Über Chalkogenolate. 104. Untersuchungen über Halbester der Monothiokohlensäure. 3. Kristallstruktur von Kaliummethyloxoxanthat

On Chalcogenolates. 104. Studies on Hemiesters of Monothiocarbonic Acid. 3. Crystal Structure of Potassium Methyl Oxoxanthate K[SOC? OCH₃] crystallizes with Z = 4 in the monoclinic space group P2₁/n with cell dimensions a = 6.742(5), b = 6.968(5), c = 10.777(6) Å, β = 104.6(6)°. The structure has been determined from single crystal X-ray data by means of Patterson and Fourier synthesis and refined to a final conventional R value of 0.037 using 1292 independent reflexions. The structure is built up of K⁺ and [SOC? OCH₃]^? ions. The potassium ion is bonded to four oxygen and four sulfur atoms from five oxoxanthate ions. The coordination polyhedron consists of two reciprocally penetrated and distorted O₄ and S₄ tetrahedra.     

Über Chalkogenolate. 152. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 2. Kristallstruktur von Tetra-n-butylammonium-N-thioformyldithiocarbamat

On Chalcogenolates. 152. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 2. Crystal Structure of Tetra-n-butylammonium N-Thioformyl Dithiocarbamate The title compound [N(ⁿC₄H₉)₄][S₂C? NH? CS? H] crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 9.694(2) Å, b = 11.478(3) Å, c = 12.551(6) Å, α = 63.03(3)°, β = 66.42(2)°, γ = 85.60(2)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.061 for 2249 independent reflections (R_w = 0.042). The structure is built up of dimeric aggregates consisting of 2[N(ⁿC₄H₉)₄]⁺ cations and 2[S₂C? NH? CS? H]^? anions. The two anions are linked together by ? CS? S…?H? N bridges. To make possible a space saving stacking of the dimeric aggregates in the crystal, one methyl group in terminal position of one n-butyl chain in the cation has gauche conformation.     

Über Chalkogenolate. 118. Kristall- und Molekülstruktur von Oxovanadin(V)-ethylxanthat

On Chalcogenolates. 118. Crystal and Molecular Structure of Oxovanadium(V) Ethylxanthate VO[S₂C? OC₂H₅]₃ crystallizes with Z = 8 in the monoclinic space group P2₁/n with cell dimensions a = 15.065(7) Å, b = 18.540(48) Å, c = 12.824(7) Å, = 99.31(7)°. The crystal and molecular structure has been determined from single crystal X-ray data at 20°C and refined to a conventional R of 0.045.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

Kristallstrukturen von Säurehydraten und Oxoniumsalzen. XX. Die Oxoniumtetrafluoroborate H3OBF4, [H5O2]BF4 und [H(CH3OH)2]BF4

Crystal Structures of Acid Hydrates and Oxonium Salts. XX. Oxonium Tetrafluoroborates H₃OBF₄, [H₅O₂]BF₄, and [H(CH₃OH)₂]BF₄ The crystal structures of three oxonium tetrafluoroborates were determined. H₃OBF₄, oxonium tetrafluoroborate proper, is triclinic with space group P1 , Z = 2 and the unit cell dimensions a = 4.758, b = 6.047, c = 6.352 Å and α = 80.40, β = 79.48, γ = 88.25° at ?26°C. Cations H₃O⁺ and anions BF₄^? are linked by hydrogen bonds O? H…?F into ribbons of condensed rings. In [H₅O₂]BF₄ (diaquohydrogen tetrafluoroborate, monoclinic, P2₁/c, Z = 4, a = 6.584, b = 9.725, c = 7.084 Å, β = 95.15° at ?100°C) the hydrogen bond in the cation H₅O₂⁺ is 2.412 Å short, asymmetric and approximately centered and the linking of cations and anions three-dimensional. In [H(CH₃OH)₂]BF₄ (Bis(methanol)hydrogen tetrafluoroborate, monoclinic, P2₁/c, Z = 4, a = 5.197, b = 14.458, c = 9.318 Å, β = 94.61° at ?50°C) the cation [H(CH₃OH)₂]⁺ is characterized for the first time in a crystal structure with an again very short (2.394 Å), asymmetric and effectively centered hydrogen bond. By further hydrogen bonds cations and anions form only dimers of the formula unit of centrosymmetric cyclic structure.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Über neue Fluoride des Kupfers Zur Kenntnis von Cs[CuF4]

