Synthese und Struktur der Cobalt(III)-Komplexe 14gliedriger cis- und trans-N2S2-Dibenzomakrocyclen mit zwei koordinierenden Acetatogruppen

Synthesis and Structure of Cobalt(III) Complexes of 14-Membered cis- and trans-N₂S₂ Dibenzo Macrocycles with two Pendant Acetato Groups The isomeric fourteen membered macrocyclic ligands 6,7,9,15,16,18-hexahydrodibenzo[f,m][1,8]dithia[4,11]diazacyclotetradecine-8,17-diacetic acid-0.5-hydrate (H₂L³), C₂₂H₂₆N₂O₄S₂ · 0.5 H₂O and 6,7,13,15,16,18-hexahydrodibenzo-[e,m][1,4]dithia[8,11]diazacyclotetradecine-14,17-diacetic acid-1.5-hydrate (H₂L⁶), C₂₂H₂₆N₂O₄S₂ · 1.5 H₂O with cis- and trans-N₂S₂ donorsets and two pendant acetato groups form the stable complexes [Co(L³)]ClO₄ · 2 H₂O ( 1 ) and [Co(L⁶)]ClO₄ · H₂O ( 2 ). Co(III) is octahedrally coordinated herein to all six donor centers of the respective ligand. The macrocyclic rings are folded. The metal ions are located outside the macrocyclic cavity. The mean Co? N, Co? O and Co? S distances are 196, 190 and 224 pm, respectively. Crystal data: 1 , monoclinic, space group C2/c, a = 3 797.7(9), b = 763.8(3), c = 2 207.0(7) pm, β = 123.17(2), Z = 8, 3 445 reflections, R(R_w) = 0.072(0.070); 2 , monoclinic, space group C2/c, a = 3 197.1(6), b = 880.4(2), c = 1 890.6(4) pm, β = 112,19(3)°, Z = 8, 4 415 reflections, R(R_w) = 0.062(0.064).     

Einkristalle von A?Nd2S3, U?Ho2S3, D?Er2S3 und E?Lu2S3 durch Oxidation reduzierter Chloride der Lanthanide mit Schwefel

Single Crystals of A? Nd₂S₃, U? Ho₂S₃, D? Er₂S₃, and E? Lu₂S₃ through the Oxidation of Reduced Lanthanide Chlorides with Sulfur The oxidation of reduced chlorides (MCl₂) or chloridehydrides (MClH_x) of the lanthanides with sulfur (850°C, 7 d, tantalum ampoule) usually results in the formation of their sesquisulfides (M₂S₃) as the main product. In the presence of appropriate fluxes (e. g., NaCl), they often are obtained as single crystals, and the flux appears to decide which modification is favourized. Single crystals of Nd₂S₃ , (from NdCl₂ + NaCl + S, 2 : 2 : 1, A-type: orthorhombic, Pnma (no. 62), Z = 4; a = 743.97(5), b = 402.78(3), c = 1551.96(9) pm, V_m = 70.015(8) cm³/mol, R , = 0.026, R_w = 0.023), Ho₂S₃ , (from Na_0.25HoClH_0.75 + S, 8 : 9, U type: orthorhombic, Pnma (no. 62), Z = 4, a = 1057.24(7), b = 384.48(4), c = 1041.15(7) pm, V_m = 63.716(9) cm³/mol, R , = 0.023, R_w = 0.020), Er₂S₃ , (from ErClH_0.67 + NaCl + S, 2 : 2 : 1, D type: monoclinic, P2₁/m (no. 11), Z = 6, a = 1744.18(9), b = 398.22(3), c = 1010.13(6) pm, β = 98.688(4)°, V_m = 69.610(7) cm³/mol, R = 0.031, R_w = 0.029) and Lu₂S₃ , (from LuClH_0.67 + NaCl + S, 2 : 2 : 1, E type: trigonal, R3 c (no. 167), Z = 6, a = 672.86(2), c = 1816.84(9) pm, c/a = 2.70, V_m = 71.497(6) cm³/mol, R = 0.023, R_w = 0.020) as well as more systematic general investigations (syntheses of the lanthanide sesquisulfides from the elements in the presence of NaCl as a flux in sealed tantalum containers at 850°C) are the main topic of the work presented here.     

