Ternäre Halogenide vom Typ A3MX6. III [1, 2]. Synthese,Strukturen und Ionenleitfähigkeit der Halogenide Na3MX6 (X = Cl,Br)

Ternary Halides of the A₃MX₆ Type. III [1, 2]. Synthesis, Structures, and Ionic Conductivity of the Halides Na₃MX₆ (X = Cl, Br) The bromides Na₃MBr₆ crystallize with the stuffed LiSbF₆-type structure (type I; M = Sm? Gd) or with the structure of the mineral cryolite (type II; M = Gd? Lu). The structure types were refined from single crystal X-ray data (Na₃SmBr₆: trigonal, space group R3 , a = 740.8(2) pm, c = 1 998.9(8) pm, Z = 3; Na₃YBr₆: monoclinic, space group P2₁/n, a = 721.3(4) pm, b = 769.9(2) pm, c = 1 074.8(4) pm, β = 90.60(4)°, Z = 2). Reversible phase transitions from one structure to the other occur. The phase transition temperatures were determined for the bromides as well as for the chlorides Na₃MCl₆ (M = Eu? Lu). The refinement of both structures for one compound was possible for Na₃GdBr₆ (I: trigonal, space group R3 , a = 737.1(5) pm, c = 1 887(2) pm, Z = 3; II: monoclinic, space group P2₁/n, a = 725.2(1) pm, b = 774.1(3) pm, c = 1 080.1(3) pm, β = 90.76(3)°, Z = 2). All compounds exhibit ionic conductivity of the sodium ions which decreases with the change from type I to type II. The conductivity of the bromides is always higher when compared with the respective chlorides.     

Die Kryolithstruktur von Na3ScF6 und die Oktaederkippung in isostrukturellen Natriumhexafluorometallaten Na3MF6

The Cryolite Structure of Na₃ScF₆ and the Tilting of Octahedra in Isostructural Sodium Hexafluorometallates Na₃MF₆ X-ray studies at single crystals of Na₃ScF₆ confirmed the monoclinic cryolite type structure of this compound: a = 559.5, b = 580.2, c = 811.6 pm, β = 90.72°, Z = 2, space group P2₁/n; R1 = 0.021 for 512 symmetry independent reflections. The octahedra of [ScF₆] (average Sc? F = 200.7 pm), as well as those of [NaF₆] (Na1? F = 229.1 pm) linked to them, are titled by about 20° with respect to the axes of the perovskite-like pseudocell. This tilting of octahedra is discussed in comparison with other cryolites and with orthorhombic perovskites NaMF₃; there results a correlation between tilt angle and tolerance factor t ? 0.88 of these compounds, the [NaF₈] coordination of which invariably exhibits a constant mean value of Na2? F = 231.5 ± 1 pm for the four shortest distances.     

Quaternäre Chloride des zweiwertigen Europiums mit dreiwertigen Übergangsmetallen: Synthese und Kristallstruktur von Na6Eu3M4Cl24 (M = Ti,V, Cr)

Quaternary Chlorides of Divalent Europium and Trivalent Transition Metal Ions: Synthesis and Crystal Structure of Na₆Eu₃M₄Cl₂₄ (M = Ti, V, Cr) The reaction of EuCl₂, NaCl and MCl₃ (M = Ti, V, Cr) yields the chlorides Na₆Eu₃M₄Cl₂₄. According to X‐ray single crystal investigations, their crystal structure is a variant of the monoclinic cryolite‐type structure. One crystallographic site is occupied by Na1 and Eu simultaneously. For charge compensation the Na2 site is not fully occupied. In Na₆Eu₃Ti₄Cl₂₄ (P2₁/n, Z = 1/2, a = 663.8(1) pm, b = 718.3(1) pm, c = 953.3(2) pm, β = 91.55(2)°, R_all = 0.0314), Na₆Eu₃V₄Cl₂₄ (P2₁/n, Z = 1/2, a = 660.4(1) pm, b = 715.8(1) pm, c = 946.5(2) pm, β = 91.41(2)°, R_all = 0.0313) and Na₆Eu₃Cr₄Cl₂₄ (P2₁/n, Z = 1/2, a = 654.8(1) pm, b = 706.5(1) pm, c = 945.4(2) pm, β = 91.07(2)°, R_all = 0.0368) the ratio of Na1 : Eu amounts to 5 : 3. The colours of the compounds, orange yellow for M = Ti, orange red for M = V and dark red for M = Cr, indicate electronic interactions between Eu²⁺ and M³⁺.     

