Structural and thermal study of asymmetric α-dioxime complexes of Co(III) with Cl and methyl-pyridines

Two new cobalt(III)-chelates, trans-bis(methyl-ethyl-dioximato)-chloro-β-picoline-cobalt (III) (1), and trans-bis(methyl-ethyl-dioximato)-chloro-3,4-lutidine-cobalt (III) (2) were obtained by oxidizing a mixture of CoCl₂, methyl-ethyl-dioxime and amines: β-picoline (3-methyl-pyridine) for (1) and 3,4-lutidine (3,4-dimethyl-pyridine) for (2). The crystal structure of (1) was determined by single crystal XRD (monoclinic, space group P2₁/c (No. 14) with a = 8.391(3) Å, b = 14.421(5) Å, c = 18.383(8) Å, β = 114.57(2)°, R = 0.0499), while both (1) and (2) were studied by middle and far FTIR spectroscopy, electrospray ionization (ESI) MS, powder XRD and thermal analysis (TG/DTA-MS). Melting of the related complexes 1 and 2 at 219 and 184 °C, respectively, results in an immediate chemical degradation of their whole structure and tarring of ligands.     

[Li(12-Krone-4){(Me3Si)2N}2TiCH2SiMe2NSiMe3] – ein Ionenpaar mit gestreckter Li–C–Ti-Achse

[Li(12-Crown-4){(Me₃Si)₂N}₂TiCH₂SiMe₂NSiMe₃] – an Ion-Pair with a Linear Li–C–Ti-Axis The title compound ( 1 ) has been prepared from Ti[N(SiMe₃)₂]₃ and n-butyllithium in OEt₂/n-hexane in the presence of 12-crown-4. Smaragd-green single crystals of 1 · C₇H₈ which were suitable for X-ray crystallography were formed from toluene solutions at –18 °C. According to the crystal structure determination 1 forms ion pairs between the lithium atom and the CH₂-carbon atom which is member of a planar Ti–C–Si–N heterocycle. The coordination geometry of the Li–C–Ti axis is linear (bond angle 172.8° in average of the two symmetry independent species) with coordination number five at the CH₂-carbon atom.     

Über röntgenographische Einkristalluntersuchungen an Na2FeAlF7, Na2MIIGaF7 (MII = Ni,Zn) und Na2ZnFeF7 und die Strukturchemie der Weberite

On X-Ray Single Crystal Studies of Na₂FeAlF₇, Na₂M^IIGaF₇ (M^II = Ni, Zn), and Na₂ZnFeF₇ and the Structural Chemistry of Weberites At single crystals of the orthorhombic weberite Na₂NiGaF₇ (a = 716.1, b = 1021.6, c = 740.9 pm; Imma, Z = 4) and of the monoclinic variants (C2/c, Z = 16) Na₂FeAlF₇ (a = 1242.6, b = 727.8, c = 2420.6 pm, β = 99.99°), Na₂ZnGaF₇ (a = 1251.9, b = 730.3, c = 2435.3 pm, β = 99.74°) and Na₂ZnFeF₇ (a = 1261.0, b = 7.359, c = 2453.8 pm, β = 99.70°) complete X-ray structure determinations were performed. The results and the influence of radii on the bridge angles M^II–F–M^II and M^II–F–M^III are discussed in connection with general features within the structural chemistry of 28 weberites.     

Zur Reaktion des Rhenium(VII)-oxids mit 1,4-Dioxan – Kristallstruktur von Re2O7(OH2)2 · 2(1,4-Dioxan)