Erdalkali-Fluoromanganate(III): BaMnF5 · H2O und SrMnF5 · H2O

Alkaline Earth Fluoromanganates(III): BaMnF₅ · H₂O and SrMnF₅ · H₂O Solid BaF₂ or SrF₂ forms with solutions of Mn³⁺ in aqueous hydrofluoric acid precipitates of hitherto unknown BaMnF₅ · H₂ and SrMnF₅ · H₂O respectively. X-ray structure determination on single crystals of both isotypic compounds (space group P2₁/m, Z = 2; BaMnF₅ · H₂O: a = 537.0(3), b = 817.2(2), c = 628.0(4) pm β = 111.17(5)°, R_w = 0.035 for 1403 reflections; SrMnF₅ · H₂O: a = 510.8(1), b = 792.0(2), c = 610.6(1) pm, β = 110.24(1)° R_w = 0.068 for 539 reflections) reveal pure [MnF₆]^3? octahedra connected with each other to infinite chains by sharing trans corners. The H₂O molecules are coordinated to the alkaline earth ions only and form weak O? H…F hydrogen bonds. The pronounced weakening of the Mn? F bonds within the chain direction (Mn? F 2X 212.7(1)/210.8(5) pm, 2X 183.8(3)/181.8(9) pm, 2X 186.9(2)/187.2(8) pm) may be due by halves to the Jahn-Teller-effect as can be deduced by bond valence calculations.     

Ethyldimethylphenylammonium‐halogenoantimonate(III)

Ethyldimethylphenylammonium‐halogenoantimonates(III) The compounds were prepared by reaction of SbX₃ with EtMe₂PhNX (X = Cl, Br, I) in ethanol. Single crystal structure determinations yielded at room temperature: [EtMe₂PhN]₄Sb₄Cl₁₆ 1 S.G. P2₁/n, No. 14, a = 1234.1(2), b = 1299.8(2), c = 1985.9(5) pm, β = 96.81(2)° and Z = 2; [EtMe₂PhN]₃[Sb₂Br₉], 2 , S.G. Pnma, No. 62, a = 3562.0(7), b = 995.4(2), c = 1276.1(3) pm and Z = 4; [EtMe₂PhN]₄[Sb₆I₂₂], 3 , S.G. P1, No. 2, a = 1146.3(3), b = 1223.1(2), c = 1743.7(3) pm, α = 88.25(2)°, β = 87.33(2)°, γ = 67.09(2)° and Z = 2. Enthalpies of transition and melting were determined with a DSC.     

Nickel-, Palladium- und Platinkomplexe funktionalisierter Makrocyclen. Die Kristallstrukturen von [Ni(py2-tasn)(H2O)](ClO4)2, [Pd(py2-tasn)](PF6)2 und [Pt(py2-tasn)](PF6)2. (py2-tasn=4,7-Bis(2-methylpyridyl)-1-thia-4,7-diazacyclononan

The Crystal Structures of [Ni(py₂-tasn)(H₂O)](ClO₄)₂, [Pd(py₂-tasn)](PF₆)₂, and [Pt(py₂-tasn)](PF₆)₂. (py₂-tasn=4,7-Bis(2-methylpyridyl)-1-thia-4,7-diazacyclononane) . The methylpyridyl functionalized macrocyclic ligand 4,7-Bis(2-methylpyridyl)-1-thia-4,7-diazacyclononane, py₂-tasn, forms the stable complexes [Ni(py₂-tasn)(H₂O)]²⁺, [Pd(py₂-tasn)]²⁺, and [Pt(py₂-tasn)]²⁺. They have been isolated in the solid state and characterized by X-ray crystal structure analyses. All five donor atoms of the ligand are bound to the respective metal atom. Ni^II is octahedrally coordinated, with the pyridyl groups in cis-positions, Pd^II and Pt^II are square pyramidally coordinated, with the thioether group in the apical position. The Pd (Pt)—S distances are 290.7(1) and 305.6(3) pm, respectively. Crystal data: [Ni(py₂-tasn)(H₂O)](ClO₄)₄, orthorhombic, space group P2₁2₁2₁, a=843.8(2), b=1 668.8(3), c=1 694.4(3) pm, Z=4, 2 444 unique data, R(R_w)=0.0825(0.0937); [Pd(py₂-tasn)](PF₆)₂: monoclinic, space group P2₁/c, a=694.7(1), b=1 906.5(4), c=1 980.9(4) pm, β=93,43°, Z=4, 5 429 unique data, R(R_w)=0.0351(0.0451); [Pt(py₂-tasn)](PF₆)₂: monoclinic, space group P2₁/n, a=1 080.1(2), b=1 175.0(2), c=2 075.6(4) pm, β=95.32(3)°, Z=4, 5 567 unique data, R(R_w)=0.0667(0.0845).     