Ternäre Halogenide vom Typ A3MX6. IV. [1]. Ternäre Halogenide des Scandiums mit Natrium,Na3ScX6 (X = F,Cl, Br): Synthese,Strukturen, Ionenleitfähigkeit

Ternary Halides of the A₃MX₆ Type. IV. Ternary Halides of Scandium with Sodium, Na₃ScX₆ (X = F, Cl, Br): Synthesis, Structures, Ionic Conductivity X-ray studies on single crystals of Na₃ScF₆ and Na₃ScBr₆ show, that Na₃ScF₆ crystallizes with the cryolite type (monoclinic, P2₁/n, Z = 2, a = 560.16(9), b = 580.31(8), c = 812.1(2)pm, β = 90.720(14)°) and Na₃ScBr₆, as the only ternary bromide of the rare earth elements with sodium, in the Na₃CrCl₆ type (trigonal, P3 1c, Z = 2, a = 728.95(7), c = 1309.29(17)pm). The ionic conductivity of powder samples of Na₃ScF₆, Na₃ScBr₆ and of Na₃ScCl₆ was studied by impedance spectroscopy. Activation energies were determined as 1.22 eV, 0.80 eV and 0.71 eV for the fluoride, chloride and bromide, respectively. The differences are explained from the crystal structures and the sizes and polarizabilities of the anions.     

Na2ZrS3: Ein ternäres Sulfid des Zirconiums mit aufgefüllter AlCl3‐Struktur

Na₂ZrS₃: A Ternary Zirconium Sulfide with Stuffed AlCl₃‐type Structure Dark green, plate‐like single crystals of Na₂ZrS₃ (monoclinic, C2/m; a = 664.69(6), b = 1152.5(1), c = 695.48(7) pm, β = 108.78(1)°; Z = 4) are obtained along with pale yellow platelets of NaZr₂N₂SCl (trigonal, R3m; a = 363.56(3), c = 2951.2(4) pm; Z = 3) upon oxidation of zirconium metal with sulfur and sodium azide (NaN₃) in the presence of fluxing NaCl (molar ratio 7:6:2:3) in evacuated silica tubes at 850°C within three weeks. The crystal structure is best described as stuffed AlCl₃ type with all cations (Na⁺ and Zr⁴⁺) in octahedral coordination of the S^2– anions, which build up a cubic closest packed host lattice. The internuclear metal sulfur distances range from 276 to 296 pm for all three crystallographically different Na⁺ cations, and from 258 to 260 pm for Zr⁴⁺.     

Neue Polyiodide des Caesiums mit Doppel‐ und Tripeldecker‐Kationen, [Cs(Benzo‐18‐Krone‐6)2]Ix und [Cs2(Benzo‐18‐Krone‐6)3](Ix)2 (x = 3, 5)

New Polyiodides of Cesium containing Double and Triple Decker Cations, [Cs(benzo‐18‐crown‐6)₂]I_x and [Cs₂(benzo‐18‐crown‐6)₃](I_x)₂ (x = 3, 5) [Cs(b18c6)₂]I_x (x = 3 (1) , 5 (3) ) and [Cs₂(b18c6)₃](I_x)₂ (x = 3 (2) , 5 (4) ) (b18c6 = benzo‐18‐crown‐6) have been synthesized by the reaction of benzo‐18‐crown‐6 (C₁₆H₂₄O₆), cesium iodide (CsI) and iodine (I₂) in acetonitrile ( 1 ), ethanol/dichloromethane ( 2 , 4 ) and 2‐methoxyethanol ( 3 ). Their crystal structures were determined on the basis of single crystal X‐ray data {( 1 ): monoclinic, C2/c, Z = 4, a = 2048.8(5), b = 1329.5(5), c = 1588.7(5) pm, β = 110.23(1)°; ( 2 ): monoclinic, C2/c, Z = 4, a = 2296.0(1), b = 2092.7(1), c = 1373.6(1) pm, β = 100.21(1)°; ( 3 ): monoclinic, P2₁/n, Z = 4, a = 1586.3(1), b = 1745.5(1), c = 1608.6(1) pm, β = 92.37(1)°; ( 4 ): triclinic, , Z = 2, a = 1241.7(1), b = 1539.8(2), c = 1938.4(2) pm, α = 91.15(1), β = 100.53(1), γ = 95.26(1)°}. As expected, double decker cations centered by Cs atoms, [Cs(b18c6)₂]⁺, are found in the structures of ( 1 ) and ( 3 ). In contrast, the triple decker cation found in ( 2 ) and ( 4 ) is less common. The triiodide anions of ( 1 ) and ( 2 ) can be regarded as normal and the chain‐type pentaiodide anions of ( 3 ) and ( 4 ) fall into the known systematic sequence of these anions. The differences in the connectivity of the crystallographically independent I₅^? anions in ( 4 ) are surprising with respect to the fact that, so far, independent pentaiodide anions do not show variations in their scheme of connectivity within one crystal structure.     