Reaction of Rhenium(VII) Oxide with 1,4-Dioxane – Crystal Structure of Re₂O₇(OH₂)₂ · 2(1,4-Dioxane) By solvolysis of polymeric Re₂O₇ with 1,4-dioxane in the presence of small amounts of H₂O two products of compositions Re₂O₆(OH)₂ · 3(1,4-dioxane) ( 1 ) and Re₂O₇ · 2H₂O · 2(1,4-dioxane) ( 2 ) are formed. From a complete X-ray single-crystal structure analysis 2 could now be characterized structurally (monoclinic, space group P2₁/c, a = 6.828(3) Å, b = 9.530(2) Å, c = 26.421(8) Å, β = 91.71(3)°, Z = 4). The compound is important as a convenient precursor for the preparation of pure rhenium trioxide. It is to be formulated as Re₂O₇(OH₂)₂ · 2(1,4-dioxane) and contains, contrary to 1 , no 1,4-dioxane coordinated to Re. The crystalline phase consists of a supramolecular arrangement of Re₂O₇(OH₂)₂ units as in “solid perrhenic acid” and of 1,4-dioxane molecules associated through O? H …? O hydrogen bridges. Analogous to dirhenium heptoxide and to solid perrhenic acid one of the rhenium atoms is in tetrahedral, the other is in distorted octahedral coordination.     

Synthese und Kristallstruktur von Ba2ScCl7, ein Bariumchlorid-hexachloroscandat(III), Ba2Cl[ScCl6]

Synthesis and Crystal Structure of Ba₂ScCl₇, a Barium Chloride Hexachloroscandate(III), Ba₂Cl[ScCl₆] Colourless single crystals of Ba₂ScCl₇ are obtained from a 1 : 1 molar mixture of BaCl₂ and ScCl₃. It crystallizes with the non-centrosymmetric monoclinic space group P2₁ with a = 688,88(7), b = 1349,4(1), c = 1207,4(1), β = 94,93(1)° in a new structure that contains isolated [ScCl₆] octahedra and one ‘‘lonesome”︁”︁ chloride ligand according to Ba₂Cl[ScCl₆].     

Sm2As4O9: Ein ungewöhnliches Samarium(III)‐Oxoarsenat(III) gemäß Sm4[As2O5]2[As4O8]

Sm₂As₄O₉: An Unusual Samarium(III) Oxoarsenate(III) According to Sm₄[As₂O₅]₂[As₄O₈] Pale yellow single crystals of the new samarium(III) oxoarsenate(III) with the composition Sm₄As₈O₁₈ were obtained by a typical solid‐state reaction between Sm₂O₃ and As₂O₃ using CsCl and SmCl₃ as fluxing agents. The compound crystallizes in the triclinic crystal system with the space group (No. 2, Z = 2; a = 681.12(5), b = 757.59(6), c = 953.97(8) pm, α = 96.623(7), β = 103.751(7), γ = 104.400(7)°). The crystal structure of samarium(III) oxoarsenate(III) with the formula type Sm₄[As₂O₅]₂[As₄O₈] (≡ 2 × Sm₂As₄O₉) contains two crystallographically different Sm³⁺ cations, where (Sm1)³⁺ is coordinated by eight, but (Sm2)³⁺ by nine oxygen atoms. Two different discrete oxoarsenate(III) anions are present in the crystal structure, namely [As₂O₅]^4? and [As₄O₈]^4?. The [As₂O₅]^4? anion is built up of two Ψ¹‐tetrahedra [AsO₃]^3? with a common corner, whereas the [As₄O₈]^4? anion consists of four Ψ¹‐tetrahedra with ring‐shaped vertex‐connected [AsO₃]^3? pyramids. Thus at all four crystallographically different As³⁺ cations stereochemically active non‐binding electron pairs (“lone pairs”) are observed. These “lone pairs” direct towards the center of empty channels running parallel to [010] in the overall structure, where these “empty channels” being formed by the linkage of layers with the ecliptically conformed [As₂O₅]^4? anions and the stair‐like shaped [As₄O₈]^4? rings via common oxygen atoms (O1 – O6, O8 and O9). The oxygen‐atom type O7, however, belongs only to the cyclo‐[As₄O₈]^4? unit as one of the two different corner‐sharing oxygen atoms.     

