate Monohydrate – Ba[C₂(COO)₂] · H₂O Ba[C₂(COO)₂] · H₂O crystallizes in the monoclinic space group P2₁/a. The lattice constants are a = 753.4(2), b = 921.8(2), c = 881.8(2) pm and β = 102.00(2)°. The crystal structure is characterized by an intricate three-dimensional framework made up by Ba²⁺ and [C₂(COO)₂]^2? ions. Ba²⁺ has coordination number 9 and is bound to two water molecules and seven oxygen atoms belonging to carboxylate groups of the dianion. The [C₂(COO)₂]^2? ion does not merely act like a multiple monodentate ligand, but coordinates Ba²⁺ in a chelate-like manner as well. The carboxylate groups of the dianion are inclined to each other by 65°.     

Hydrogensulfate mit fehlgeordneten Wasserstoffatomen – Synthese und Struktur von Li[H(HSO4)2](H2SO4)2 sowie Verfeinerung der Struktur von α-NaHSO4

Hydrogen Sulfates with Disordered Hydrogen Atoms – Synthesis and Structure of Li[H(HSO₄)₂](H₂SO₄)₂ and Refinement of the Structure of α-NaHSO₄ The structure of Li[H(HSO₄)₂](H₂SO₄)₂ has been determined for the first time whereas the structure of α-NaHSO₄ has been refined, so that direct determination of the hydrogen positions was possible. Both compounds crystallize triclinic in the space group P1 with the lattice constants a = 6.708(2), b = 6.995(1), c = 7.114(1) Å, α = 75.53(1), β = 84.09(2) and γ = 87.57(2)° (Z = 4) for α-NaHSO₄ and a = 4.915(1), b = 7.313(1), c = 8.346(2) Å, α = 82.42(3), β = 86.10(3) and γ = 80.93(3)° (Z = 1) for Li[H(HSO₄)₂](H₂SO₄)₂. In both compounds there are disordered hydrogen positions. In the structure of α-NaHSO₄ there are two crystallographically different HSO₄^? tetrahedra and two different coordinated Na atoms. The system of hydrogen bonds can be described by chains in [0–11] direction. The disordering of the H atoms reduces the differences between the S? O and S? OH distances (1.45 and 1.50 Å) while in the ordered HSO₄ unit “regular” bond lengths are observed (1.45 und 1,57 Å). In the structure of Li[H(HSO₄)₂](H₂SO₄)₂ there are two crystallographically different SO₄-tetrahedra. The first one belongs to the [H(HSO₄)₂]^? unit while the second one represents H₂SO₄ molecules. The H atom which is located nearby the symmetry centre and connects two HSO₄ units by a short O…?O distance of 2.44 Å. Li is located on a symmetry centre and is slightly distorted octahedrally coordinated by oxygen atoms of six different SO₄ tetrahedra. The system of hydrogen bonds can be regarded as consisting of double layers parallel to the xy-plane.     

Neue ein- und mehrkernige Komplexe der Lanthanoiden. Zur Reaktion von Ph2Se2 mit Ytterbium

New Mono- and Polynuclear Complexes of the Lanthanides. On the Reaction of Ph₂Se₂ with Ytterbium Surprising formation of different complexes during the reaction of Ytterbium with Dichalcogenides. With THF is the mononuclear complex [Yb(SePh)₃(thf)₃] 1 (space group P31c (No. 159), Z = 2, a = 15.353(3) Å, c = 7.8920(10) Å) built up. In this compound is the Lanthanidion octahedrally souronded by the ligands. Reaction in Toluol/THF leads in contrast to the tetranuclear complex [Yb₄(SePh)₈O₂(thf)₆] 2 (space group C2/c (No. 14), Z = 4, a = 27.084(9) Å, b = 13.021(4) Å, c = 24.002(8) Å, β = 106.13(3)°). In DME it is possible to isolate the ionic species [Yb₃(SePh)₆(dme)₄][Yb(SePh)₄(dme)] 3 (space group P1 (No. 2), Z = 2, a = 11.109(3) Å, b = 11.664(2) Å, c = 36.303(10) Å, α = 84.60(4)°, β = 89.52(3)°, γ = 73.69(2)°). In this reactions are neutral and also ionic complexes accesible.     

Zur Kristallstruktur von SrZn(OH)4 · H2O

Crystal Structure of SrZn(OH)₄ · H₂O Colorless crystals of SrZn(OH)₄ · H₂O are obtained by electrochemical oxidation of Zn in a zinc/iron pair in an aqueous ammonia solution saturated with strontium hydroxide. The X-ray crystal structure determination was now successful including all hydrogen positions: P1 , Z = 2, a = 6.244(1) Å, b = 6.3000(8) Å, c = 7.701(1) Å, α = 90.59(1)°, β = 112.56(2)°, γ = 108.66(2)°, N(F ≥ 3σF) = 1967, N(Var.) = 84, R/R_w = 0.020/0.024. In SrZn(OH)₄ · H₂O Zn²⁺ is tetrahedrally coordinated by four OH^? -ions while Sr²⁺ has 6 OH^? and one H₂O as neighbours. The polyhedra around Sr²⁺ are connected to chains which are linked three-dimensionally by isolated tetrahedra [Zn(OH)₄]. Hydrogen bonds between H₂O as donor and OH^? are characterized by raman spectroscopy.     