New Fluorides of Copper. On Cs[CuF₄] Due to powder diagrams, Cs[CuF₄], the first diamagnetic fluoride (χ_Mol = ?516·10^?6 cm³/Mol) of trivalent copper, with planar coordination orange-coloured, crystallizes tetragonal, K[BrF₄]-type of structure with planar [CuF₄]-units (a = 5.8488(4) Å, c = 12.043(1) Å). We obtained Cs[CuF₄] by high pressure fluorination (p_F2 = 350 bar, 400°C, 7 h) of CsCuCl₃ in autoclaves.     

Über Oxocobaltate der Alkalimetalle. Zur Kenntnis von Li8CoO6

Oxocobaltates of Alkali Metals. On Li₈CoO₆. Hitherto unknown Li₈CoO₆, rubin- red single crystals, cristallizes according to WEISSENBERG and precession photographs (MoK_α) hexagonal with a = 5.44 Å, c = 10.87 Å; c/a = 2.0; Z = 2, space group C? P6₃cm. Atomic parameters see text. The structure derives from a closest packing of O^2?, ABACA … (The tetrahedral, ?isolated”? groups [CoO₄] show remarkable short distances Co–O (1.66 Å), comparable with [CoO₄] in Li₄CoO₄, being isotypic with Li₄SiO₄. The MADELUNG Part of Lattice Energy is calculated and discussed.     

Über Chalkogenolate. 170. Reaktion von N,N′-Diphenylformamidin mit Kohlenstoffdisulfid 3. Kristallstruktur von Kalium-N,N′-diphenyl-N-formimidoyldithiocarbamat · Dioxan

On Chalcogenolates. 170. Reaction of N,N′-Diphenyl Formamidine with Carbon Disulfide 3. Crystal Structure of Potassium N,N′-Diphenyl N-Formimidoyl Dithiocarbamate · Dioxane The title compound K[S₂C? N(C₆H₅)? CH?NC₆H₅] · C₄H₈O₂ crystallizes with Z = 4 in the monoclinic space group P2₁/a with cell dimensions a = 10.703(2) Å, b = 18.068(3) Å, c = 10.504(3) Å, β = 100.96(3)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.052 for 4556 independent reflections (R_w = 0.054). The K⁺ cation is surrounded of one oxygen, one nitrogen, and three sulfur atoms to form a distorted trigonal bipyramid. The S₂CNCN part of the anion, which exists as E, E conformer, is plane. The dioxane molecule has chair conformation without symmetry centre.     

Structure Cristalline du Trimétaphosphate d'Indium(III)

Crystal Structure of In (PO₃)₃ Indium(III) trimetaphosphate In(PO₃)₃ crystallizes in the monoclinic space group Ic with a = 10.876(2) Å, b = 19.581(2) Å, c = 9.658(2) Å, β = 97.77(1)° and Z = 12. The structure was refined to R = 0.027 utilizing 1171 independent reflections. The structure consists of infinite chains of [PO₄] tetrahedra sharing corners with each other. InO₆ octahedra connect parallel chains. Each oxygen atom is shared between two [PO₄] tetrahedra (in the infinite chains (PO₃)_n) or one [PO₄] tetrahedron and one [InO₆] octahedron. For the first type of oxygen atoms (O_M) the P? O distances are about 0.1 Å greater than the P? O distances of the second type of oxygen atoms (O_m). The [InO₆] groups are moderately distorted and the average In? O bond length for the three In³⁺ ions is 2.117 Å.     

Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Neue Kronenether‐stabilisierte Oxoniumhalogenochalkogenate: [H3O(Dibromo‐benzo‐18‐Krone‐6)]2[Se3Br10] und [H5O2(Bis‐dibromo‐dibenzo‐24‐Krone‐8]2[Se3Br8]

Novel Oxonium Halogenochalcogenates Stabilized by Crown Ethers: [H₃O(Dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] and [H₅O₂(Bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] Two novel complex oxonium bromoselenates(II,IV) and –(II) are reported containing [H₃O]⁺ and [H₅O₂]⁺ cations coordinated by crown ether ligands. [H₃O(dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] ( 1 ) and [H₅O₂(bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] ( 2 ) were prepared as dark red crystals from dichloromethane or acetonitrile solutions of selenium tetrabromide, the corresponding unsubstituted crown ethers, and aqueous hydrogen bromide. The products were characterized by their crystal structures and by vibrational spectra. 1 is triclinic, space group (Nr. 2) with a = 8.609(2) Å, b = 13.391(3) Å, c = 13.928(3) Å, α = 64.60(2)°, β = 76.18(2)°, γ = 87.78(2)°, V = 1404.7(5) ų, Z = 1. 2 is also triclinic, space group with a = 10.499(2) Å, b = 13.033(3) Å, c = 14.756(3) Å, α = 113.77(3)°, β = 98.17(3)°, γ = 93.55(3)°. V = 1813.2(7) ų, Z = 1. In the reaction mixture complex redox reactions take place, resulting in (partial) reduction of selenium and bromination of the crown ether molecules. In 1 the centrosymmetric trinuclear [Se₃Br₁₀]^2? consists of a central Se^IVBr₆ octahedron sharing trans edges with two square planar Se^IIBr₄ groups. The novel [Se₃Br₈]^2? in 2 is composed of three planar trans‐edge sharing Se^IIBr₄ squares in a linear arrangement. The internal structure of the oxonium‐crown ether complexes is largely determined by the steric restrictions imposed by the aromatic rings in the crown ether molecules, as compared to complexes with more flexible unsubstituted crown ether ligands.     

Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. XIV. Kristallstruktur eines 3, 5-Diphenyl-1, 2, 4-dithiazolium-Salzes mit käfigförmigem [P4NS9]-Anion

Contributions to the Chemistry of Phosphorus Compounds with Adamantane Structure. XIV. Crystal Structure of a 3, 5-Diphenyl-1, 2, 4-dithiazolium Salt with the Cage-like Anion [P₄NS₉] The compound 3, 5-Diphenyl-1, 2, 4-dithiazolium 1, 3, 5, 7-pentathioxo-10-aza-2, 4, 6, 8, 9-pentathia-1α⁵,3λ⁵,5λ⁵,7λ⁵-tetraphosphatricyclo[3.3.1.1^3,7]decanide has been prepared by the reaction of P₄S₁₀ with benzonitrile. It crystallizes in the triclinic space group P1 with a = 9.914 Å, b = 15.025 Å, c = 9.186 Å, α = 100.48°, β = 99.90°, γ = 90.66°, and Z = 2. The anion has the structure of a P₄S₁₀-like cage, in which one P? S? P group is replaced by the P? N? P group.     

Einkristall-Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall—Metall-Bindung. II. Die Molekül- und Kristallstruktur von X2Sn[Mn(CO)5]2 (XCl,Br) Verbindungen

Single Crystal X-Ray Analysis of Compounds with Covalent Metal–Metal Bonds. II. Molecular and Crystal Structure of X₂Sn[Mn(CO)₅]₂ (X?Cl, Br) Both X₂Sn[Mn(CO)₅]₂ compounds (X?Cl, Br) crystallize in the monoclinic crystal system with at times different values in the lattice parameters. They belong to the space group C_2h⁵. The structures have been solved using 2 107 symmetrical independent reflection for Cl₂Sn[Mn(CO)₅]₂ and 1 470 reflections for Br₂Sn[Mn(CO)₅)₂] by applying the heavy atom method. The following interatomic distances have been found: Cl₂Sn[Mn(CO)₅]₂, Sn? Mn = 2.635(1) Å, Sn? Cl = 2.385(2) Å, Mn? C = 1.852(8) Å, C? O = 1.128(10) Å; Br₂Sn[Mn(CO)₅]₂, Sn? Mn = 2.642(3) Å, Sn? Br = 2.548(2) Å, Mn? C = 1.851(21) Å, C? O = 1.124(25) Å. In addition, bond angles of X? Sn? X and Mn? Sn? Mn of these compounds have also been estimated in the case of X = Cl: 95.80(7)° and 126.25(4)° and for X?Br: 98.44(8)° and 125.88(9)°. The individual molecules of the X₂Sn[Mn(CO)₅]₂ solids are surrounded by ligands showing distorted tetrahedral configuration at the Sn atom and distorted octahedral configuration at the Mn atom.     