Über die komplexen Hydroxide des Chroms: Na9[Cr(OH)6]2(OH)3 · 6 H2O und Na4[Cr(OH)6]X · H2O (X = Cl, (S2)1/2) – Synthese,Kristallstruktur und thermisches Verhalten

Complex Hydroxides of Chromium: Na₉[Cr(OH)₆]₂(OH)₃ · 6 H₂O and Na₄[Cr(OH)₆]X · H₂O (X = Cl, (S₂)_1/2) – Synthesis, Crystal Structure, and Thermal Behaviour Green plate‐like crystals of Na₉[Cr(OH)₆]₂(OH)₃ · 6 H₂O (triclinic, P1, a = 872.9(1) pm, b = 1142.0(1) pm, c = 1166.0(1) pm, α = 74.27(1)°, β = 87.54(1)°, γ = 70.69(1)°) are obtained upon slow cooling of a hot saturated solution of Cr^III in conc. NaOH (50 wt%) at room temperature. In the presence of chloride or disulfide the reaction yields green prismatic crystals of Na₄[Cr(OH)₆]Cl · H₂O (monoclinic, C2/c, a = 1138.8(2) pm, b = 1360.4(1) pm, c = 583.20(7) pm, β = 105.9(1)°) or green elongated plates of Na₄[Cr(OH)₆](S₂)_1/2 · H₂O (monoclinic, P2₁/c, a = 580.8(1) pm, b = 1366.5(3) pm, c = 1115.0(2) pm, β = 103.71(2)°), respectively. The latter compounds crystallize in related structures. All compounds can be described as distorted cubic closest packings of the anions and the crystal water molecules with the cations occupying octahedral sites in an ordered way. The thermal decomposition of the compounds was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In all cases the final decomposition product is NaCrO₂.     

Cycloadditionsreaktionen von Isocyaniden an Bis[tris(trimethylsilyl)methyl]diphosphen

Cycloaddition Reactions of Isocyanides with Bis[tris(trimethylsilyl)methyl]diphosphene The [2 + 1] cycloaddition reactions of isocyanoacetonitrile ( 1 a ), pentacarbonyl(diisocyanomethane)chromium ( 1 b ), and 2,2,2-trifluoroethylisocyanide ( 1 c ) with the diphosphene R–P=P–R (R = C[Si(CH₃)₃]) ( 2 ) yield the expected diphosphirane imines 3 a – c . All compounds are thermally very stable and show no evidence for a [2 + 1] cycloreversion reaction. The structures of 3 a : triclinic, P 1, a = 918.0(2), b = 1174.7(4), c = 1821.9(5) pm, α = 93.83(2), β = 97.22(2)°, γ = 97.08(2)°, Z = 2, R₁ = 0.069; 3 c : monoclinic, P2₁, a = 928.6(2), b = 1659.8(3), c = 1261.2(3) pm, β = 107.65(2)°, Z = 2, R₁ = 0.073, and 1,2-Bis[tris(trimethylsilyl)]methyl-N-trifluormethyl-3-diphosphiranimin: monoclinic, P2₁/n, a = 1374.6(3), b = 1685.9(1), c = 1658.6(5) pm, β = 108.99(9)°, Z = 4, R₁ = 0.092, were elucidated by X-ray crystallography. All three compounds possess a similar three membered PCP ring system with an exocyclic C–N double bond.     