Direct Synthesis of a Dimeric Mixed-Anions Bismuth(III) Complex: Synthesis and Structural Characterization of [Bi2(Phen)4(No3)4.4I0.6]I3 (A New Dimeric Compound)

A direct synthetic method of mixing Bi(NO₃)₃ and NaI with 1,10-phenanthroline yielded red crystals of [Bi₂(phen)₄(NO₃)_4.4I_0.6]I₃. In this complex the cationic part is in fact binuclear and contains two [Bi(phen)(NO₃)_1.7I_0.3] groups linked via a bridging NO^? ₃ anion. The I^? ₃ anion was not coordinated to bismuth(III) and the lone pair of valence electrons of the bismuth(III) ions appears to be stereochemically inactive. There are two independent NO^? ₃ anions, one coordinated to bismuth but another shares a position with I^? anion. The final results of crystallography show that 40% of these positions are occupied by NO^? ₃ anions and 60% by I^? anions that are coordinated to bismuth atom in bidentate fashion (NO^? ₃) and in unidentate fashion (I^?). An interesting point is that the I^? ₃ anion was produced by direct synthetic method (Branched tube method). There is a π-π stacking interaction between the parallel aromatic rings around the Bi(III) ion.     

Pr(CH3COO)3, ein wasserfreies Selten-Erd-Acetat mit Netzwerkstruktur

Pr(CH₃COO)₃, an Anhydrous Rare-Earth Acetate with a Network Structure Pr(CH₃COO)₃ may be prepared by dehydration of Pr(CH₃COO)₃ · 1,5 H₂O at 180°C as an amorphous green powder. Single crystals were grown from the powder by addition of (NH₄)CH₃COO as ?mineralisator”? at 180°C in a sealed glass ampoule. The crystal structure (tetragonal, P4 2₁c (no. 114), Z = 24, a = 2106.5(3), c = 1323.6(1) pm, V_m = 147.39(3) cm³/mol, R = 0.055, R_w = 0.029) was determined from four-circle-diffractometer data. The Pr³⁺ ions occupy three crystallographically independent positions and are surrounded by 9 and 10 oxygen atoms, respectively. Acetate ions connect the cations to a complicated three-dimensional network.     

Crystal and Molecular Structure of Potassium trans-bis(iminodiacetato)-cobaltate(III)-2H2O

The combination of iminodiacetic acid (H₂ida) with cobalt(II) chloride hexahydrate in the presence of sodium hydroxide, followed by heating, produces the trans-facial isomer of K[Co(ida)₂]·2H₂O. This compound contains extensive intermolecular and intramolecular coordination and hydrogen bonding involving the potassium ions, and results in a complex three-dimensional structure in which each potassium ion is immediately surrounded by six cobalt centers.     

Neutrale Thiolate und ein Iodidthiolat von Antimon(III). Die Kristallstrukturen von Sb(SC6H5)3, Sb(SC6H2Me3-2,4,6)3 und SbI(SC6H2Me3-2,4,6)2

Neutral Thiolates and a Iodothiolate of Antimony(III). Crystal Structures of Sb(SC₆H₅)₃, Sb(SC₆H₂Me₃-2,4,6)₃, and SbI(SC₆H₂Me₃-2,4,6)₂ The crystal structures of Sb(SC₆H₅)₃ ( 1 ), Sb(SC₆ · H₂Me₃-2,4,6)₃ ( 2 ), and the novel compound SbI(SC₆H₂Me₃-2,4,6)₂ ( 3 ) have been determined by X-ray crystallography. In addition to the expected trigonal pyramidal coordination of antimony intermolecular interactions are observed for 1 (Sb … O: 363.3 pm) and 3 (Sb … S: 2 × 369.4 pm) but not for 2 . The reasons for these differences are discussed.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

AlIII-Phthalocyanine: Darstellung,Eigenschaften und Kristallstruktur von Tetra(n-butyl)ammonium-trans-di(nitrito(O))phthalocyaninato(2−)aluminat(III)

Al^III Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)-ammonium-trans-di(nitrito(O))phthalocyaninato(2?)aluminate(III) [Al(Cl)Pc^2?] reacts with excess (ⁿBu₄N)NO₂ in dimethylformamide yielding less soluble blue tetra(n-butyl)ammonium-trans-di(nitrito(O))phthalocyaninato(2?)aluminate(III), (ⁿBu₄N)^trans[Al(ONO)₂Pc^2?], which crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4. The Al atom is in the special position 4 d in the center of the Pc^2? ligand and the two nitrit ions are monodentate O-coordinated in a mutually trans arrangement to the Al atom. The Al? O and average Al? N_iso bond distances are 1.927(2) and 1.956 Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.277(4) Å; d(N? O) = 1.221(4) Å; ?(O? N? O) = 114.3(3)°; ?(Al? O? N) = 121.3(2)°. The non-bonded O atoms are trans to the Al atom. The Pc^2? ligand is slightly ruffled. The UV-VIS-NIR spectra and the vibrational spectra are discussed.     