Syntheses and Structures of Two New Cu/Nb/pyrazine Complexes: Three dimensional CuNb(pyz)2OF5 · (pyz)(H2O) and two dimensional [Cu(pyz)2.5]+ [NbF6]− · (pyz)

Crystals of CuNb(pyz)₂OF₅ · (pyz)(H₂O) ( 1 ) and [Cu(pyz)_2.5]⁺ [NbF₆]^? · (pyz) ( 2 ) were grown (150°C and autogeneous pressures) from CuO, 1/2(Nb₂O₅), (HF)_x · pyridine, and H₂O in excess pyrazine. Light blue single crystals of ( 1 ) are orthorhombic, crystallizing in space group Cccm (No. 66), with a = 14.547(1) Å, b = 16.135(2) Å, c = 13.803(2) Å, and Z = 8. The structure of ( 1 ) contains corner shared [Cu(pyz)_4/2F_2/2]⁺, [Cu(pyz)_4/2O_2/2], and [NbF₄O_1/2F_1/2]^?0.5 octahedra. Orange crystals of ( 2 ) are monoclinic, crystallizing in space group C2/c (No. 15), with a = 11.792(8) Å, b = 17.123(3) Å, c = 17.051(5) Å, β = 90.04(4)°, and Z = 8. The structure of ( 2 ) contains puckered rings of corner shared [Cu(pyz)(pyz)_3/2]⁺ tetrahedra and isolated [NbF₆]^? anions within the rings.     

Über Oxobismutate. Zur Kenntnis von Na3BiO4 und Na3SbO4

On oxobismuthates. The compounds Na₃BiO₄ and Na₂SbO₄ Na₃BiO₄ crystallizes monoclinic in C⁴_2h; a = 5.87₁ b = 6.69⁶, c = 5.65₀ Å and β = 109,8° with Z = 2. We have a variant of the NaCl type, forming chains ¹_∞[BiO_4/2+2/1] along [001]. The MADELUNG part of lattice energy (MAPLE) of Na₃BiO₄ and different other structure models are calculated und discussed. Na₃SbO₄[a = 5.79₅, b = 6.59₅, c = 5.41₈ Å, β = 109.4°] is isotypic with Na₃BiO₄.     

Über Tetraiodomercurate des Calciums und Strontiums

On Tetraiodomercurates of Calcium and Strontium Tetraiodomercurates MHgI₄ · 8 H₂O (M ? Ca, Sr) as yellow crystals are obtainable by crystallization from aqueous solutions. Both compounds are not isotype in spite of consisting isolated [M(OH₂)₈] cations and tetrahedral [HgI₄] anions which are cubic closed packed. In the structure of the tetragonal CaHgI₄ · 8 H₂O (a = 13.972(3) Å; c = 18.155(4) Å; Z = 8; P4₂/mbc) are dodecahedral [Ca(OH₂)₈] cations, but antiprismatic [Sr(OH₂)₈] groups in the orthorhombic compound SrHgI₄ · 8 H₂O (a = 9.616(3) Å; b = 10.610(3) Å; c = 17.731(4) Å; Z = 4; Pcmn). The relations between both structure concerning a tetragonal “Aristotype” are discussed.     