Peroxofluorokomplexe der Übergangsmetalle. VI. Darstellung,Schwingungsspektren und Kristallstruktur von (NH4)3Zr(O2)F5. Ein neues Fehlordnungsmodell für Ammonium-peroxopentafluorometallate(IV) mit Elpasolith-Struktur

Transition Metal Peroxofluoro Complexes. VI. Preparation, Vibrational Spectra, and Crystal Structure of (NH₄)₃Zr(O₂)F₅. A New Disorder Model for Ammonium Peroxopentafluoro Metallates(IV) with Elpasolite Structure (NH₄)₃Zr(O₂)F₅ has been prepared from solution and characterized by the i.r. and raman spectra. The disordered crystal structure was determined: space group Fm3 m, Z = 4, a = 944.01(8) pm, R_w = 0.014 for 162 reflections. A new disorder model – revised with respect to former proposals made for the isotypic Ti compound – allows now to derive unambiguously the geometry of the complex anions: d(O? O) = 157(1), d(Zr? O) = 206.3(9), d(Zr? F), average 203.8 pm. An analogous treatment of the disorder for (NH₄)₃Ti(O₂)F₅ also led to a significant improvement of the results (R_w = 0.019, d(O? O) = 151(2), d(Ti? O) = 197(1), d(Ti? F), average 191.6 pm).     

Die Kristallstrukturen von (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN und [ReCl4(18-Krone-6)]

The Crystal Structures of (NH₄)₂[ReCl₆], [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN and [ReCl₄(18)(Crown-6)] Brown single crystals of (NH₄)₂[ReCl₆] are formed by the reaction of NH₄Cl with ReCl₅ in a suspension of diethylether. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN crystallizes as brown crystal plates from a solution of ReCl₅ in acetonitrile. Lustrous green single crystals of [ReCl₄(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl₅ in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH₄)₂[ReCl₆]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH₄)₂[PtCl₆] type, the Re? Cl distance is 235.5(1) pm. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl₂(CH₃CN)₄]⁺ ions with trans chlorine atoms, [ReCl₆]^2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl₄(18-crown-6)]: Space group P2₁/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.     

Synthese und Kristallstruktur von Cu4[PhN3C6H4N3(H)Ph]4(μ2-O)2, einem vierkernigen Kupfer(II)-Komplex mit 1-Phenyltriazenido-2-phenyltriazenobenzol als Ligand

Synthesis and Crystal Structure of Cu₄[PhN₃C₆H₄N₃(H)Ph]₄(μ₂-O)₂, a Tetranuclear Copper(II) Complex with 1-Phenyltriazenido-2-phenyltriazeno-benzene as Ligand Cu₄[PhN₃C₆H₄N₃(H)Ph]₄(μ-O)₂ ( 1 ) results from the reaction of an aqueous solution of [Cu(NH₃)₄]²⁺ with 1,2-bis(phenyltriazeno)benzene in ether. 1 crystallizes in the orthorhombic space group Pba2 with the lattice parameters a = 1661.5(5), b = 1914.7(7), c = 1269.2(5) pm; Z = 2. In the tetrameric complex with the symmetry C₂ the Cu²⁺ cations form a tetrahedron (Cu? Cu: 298.3(1)?337.1(1) pm). The μ₂-oxo ligands occupy the twofold axis and bridge two opposite edges of the Cu₄ tetrahedron (Cu? O: 190.0(3) and 192.5(4) pm). The 1-phenyltriazenido-2-phenyltriazeno benzene anions bridge two Cu²⁺ ions chelating one metal ion and coordinating monodentate the neighbouring one (Cu? N: 191.0(5)–204.1(4) pm).     