Ein- und zweikernige Fluorokomplexe des Titan(III), Chrom(III) und Eisen(III) Darstellung und Struktur von (NMe4)(Ti(H2O)4F2)TiF6 · H2O, (NMe4)3Cr2F9 und (NMe4)3Fe2F9

Mono- and Dinuclear Fluoro Complexes of Titanium (III), Chromium (III), and Iron(III). Syntheses and Structures of (NMe₄) (Ti(H₂O)₄F₂)TiF₆ · H₂O, (NMe₄)₃Cr₂F₉, and (NMe₄)₃Fe₂F₉ The title compounds have been prepared by reaction of MCl₃ (M = Ti, Cr, Fe) with NMe₄F in dimethylformamide. (NMe₄)₃Cr₂F₉ and (NMe₄)₃Fe₂F₉ contain the face-sharing biocathedral M₂F₉^3? unit. The M…M distances are 277.1(1) and 289.8(3) pm in (NMe₄)₃Cr₂F₉ and (NMe₄)Fe₂F₉, respectively. (NMe₄)(Ti(H₂O)₄F₂)TiF₆ · H₂O contains trans-Ti^III(H₂O)₄F₂⁺ cations and Ti^IVF₆^2? anions. Crystal data: (NMe₄)₃Cr₂F₉: hexagonal, space group P6₃/m, a = 804.1(3), c = 1857.5(4) pm, Z = 2, 529 reflections, R = 0.049; (NMe₄)₃Fe₂F₉: hexagonal, space group P6₃/m, a = 804.7(5), c = 1 861.6(5) pm, Z = 2, 635 reflections, R = 0,046; (NMe₄)(Ti(H₂O)₄F₂)TiF₆ · H₂O: orthorhombic, space group Pbca, a = 776.9(2), b = 1 616.3(3), c = 2 428.6(7) pm, Z = 8, 2 784 reflections, R = 0,056.     

Cs2(H3O)Pr(CH3COO)6 und Cs2Pr(CH3COO)5: Synthese,Kristallstrukturen und Thermolyse. Über die analogen Acetate mit Lanthan bis Terbium

Cs₂(H₃O)Pr(CH₃COO)₆ and Cs₂Pr(CH₃COO)₅: Synthesis, Crystal Structures and Thermolysis. Analogous Acetates with Lanthanum through Terbium Single crystals of Cs₂(H₃O)Pr(CH₃COO)₆ are obtained as green plates from an acetic acid solution (≈50%) of Cs₂CO₃ and Pr(CH₃COO)₃ · 1,5 H₂O. The crystal structure monoclinic, Cm, Z = 2, a = 1 540.4(4), b = 691.3(2), c = 1 221.5(4) pm, β = 104.60(5)°, V_m = 379.1(2) cm³/mol, R = 0.040, R_w = 0.035 was determined from four-circle-diffractometer data. The structure consists of monomeric Pr(CH₃COO)₃ units, in which Pr³⁺ is surrounded by nine oxygen atoms. These monomers are linked together to infinite layers parallel (001) by common acetate oxygen atoms with two ?molecules”? of Cs(CH₃COO). Together with an additional acetate ion coordinated to one of the Cs⁺ ions the composition of the layers is [Cs₂Pr(CH₃COO)₆]^?. Between these layers H₃O⁺ is located for electroneutrality. Thermal decomposition of Cs₂(H₃O)Pr(CH₃COO)₆ was examined with thermoanalytical methods (TG/DTA with coupled gas analysis), Guinier-Simon technique and IR spectroscopy: beginning at 70°C the compound looses water and acetic acid. It decomposes topotactically to Cs₂Pr(CH₃COO)₅. At 270°C this acetate decomposes to Cs₂CO₃ and Pr₂O₂CO₃ which emits CO₂ at 600°C form ing Pr₂O₃or PrO_2?x Single crystals of Cs₂Pr(CH₃COO)₅ were obtained from Pr(CH₃COO)₃, in molten Cs(CH₃COO) at about 200°C. The crystal structure tetragonal, P4₃, Z = 4, a = 1 174,5(2), c = 1 480,5(3) pm, V_m = pin,307,5(1) cm³/mol, R = 0,061, R_w= 0,031 again consists of Pr(CH₃COO)₃, monomers where Pr³⁺ has 9 oxygen ligands in its first coordination sphere. They are linked together by two ”molecules“ of cesium acetate to infinite chains along [00l] around the 4, screw axis. There are also acetate bridges between these chains. Isotypic compounds Cs₂(H₃O)M(CH₃COO)₆ and Cs₂M(CH₃COO)₅, and Cs₂M(CH₃COO)₅with M = La? Tb, were obtained from acetic acid solutions or thermal decomposition and were characterized by X-ray Guinier techniques.     