Alkalimetall‐Oxoantimonate: Synthesen,Kristallstrukturen und Schwingungsspektren von ASbO2 (A = K,Rb), A4Sb2O5 (A = K,Rb, Cs) und Cs3SbO4

Alkaline Metal Oxoantimonates: Synthesis, Crystal Structures, and Vibrational Spectroscopy of ASbO₂ (A = K, Rb), A₄Sb₂O₅ (A = K, Rb, Cs), and Cs₃SbO₄ The compounds ASbO₂ (A = K/Rb; monoclinic, C2/c, a = 785.4(3)/799.6(1) pm, b = 822.1(4)/886.32(7) pm, c = 558.7(3)/559.32(5) pm, β = 124.9(1)/123.37(6)°, Z = 4) are isotypic with CsSbO₂ and the corresponding bismutates. The structures of the antimonates A₄Sb₂O₅ (A = K/Rb: orthorhombic, Cmcm, a = 394.9(1)/407.34(7) pm, b = 1807.4(1)/1893.5(1) pm, c = 636.34(9)/655.60(8) pm, Z = 2) and Cs₄Sb₂O₅ (monoclinic, Cm, a = 1059.81(7) pm, b = 692.68(8) pm, c = 811.5(1) pm, β = 98.7(1)°, Z = 2) both contain the anion [O₂SbOSbO₂]^4–. Cs₃SbO₄ (orthorhombic, Pnma, a = 1296.1(1) pm, b = 919.24(8) pm, c = 679.95(6) pm, Z = 4) crystallizes with the K₃NO₄ structure type.     

Kristallstrukturbestimmungen an vier monoklinen Weberiten Na2MIIMIIIF7 (MII = Fe,Co; MIII = V,Cr)

Crystal Structure Determinations of Four Monoclinic Weberites Na₂M^IIM^IIIF₇ (M^II = Fe, Co; M^III = V, Cr) By solid state reaction of the binary fluorides single crystals of the following weberites were prepared and their monoclinic structure (space group C2/c, Z = 16) determined by X-ray methods: Na₂FeVF₇ (a = 1 271.0(3), b = 742.9(1), c = 2 471.6(5) pm, β = 100.03(3)°; R₁ = 0.043 (1 545 Reflexe); Fe? F = 203.8, V? F = 193.0 pm); Na₂FeCrF₇ (a = 1 262.5(3), b = 739.1(1), c = 2 460.5(5) pm, β = 99.93(3)°; R₁ = 0.029 (2 340); Fe? F = 203.6, Cr? F = 190.5 pm); Na₂CoVF₇ (a = 1 270.3(5), b = 739.1(3), c = 2 465.1(10) pm, β = 100.02(3)°; R₁ = 0.028 (2 250); Co? F = 201.6, V? F = 193.6 pm); Na₂CoCrF₇ (a = 1 257.8(3), b = 733.5(1), c = 2 441.5(5) pm, β = 99.64(3)°; R₁ = 0.030 (2 227); Co? F = 201.2, Cr? F = 190.2 pm). Concerning the above average distances within the distorted [MF₆] octahedra and the shape of [NaF₈] coordination details are given and discussed.     

Über die Kristallstruktur von (C6H5)3SiSH und (C6H5)3SiSBr und die Darstellung des Iodsulfans (C6H5)3SiSI

The Crystal Structure of (C₆H₅)₃SiSH and (C₆H₅)₃SiSBr and the Preparation of the Iodosulfane (C₆H₅)₃SiSI The preparation of the halogenosulfanes Ph₃SiSBr and Ph₃SiSI from Ph₃SiSH and N-halogenosuccinimide is reported. They are characterized by vibrational spectroscopic measurements. Ph₃SiSBr crystallizes in space group P1 with a = 899.3(8) pm, b = 941.3(7) pm, c = 1 051.4(7) pm, α = 109.88(5)°, β = 99.23(6)°, γ = 96.78(6)° and Z = 2. Ph₃SiSH crystallizes in space group P2₁/c with a = 1 879.4(8), b = 966.3(5), c = 1 845.2(9), β = 107.84(4), Z = 8. The halogenosulfanes decompose in polar solvents by formation of sulphur and triphenylsilanhalide.     

Phosphaniminato-Komplexe des Titans. Die Kristallstrukturen von [TiCl2(NPPh3)2] und [TiCl3(NPMe2Ph)(CH3CN)]2