Wasserfreie Selten-Erd-Acetate,M(CH3COO)3 (M = Sm?Lu,Y) mit Kettenstruktur. Kristallstrukturen von Lu(CH3COO)3 und Ho(CH3COO)3

Anhydrous Rare-Earth Acetates, M(CH₃COO)₃ (M = Sm? Lu, Y) with Chain Structures. Crystal Structures of Lu(CH₃COO)₃ and Ho(CH₃COO)₃ Single crystals of the anhydrous rare-earth acetates containing lutetium (type 1) and holmium (type 2) were obtained by crystallisation at 120°C from diluted acetic acid solutions of their oxides and cesium acetate. The crystal structures [Lu(CH₃COO)₃: orthorhombic, a = 825.85(8), b = 1 398.1(2), c = 823.9(1) pm, V_m = 143.24(3) cm³/mol, space group Ccm2₁ (No. 36), Z = 4, R = 0.035, R_w = 0.030; Ho(CH₃COO)₃: monoclinic, a = 1 109.1(3), b = 2 916.3(10), c = 786.8(2) pm, β = 131.90(1)°, V_m = 142.58(8) cm³/mol, space group C2/c (No. 15), Z = 8, R = 0.039, R_w = 0.039, R_w = 0.026] were determined from four-circle diffractometer data sets. The structures consist of one-dimensional infinite chains built up by bridging acetate ions. Ho³⁺ is coordinated by 8 oxygen atoms, whereas Lu³⁺ has only 7 nearest oxygen neighbours. The chains are stacked parallel to the [001] direction. Isotypic compounds with Tm? Lu (type 1) and Sm? Er, Y (type 2) were prepared as powders and characterized by X-ray powder patterns. Thermoanalytical investigations (DTA, Guinier-Simon technique) of all compounds have shown that there is a first-order phase transition at 180°C (type 2) and in the range of 230–255°C (type 1). The high-temperature phase crystallizes with the known Sc(CH₃COO)₃ structure (type 0) where the rare earth cations are surrounded by 6 oxygen atoms. In the case of the type 1 compounds the phase transition is reversible.     

Die Kristallstruktur von [TeCl3(15-Krone-5)]SbCl6

The Crystal Structure of [TeCl₃(15-crown-5)]SbCl₆ The title compound is synthesized by the reaction of tellur tetrachloride, 15-crown-5 and antimony pentachloride in acetonitrile solution, forming colourless crystals, which were characterized by IR spectroscopy and an X-ray structure determination. Space group Pnma, Z = 4, 1966 observed unique reflections, R = 0.072, R_w = 0.052. The compound forms ions [TeCl₃(15-crown-5)]⁺ and SbCl₆^?; in the cation the tellurium atom is eightfold coordinated by the three chlorine atoms and the five oxygen atoms of the crownether molecule (Te? O bond lengths 266 and 279 pm).     

Synthese und Kristallstrukturen der Polytelluridokomplexe (PPh4)4[M2Te12] von Kupfer(I) und Silber(I)

Syntheses and Crystal Structures of the Polytellurido Complexes (PPh₄)₄[M₂Te₁₂] of Copper(I) and Silver(I) The title compounds have been prepared as black crystal needles by reactions of Na₂Te₃ with CuCl and AgNO₃, respectively, in dimethylformamide in the presence of PPh₄Br. With regard to the large cell dimensions the crystal structure determinations were done by an imaging plate instrument. (PPh₄)₄[Cu₂Te₁₂]: Space group P2₁/n, Z = 6, 51 338 detected reflections, structure determination with 14 177 unique reflections with I > 4σ(I), R = 0.081. Lattice dimensions at ? 50°C: a = 1 704.5, b = 1 694.5, c = 5 044 pm, β = 94.20°. (PPh₄)₄[Ag₂Te₁₂]: Space group P2₁/n, Z = 6, 80 811 detected reflections, structure determination with 16 092 unique reflections with I > 3σ(I), R = 0.052. Lattice dimensions at ? 50°C: a = 1 703.8, b = 1 722.9, c = 5 123 pm, β = 94.65°. The structures of the isotypic compounds consist of six symmetry independent PPh₄⁺ ions and two symmetry independent anions [M₂Te₁₂]^4?, in which the metal atoms of two (MTe₄)^?-fivering fragments are linked by a Te₄^2? chain.     