Synthesis,Structure and Characterization of the Cyano-Bridged Heteropolymer Poly{[Bis(Trimethylenediamine)Copper(II)][Hexacyanocobalt(III)]} Perchlorate Dihydrate with a Two-Dimensional Framework

The complex [Cu(tn)₂]₂[Co(CN)₆](ClO₄)·2H₂O (tn = trimethylenediamine) has been prepared and characterized by elemental analysis, IR, electronic and electronic spin resonance spectra and magnetic properties. The x-ray structure analysis shows that each [Co(CN)₆]^3? ion coordinates to four [Cu(tn)₂]²⁺ cations through four cyano nitrogen atoms in the same plane, providing a two-dimensional square network structure, formed from Co-CN-Cu(tn)₂-NC-Co linkages.     

Polyol-Metall-Komplexe. 17. Kristalline Eisen(III)-Komplexe mit zweifach deprotonierten Anhydroerythrit-Liganden

Polyol Metal Complexes. 17. Crystalline Iron(III) Complexes with Twofold Deprotonated Anhydroerythritol Ligands Three new crystalline ferrates(III) with diolato ligands derived from anhydroerythritol by deprotonation have been synthesized from wet alcoholic and from aqueous solution. Almost colourless, monoclinic crystals of Na₂[Fe(AnEryt-H_-2)₂(OH)] · 0.5 NaNO₃ · 3.5 H₂O ( 1 ) have been prepared from ethanolic solutions. They content mononuclear bis diolato hydroxo ferrate(III) dianions. Trinuclear hexakis diolato μ₃-methoxo triferrat(III) tetraanions constitute the anionic part of Na₄[Fe₃(AnErytH_-2)₆(OMe)] · 2.5 NaNO₃ ( 2 ), yellow-green hexagonal crystals of which are formed from wet methanolic solutions. Yellow-green triclinic crystals of Ba₂[Fe₂(AnEryt-H_-2)₄(μ-OH)₂] · 12 H₂O ( 3 ) have been precipitated from aqueous solutions. In 3 , the anions of 1 are dimerized to give tetrakis diolato di-μ-hydroxo diferrat(III) tetraanions.     

Ternäre Acetate der Lanthanide mit Caesium: Dimere und Trimere in CsLu(CH3COO)4 bzw. Cs2[Lu3(CH3COO)10(OH)(H2O)]. Synthese,Kristallstrukturen und Thermolyse

Ternary Acetates of the Lanthanides with Cesium: Dimers in CsLu(CH₃COO)₄ and Trimers in Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)]. Synthesis, Crystal Structures, Thermolysis Single crystals of CsLu(CH₃COO)₄ and Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)] were obtained from an aqueous solution of lutetium and cesium acetate in a 1:1 molar ratio. The crystal structures (CsLu(CH₃COO)₄: monoclinic, P2₁/n (no. 14), Z = 8, a = 1 293.1(2), b = 1 323.8(2), c = 1 622.5(3) pm, β = 92.01(2)°, V_m = 208.97(6) cm³/mol, R = 0.056, R_w = 0.034; Cs₂[Lu₃(CH₃COO)₁₀(OH)(H₂O)]: monoclinic, C2/c (no.15), Z = 4, a = 2 138.5(6), b = 1 378.0(3), C = 1 482.9(4) pm, β = 106.15(2)°, V_m = 632.0(3) cm³/mol, R = 0.049, R_w = 0.036) were determined from four-circle-diffractometer data. The structures consist of dimers and trimers, respectively, that are built by bridging acetate groups. These units are fragments of the infinite chains of the Ho(CH₃COO)₃ type of structure. The isotypic compounds CsM(CH₃COO)₄ with M=Eu? Lu were synthesized and characterized by the X-ray Guinier technique. The thermal decomposition of CsLu(CH₃COO)₄ was examined with thermoanalytical methods (TG/DSC with coupled gas analysis) and the Guinier-Simon technique: it decomposes at 260°C in an endothermic reaction to Lu₂O₃ and Cs₂CO₃.     