Ein oktaedrischer Niobcluster mit sechs terminalen Azidgruppen: Die Struktur von Rb4[Nb6Br12(N3)6](H2O)2

An Octahedral Niobium Cluster containing Six Terminal Azide Groups: The Structure of Rb₄[Nb₆Br₁₂(N₃)₆](H₂O)₂ Six terminal halide ligands of [Nb₆Br₁₂Br₆]^4? can be substituted in solution by azide ions. Single-crystals of Rb₄[Nb₆Br₁₂(N₃)₆](H₂O)₂ were obtained during the evaporation of the water/methanol solvent, and structurally characterized by X-ray methods: Space group P2₁/c, Z = 2, a = 970.8(5) pm, b = 1525.4(7) pm, c = 1280.0(7) pm, β = 97.15(6)°. The [Nb₆Br₁₂(N₃)₆]^4? ions contain six terminal azide groups at the corners of the octahedral niobium cluster (d _Nb–N = 227 pm). The [Nb₆Br₁₂(N₃)₆]^4? ions are interconnected by Rb⁺ and H₂O. Crystals of Rb₄[Nb₆Br₁₂(N₃)₆](H₂O)₂ are explosive towards heat or mechanic pressure.     

Die Struktur von [Li(tmeda)2][Zn(2,4,6-i-Pr3C6H2)3]

X-Ray Structure of [Li(tmeda)₂][Zn(2,4,6- i Pr₃C₆H₂)₃] A side reaction of zinc halide containing VCl₂(tmeda)₂ and Li(2,4,6-iPr₃C₆H₂) formed [Li(tmeda)₂][Zn(2,4,6-iPr₃C₆H₂)₃] · 0,5[(tmeda)Li(μ-Cl)]₂. The crystal structure (orthorhombic, Pbca, a = 26,226(2), b = 19,739(2), c = 27,223(5) Å, Z = 8, R = 0,062, wR² = 0,154) contains trigonal planar zinc anions with Zn–C distances of 2,039(7) Å (average) and a propeller like arrangement of the aryl rings.     

Zur Struktur eines ungewöhnlichen Tetramers des Lithiumphenolats: [C6H5OLi · C4H8O]4 · C6H5OH

The Structure of an unusual Tetramere of Lithium Phenoxide: [C₆H₅OLi · C₄H₈O]₄ · C₆H₅OH Single crystals of lithium phenoxide have been obtained from THF. In the structure (P 2₁/n, Z = 4, a = 11.69 Å, b = 21.15 Å, c = 18.55 Å, β = 91.11°) four lithium atoms and four phenoxide oxygen atoms are cubically arranged. Further, each lithium atom coordinates the oxygen atom of a tetrahydrofuran molecule. The ideal cubeform structure is disturbed by one phenol molecule which is coordinated in addition to four phenoxide and four THF molecules. Hence, one edge of the cube (Li4? O4) is substituted by the coordination of the phenol oxygen atom O5 with Li4 and hydrogen bonding between O4 and the hydroxy group of phenol. Van der Waals forces are the only interaction between these complexes.     

Zur Existenz des Tetrahydrogenorthoperiodations Die Kristallstruktur von LiH4IO6 · H2O

On the Existence of the Tetrahydrogenorthoperiodate Ion. The Crystal Structure of LiH₄IO₆ · H₂O The crystal structure of LiH₄IO₆ · H₂O has been determined (P1 ; a = 564.74(12), b = 574.41(13), c = 970.4(6) pm, α = 101.37(2), β = 96.37(2), γ = 114.72(2)°; Z = 2; 5 731 independent reflections; R = 0.038). All hydrogen-atoms were localized from difference fourier map and refined without applying constraints. Thus the existence of the tetrahydrogenorthoperiodate-ion in the solid state is proved, unambigously. The crystal structure is discussed and compared to other alkaliorthoperiodates.     

Die Reaktion von Molybdänpentachlorid mit Trichlornitromethan; die Kristallstruktur von [MoOCl3 · POCl3]2

Reaction of Molybdenum Pentachloride with Trichloronitromethane. Crystal Structure of [MoOCl₃ · POCl₃]₂ An improved method for the preparation of MoO₂Cl₂ by the reaction of MoCl₅ with CCl₃NO₂ is reported. In the presence of the solvens POCl₃, molybdenum pentachloride reacts with trichloronitromethane forming the oxonitrosyl complex Mo(NO)OCl₃ · POCl₃. In CH₂Cl₂ solution this complex is decomposed forming [MoOCl₃ · POCl₃]₂. The crystal structure was solved by X-ray methods. [MoOCl₃ · POCl₃]₂ crystallizes monoclinic in the space group P2₁/c with two dimers in the unit cell (R = 0.07, 2327 independent reflexions). The complex dimerizes by symmetric chloro bridges; the oxoligand is in terminal position. The MoO bond length of 163 pm corresponds with a Mo?O triple bond. The POCl₃ molecule is coordinated in position trans to the oxoligand. The IR spectra are reported and assigned.     

Derivate des Imidazols. XXIV [1].[Li12O2Cl2(ImN)8(THF)4] · 8 THF: Ein Peroxo-Komplex des Lithiums mit neuartiger Käfigstruktur

Imidazole Derivatives. XXIV. [Li₁₂O₂Cl₂(ImN)₈(THF)₄] · 8 THF: a Peroxo Lithium Fragment in a Novel Cage Structure 1,3-dimethyl-2-iminoimidazoline ( 8 , ImNH) reacts with methyl lithium to give [ImNLi]_n ( 9 ). In tetrahydrofuran, crystals of C₅₆H₉₆Cl₂Li₁₂N₂₄O₆ · 8 C₄H₈O ( 10 ) are obtained. The structure of 10 consists of a Li₁₂Cl₂N₈O₂ core in which a peroxo unit is incorporated into a stack of ladder fragments. Over all, four tetrahydrofuran and eight imidazoline ligands are attached at the lithium and nitrogen atoms.