Chemical Transformations of (2,3,9,10-Tetramethyl-1,4,5,7,8,11,12,14-Octa-Azacyclotetradeca-1,3,8,10-Tetraenato)Cobalt(II)Perchlorate

The monomeric octa-aza bis-α-diimine macrocyclic complex [Co^II(C₁₀H₂₀N₈)(H²O)](ClO₄)₂ I, undergoes various reactions on the macrocyclic ligand. Reaction of complex I with triethylamine in double molar proportions, followed by slow aerial oxidation, produces a molecular dimeric complex [Co^II(C₁₀H₁₄N₈)]₂, III, and a novel Co(I) complex [Co^I(C₁₀H₁₉N₈)], IV. Complex III is a staggered cofacial dimer with a cobalt-cobalt bond length 2.86(1) Å. The macrocyclic ligand of the complex contains an a-diimine function in each five-membered chelate ring, and a three-atom N-C-N^? delocalized system in each six-membered chelate ring. Complex IV has the 5-5-6-6 chelate arrangement because one α-diimine moiety is rearranged to a syn-anti configuration. In the structure, the two fused six-membered chelate rings are fully conjugated and the two fused five-membered rings are saturated. However, when complex I reacts with excess triethylamine under the similar conditions, a dimeric complex of another type, [Co^II(C₁₀H_l6N₈)]₂, II, was generated, in which one N-N bond of the macrocyclic ligand is broken. Complex IV can be isolated also from the reaction of complex I with excess hydrazine, followed by slow aerial oxidation. When hydrazine in double molar proportions was used, complex [Co^I(C₁₀H₁₇N₈)(NHNH)] V, which contains a coordinated diazene ligand, was obtained. Only one six-membered chelate ring of complex V is deprotonated and oxidized to form a three-atom N-C-N^? delocalized system. The structures of octa-aza complexes I-V are determined by X-ray crystallography: I, orthorhombic, C mca, a = 11.646(4), b = 17.049(3), c = 10.706(3) Å, Z = 4, R = 0.045, R_w = 0.047, based on 1024 reflections with I > 2σ(I); II, monoclinic, P 2₁/c, a = 9.814(3), b = 22.583(6). c = 14.632(9) Å, β = 98.90(5)°, Z = 4, R = 0.085, R_w = 0.101, based on 2033 reflections with I > 2σ(I); III, tetragonal, P 4/nmm, a = 15.614(3), c = 6.498(2) Å, Z = 4, R = 0.081, R_w = 0.115, based on 340 reflections with I > 2σ(I); IV, orthorhombic, P bca, a = 8.484(1), b = 16.662(3), c = 18.760(2) Å, Z = 8, R = 0.029, R_w = 0.024, based on 1441 reflections with I > 2σ(I); V, monoclinic, P 2₁/m, a = 7.892(3), b = 11.713(6), c = 9.326(4) Å, β = 108.03(3), Z = 2, R = 0.047, R_w = 0.056, based on 948 reflections with I > 2σ(I).     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [O3SS(NPPh3)2] · CH3CN, [SO(NPPh3)2] und [SCl(NPMe3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Syntheses and Crystal Structures of [O₃SS(NPPh₃)₂] · CH₃CN, [SO(NPPh₃)₂], and [SCl(NPMe₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SO₂ and SOCl₂, respectively, and by the reaction of Me₃SiNPMe₃ with S₂Cl₂. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O₃SS((NPPh₃)₂)] · CH₃CN : Space group Pca2₁, Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at ?60°C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S? S bond length of 218.2 pm and bond lengths S? N of 161.2 and P? N of 160.1 pm. [SO(NPPh₃)₂] : Space group P2₁/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at ?50°C: a = 1173.1, b = 1585.6, c = 1619.2 pm, b? = 98.13°. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S? N 166 pm and P? N 163 pm in average. [SCl(NPMe₃)₂]Cl : Space group P1 , Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 613.2, b = 1030.3, c = 1111.4 pm, α = 88.48°, b? = 88.01°, γ = 83.10°. The compound forms ions [SCl(NPMe₃)₂]⁺ and Cl^?. In the cation the sulfur atom is ?-tetrahedrally coordinated with a long S? Cl distance of 246.9 pm and bond lengths S? N of 155.3 pm and P? N of 164.3 pm in average.     

BaClSCN und Na4Mg(SCN)6: Zwei neue wasserfreie Thiocyanate der Erdalkalimetalle

BaClSCN and Na₄Mg(SCN)₆: Two New Thiocyanates of the Alkaline Earth Metals The reaction of BaCl₂ and NaSCN yielded single crystals of BaClSCN (P 2₁/m, Z = 2, a = 588.6(1) pm, b = 465.8(1) pm, c = 864.4(2) pm, β = 100.20(3)°, R_all = 0.0214). According to X‐ray single crystal investigations, the structure consists of anionic SCN^– and Cl^– layers, respectively, alternating in [001] direction. The SCN^–‐ions are connected via the N and the S atoms to the cations. Na₄Mg(SCN)₆ (P 3 1c, Z = 2, a = 863.8(1) pm, c = 1399.3(2) pm, R_all = 0.0870), which was obtained from a melt of NaSCN and MgCl₂, consists of anionic layers with the cations between the sheets. The holes are filled altenatingly by Na⁺ or Na⁺ and Mg²⁺. Regarding only the C‐atoms of the SCN^– group, the structure can be described as a hexagonal closest packing whith the cations occupying 5/6 of the octahedral voids.     