Preparation,spectral characterization,and single crystal X-ray structures of cis and trans isomers of 2,4,6-trifluoroethoxy-1,3,5-triethyl-1,3,5,2λ5, 4λ5, 6λ5-triazatriphosphorinane-2,4,6-trioxide, [ETNP(O)(OCH2CF3)]3

Oxidation of the cis isomer of the λ³-cyclotriphosphazane [EtNP(OCH₂CF₃)]₃ with trimethylamine-N-oxide (TMNO) gives the cis isomer of trioxo-λ⁵-cyclotriphosphazane [EtNP(O)(OCH₂CF₃)]₃; the trans isomer of [EtNP(O)(OCH₂CF₃)]₃ is obtained by the treatment of a cis and trans mixture of [EtNP(OCH₂CF₃)]₃ with aqueous H₂O₂. The two trioxocyclotriphosphazanes have been characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ¹⁹F, and ³¹P) spectroscopy. The solid state structures of both the isomers have been determined by single crystal X-ray diffraction. The six-membered P₃N₃ ring in both the isomers exhibits a twist-boat conformation; in the cis isomer, the trifluoroethoxy substituents lie on the same side of the ring, whereas, in the trans isomer, two trifluoroethoxy groups are on one side of the ring and the third on the other side of the ring. Crystal data for cis-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 13.593(3), b = 9.721(2), c = 17.539(3) Å, β = 99.49(2)°, V = 2286(1) ų, Z = 4, and Final R = 0.047. Crystal data for trans-[EtNP(O)(OCH₂CF₃)]₃: monoclinic, P 2₁/ n , a = 11.685(4), b = 15.115(5), c = 13.233(5) Å, - = 102.21(3)°, V = 2284(1) ų, Z = 4, and Final R = 0.078.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse der bindungsisomeren Chlororhodanoiridate(III) trans-[IrCl2(SCN)4]3− und trans-[IrCl2(NCS)(SCN)3]3−

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? By treatment of Na₂[IrCl₆] with NaSCN in 2N HCl the linkage isomers trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu₄N)₃[IrCl₂(SCN)₄] ( 1 ) (monoclinic, space group P2₁/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me₄N)₃[IrCl₂(NCS)(SCN)₃] ( 2 ) (monoclinic, space group P2₁/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are f_d(IrS) = 1.52 and f_d(IrCl) = 1.72 mdyn/Å.     

Darstellung der Halogeno-Pyridin-Rhenate(III), [ReX6−n (Py)n](3−n)− (X = Br,Cl; n = 1−3), sowie Kristallstrukturen von trans-[(C4H9)4N][ReBr4(Py)2], mer-[ReCl3(Py)3] und mer-[ReBr3(Py)3]

Preparation of Halogeno Pyridine Rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl; n = 1?3) Crystal Structures of trans-[(C₄H₉)₄N][ReBr₄(Py)₂], mer-[ReCl₃(Py)₃], and mer- [ReBr₃(Py)₃] The mixed halogeno-pyridine-rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl), n = 1?3, have been prepared for the first time by reaction of the tetrabutylammoniumsalts (TBA)₂[ReX₆] (X = Br, Cl) in pyridine with (TBA)BH₄ and separation by chromatography on Al₂O₃. Apart from the monopyridine complexes only the trans and mer isomers are formed from the bis-and tris-pyridine compounds. The X-ray structure determinations of the isotypic neutral complexes mer- [ReX₃(Py)₃] (monoclinic, space group P 2₁/n, Z = 4; for X = Cl: a = 9,1120(8), b = 12,5156(14), c = 15,6100(13) Å, β = 91,385(7)°; for X = Br: a = 9,152(5), b = 12,852(13), c = 15,669(2) Å, β = 90,43(2)°) reveal, due to the stronger trans influence of pyridine compared with Cl and Br, that the Re? X distances in asymmetric Py? Re? X3 axes with ReCl3 = 2,397 Å and ReBr3 = 2,534 Å are elongated by 1,3 and 1% in comparison with symmetric X1? Re? X2 axes with ReCl1 = ReCl2 = 2,367 Å and ReBr1 = 2,513 and ReBr2 = 2,506 Å, respectively. The Re? N bond lengths are roughly equal with 2,12 Å. Trans-(TBA)[ReBr₄(Py)₂] crystallizes triclinic, space group P1 , a = 9,2048(12), b = 12,0792(11), c = 15,525(2) Å, α = 95,239(10), β = 94,193(11), γ = 106,153(9)°, Z = 2. The unit cell contains two independent but very similar complex anions with approximate D_2h(mmm) point symmetry.