Synthesis,Structure, and Polarized Optical Spectra of a New Fluoromanganate(III): [(H3N(CH2)2)2NH2]2[MnF5(H2O)]3

The synthesis and crystal structure of a new fluoromanganate(III), [(H₃N(CH₂)₂)₂NH₂]₂[MnF₅(H₂O)]₃, is reported. The unit cell is unusually large: monoclinic, P2₁/c (no. 14), a = 41.0512(13) Å; b = 9.6469(4) Å; c = 12.8021(7) Å; β = 91.927(4)°; Z = 8, R = 0.0627 and wR₂ = 0.1347. The [MnF₅(H₂O)]^2– anions are octahedral with a strong distortion along the F–Mn OH₂ axes due to the Jahn-Teller effect. A very rich intermolecular hydrogen bond framework is present, leading to chains of octahedra linked by double-hydrogen bonds. The polarized optical spectra on single crystals are explained in terms of the intraconfigurational d⁴ transitions split by a ligand field of C_4v symmetry.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsCl(acac)(EPh3)], E = P,As, Sb

Synthesis, Crystal Structures, and Vibrational Spectra of [OsCl(acac)(EPh₃)], E = P, As, Sb By reaction of tetrachloroacetylacetonatoosmate(IV) with PPh₃, AsPh₃ or SbPh₃ in ethanol the complexes [OsCl(acac)(EPh₃)], E = P, As, Sb are formed, which are purified by chromatography on silica gel. X-ray crystal structure determinations of the isotypic single crystals of [OsCl(acac)(EPh₃)] (monoclinic, space group P 2₁/c, Z = 4; E = P ( 1 ): a = 12.972(2), b = 18.255(2), c = 16.517(2) Å, β = 112.61(2)°; E = As ( 2 ): a = 13.173(5), b = 18.299(5), c = 16.429(5) Å, β = 112.346(5)°; E = Sb ( 3 ): a = 13.573(3), b = 18.520(3), c = 16.440(9) Å, β = 111.78(2)°) result in mean bond distances Os–P = 2.412, Os–As = 2.485, Os–Sb = 2.619, Os–Cl = 2.354 and Os–O = 2.032 Å. The IR spectra (10 K) exhibit the inner ligand vibrations of the acac and EPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 500–524, of OsAs at 330–339, of OsSb at 271–278, of OsCl at 317–322 and of Os–O in the range 460–694 cm^–1.     

Darstellung und Kristallstruktur von (n-Bu4N)3[Ir(NCS)(SCN)5]

Preparation and Crystal Structure of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] The evaporated ethanolic extrakt of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6?-n]^3?, n = 0? 2, and small amounts of linkage isomeric chloropentarhodanoiridates(III), from which [Ir(NCS)(SCN)₅]^3? has been isolated by ion exchange chromatography on DEAE-cellulose. The X-Ray structure determination on a single crystal of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] (monoclinic, space group P 2₁/a, a = 17.513(5), b = 32.607(5), c = 23.661(5) Å, β = 94.757(5)°, Z = 8) confirms the existance of a heteroleptic hexakis(thiocyanato(N)-thiocyanato(S))iridate(III) with an Ir? N distance of 2.03 Å and Ir? S bond lengths between 2.29 and 2.38 Å. The SCN groups with angles between 166 and 175° are nearly linear with Ir? S? C angles from 99.9 to 109.4°. The Ir? N? C angles of the two crystallographic independent anions are 166 and 174°.