[Cu3(S4)3]−, ein neues kondensiertes anorganisches Ringsystem Strukturvergleich mit anderen Polysulfido-Clustern des Kupfers

[Cu₃(S₄)₃]^3?, a New Condensed Inorganic Ring System. Comparison with the Structures of Other Polysulfido Clusters of Copper By reaction of Cu(CH₃COO)₂ · H₂O with a polysulfide solution [(C₆H₅)₄P]₂(NH₄)-[Cu₃(S₄)₃] · 2CH₃OH ( 1a ) could be obtained in a pure form. The anion [Cu₃(S₄)₃]^3? ( 1 ) consists of a central Cu₃S₃ ring and three CuS₄ rings. An X-ray structure analysis yields the following results for 1a : Space group P2₁/c, a = 2317.4(7), b = 1458.4(4), C = 1843. 1(5) pm, β = 108.68(2)°, V = 5901.0 10⁶ pm³, Z = 4; R = 0.101 for 3817 independent reflections (Fo > 3.92° (Fo)). 1a was also characterized by its Raman spectrum.     

Synthesis,Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)₄Pd]Cl₂·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)₂PdI₂]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na₂[PdCl₄] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L₄Pd₂)NaCl]₂·8MeOH ( 4 ) and [L₄Pt₂Cl₂]·6MeOH·H₂O ( 5 ). The latter is the first Pt^III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R₁ = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R₁ = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R₁ = 0.0341 and for 5 at ?80 °C: monoclinic space group P2₁/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R₁ = 0.0429.     

Water-rich molybdotellurates: Preparation and crystal structure of Li6[TeMo6O24] · 18 H2O and Li6[TeMo6O24] · Te(OH)6 · 18 H2O

Li₆[TeMo₆O₂₄] · 18 H₂O is triclinic (space group P1 , a = 1 041.7(1), b = 1 058.6(1), c = 1 070.8(1) pm, α = 61.08(1), β = 60.44(1), γ = 73.95(1)°). Single crystal X-ray structure analysis (Z = 1, 295 K, 317 parameters, 3 973 reflections, R_g = 0.0250) revealed an infinite branched chain of edge-sharing Li coordination polyhedra to be the prominent structural feature. One of the four crystallographically independent Li⁺ is coordinated octahedrally. The coordination polyhedra of the remaining Li⁺ are distorted trigonal bipyramids. Only three unique oxygen atoms (O(9), O(10), O(12)) of the centrosymmetric [TeMo₆O₂₄]^6? anion are bound to Li⁺. The further positions in the coordination spheres of the Li⁺ are occupied by water molecules. Intermolecular hydrogen bonds involve mainly oxygen atoms of the [TeMo₆O₂₄]^6? anion as nearly equivalent proton acceptors without regard to their different bonding modes to Te and Mo, respectively. Li₆[TeMo₆O₂₄] · Te(OH)₆ · 18 H₂O crystallizes monoclinically in space group P2₁/n with Z = 4, a = 994.1(3), b = 2 344.8(10), c = 1 764.9(4) pm, and β = 91.36(4)°. Single crystal structure analysis with least squares refinement of 627 parameters (5 900 reflections, 295 K) converged to R_g = 0.0324. There are six unique Li⁺ cations. The coordination polyhedra of Li(1), Li(2), Li(3), and Li(4) are linked by common edges to yield an eight membered centrosymmetric strand. The coordination polyhedra of the remaining two Li⁺ sites (Li(5), Li(6)) are connected to a dimeric unit via a common corner. All oxygen atoms of the Te(OH)₆ molecule are involved in the coordination of Li⁺. However, only three oxygen atoms (O(13), O(18), O(23)) of the [TeMo₆O₂₄]^6? anion which lacks crystallographic symmetry are involved in the coordination of Li⁺. The oxygen atoms of the anion act as proton acceptors in hydrogen bonds of predominantly medium strength. Te(OH)₆ molecules and [TeMo₆O₂₄]^6? anions connected by strong hydrogen bonds form an infinite chain.     

Syntheses and Characterization of New Copper Complexes with the Heterocyclic Thione,AMTTO. X‐Ray Structures of [Cu(AMTTO)Cl2], [Cu(AMTTO)2]Cl,and [Cu(AMTTO)(PPh3)2Cl] (AMTTO = 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3‐thione‐5‐one)

The complexes [Cu(AMTTO)Cl₂] ( 2 ), [Cu(AMTTO)₂]Cl ( 3 ), and [Cu(AMTTO)(PPh₃)₂Cl] ( 4 ) have been prepared and characterized by IR spectroscopy and elemental analyses. Also single‐crystal X‐ray diffraction studies on compound 2 , 3 and 4 revealed that AMTTO acts in 2 as a bidentate ligand via nitrogen and sulfur atoms, in 3 and 4 as a monodentate via sulfur atoms. Complex 3 was already mentioned in literature, but the structure was not described in detail. The molecules in 2 form infinite chains through additional weak Cu—S interactions along [010] indicating the Jahn‐Teller distortion of the d⁹ ion Cu²⁺. The infinite chains are connected by hydrogen bonding along [100]. Crystal data for 2 at —80°C: monoclinic, space group P2₁/m, a = 666.7(1), b = 609.4(1), c = 1132.6(2) pm, b = 95.46(2)°, Z = 2, R₁ = 0.0365; for 3 at —80°C: orthorhombic, space group Pbcn, a = 1291.2(2), b = 1146.5(1), c = 1000.5(1) pm, Z = 4, R₁ = 0.0315; for 4 at —80°C: monoclinic, space group, P2₁/n, a = 879.4(1), b = 1849.3(2), c = 2293.8(3) pm, β = 92.38(1)°, Z = 4, R₁ = 0.0688.     

Polymorphie von Cs2NaMnF6. Die Kristallstrukturen der Hochdruck- und der Hochtemperaturmodifikation

Polymorphism of Cs₂NaMnF₆. Crystal Structures of the High Pressure and the High Temperature Phase Cs₂NaMnF₆ has been prepared in three polymorphous forms and investigated by X-ray diffraction. Under high pressure (> 5 kbar) a cubic α-phase was formed with elpasolite structure (space group Fm3m, a = 876.2 pm, Z ? 4, R ? 0.045 for 12 powder reflections). By quenching from 700°C a high temperature γ-form could be trapped with 12L-Cs₂NaCrF₆ structure (space group R¯3m, Z = 6, R_w ? 0.041 for 419 independent single crystal reflections). The “normal” β-phase is a low symmetric variant of this 12L-type. The influence of the Jahn-Teller effect on the structures and the polymorphism is discussed.     

Oxometallate neuen Typs: Über Ba3NaNbO6 und Ba3NaTaO6

Oxometallates of a new Type: On Ba₃NaNbO₆ and Ba₃NaTaO₆ For the first time in form of colourless, transparent single crystals of Ba₃NaNbO₆ [annealed mixtures of BaO, Na₂O and Nb₂O₅, Ba : Na : Nb = 3.3 : 1.1 : 1, Ni-cylinder, 1100°C, 3d] as well as Ba₃NaTaO₆ [annealed mixtures of BaO, Na₂O and Ta₂O₅, Ba : Na : Ta = 3.3 : 1.1 : 1, Ni-cylinder, 1100°C, 3d] have been prepared. The crystal structure was solved by fourcycle-diffractometer data [Ba₃NaNbO₆: Mo? Kα , 356 out 356 I₀ (hkl), space group R3 c with a = 1026.6(1)pm, c = 1195.3(2)pm (Guinier-Simon powder data), Z = 6, R = 2.4%, R_w = 2.0% and Ba₃NaTaO₆: Ag? Kα , 498 out of 498 I₀ (hkl), space group R3 c with a = 1027.6(1)pm, c = 1196.0(2)pm (Guinier-Simon powder data), Z = 6, R = 4.9%, R_w = 4.4%], parameters see text. The Ba₃M part of structure (M = Nb, Ta) corresponds to a slightly (hexagonal) deformed Nb₃Al arrangement with Na inserted along [001] between adjacent M^v, which are nearly perfectly octahedrally surrounded by 6 O. The structural relations are deduced by Schlegel Diagrams. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Ionic Radii, MEFIR, as well as Charge Distribution, CHARDI, are calculated.