Phosphorane Iminato Complexes of Titanium. The Crystal Structures of [TiCl₂(NPPh₃)₂] and [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ [TiCl₂(NPPh₃)₂] has been prepared by the reaction of [TiCl₃(NPPh₃)] with excess Me₃SiNPPh₃ in a melt at 220°C, forming colourless crystals. [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ is formed as yellow, moisture sensitive crystals from acetontrile solutions of [TiCl₃(NPMe₂Ph)]₂, which on its part has been obtained by the reaction of TiCl₄ with Me₃SiNPMe₂Ph. The complexes are characterized by IR spectroscopy and by crystal structure determinations. [TiCl₂(NPPh₃)₂] . Space group Fdd2, Z = 8, structure refinement with 2875 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 2080.9, b = 3308.5, c = 973.6 pm. The compound forms monomeric molecules with bond lengths TiN of 179.0 pm and PN of 156.8 pm, which correspond with double bonds. The bond angle TiNP is 166.6°. [TiCl₃(NPMe₂Ph)(CH₃CN)]₂ . Space group P1 , Z = 1, structure refinement with 2577 unique reflections, R = 0.039 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 856.6, b = 923.1, c = 1008.3 pm, α = 81.23°, β = 71.63°, γ = 81.41°. The compound forms centrosymmetric, dimeric molecules, in which the titanium atoms are linked via chloro bridges TiCl₂Ti with TiCl bond lengths of 243.9 and 270.3 pm. In trans-position to the longer TiCl bonds the nitrogen atoms of the phosphorane iminato groups are coordinated with bond lengths TiN of 173.9 pm and PN of 161.4 pm which again correspond with double bonds. The bond angle TiNP is 156.4°.     

Cs5Sb8 und β‐CsSb: Zwei neue binäre Zintl‐Phasen

Cs₅Sb₈ and β‐CsSb: Two New Binary Zintl Phases The anion in the crystal structure of the new Zintl phase Cs₅Sb₈ synthesized from the elements (monoclinic, space group P2₁/c, a = 724.4(2) pm, b = 1135.2(3) pm, c = 2750.9(8) pm, β = 96.663(5)°, Z = 4) consists of two and three bonded Sb atoms, which are connected to form puckered nets with 5 and 28 membered rings. β‐CsSb (monoclinic, space group P2₁/c, a = 1519.4(3) pm, b = 734.0(2) pm, c = 1432.2(2) pm, β = 113.661(3)°, Z = 4) crystallizes with a superstructure of the LiAs structure type. As in the α phase (NaP type), twobonded Sb^‐ atoms form neary ideal 4₁ screx chains. In contrast to the α phase the helices have opposite chirality.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Neue Untersuchungen zum Reaktionsverhalten von Triorganylcyclotriphosphanen. Die Kristallstrukturen von [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)6(μ2-CO)3{(PtBu)2}2] und [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)]–

New Research of Reaction Behaviour of Triorganylcyclotriphosphines. The Crystal Structures of [(PPh₃)₂Pt(P^tBu)₃], [(PPh₃)₂Pd(P^tBu)₂], [(CO)₄Cr{(PⁱPr)₃}₂], [RhCl(PPh₃)(P^tBu)₃], [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂], and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– By the reaction of triorganylcyclotriphosphines with transition metal complexes single- and polynuclear compounds are formed, in which the cyclophosphines are bonded in different ways to the metal, the ring either preserving structure or under going ring opening. Depending on the reaction conditions the following compounds can be characterized: [(PPh₃)₂Pt(P^tBu)₃] ( 1 ), [(PPh₃)₂Pd(P^tBu)₂] ( 2 ), [(CO)₄Cr{(PⁱPr)₃}₂] ( 3 ), [RhCl(PPh₃)(P^tBu)₃] ( 4 ), [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂] ( 5 ) and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– ( 6 ). The structures of 1 – 6 were obtained by X-ray single crystal structure analysis ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1279.6(3) pm, b = 1733.1(4) pm, c = 2079.1(4) pm, β = 90.20(3)°; 2 : space group P2₁/c (No. 14), Z = 4, a = 1053.3(2) pm, b = 2085.2(4) pm, c = 1855.7(4) pm, β = 98.77(3)°; 3 : space group P 1 (No. 2), Z = 2, a = 1022.6(2) pm, b = 1026.4(2) pm, c = 1706.0(3) pm, α = 82.36(3)°, β = 86.10(3)°, γ = 64.40(3)°; 4 : space group P 1 (No. 2), Z = 2, a = 980.2(2) pm, b = 1309.5(3) pm, c = 1573.4(3) pm, α = 99.09(3)°, β = 99.46(3)°, γ= 111.87(3)°; 5 : space group P2₁/c (No. 14), Z = 4, a = 1804.0(5) pm, b = 2261.2(6) pm, c = 1830.1(7) pm, β = 96.99(3)°; 6 : space group P2₁/c (No. 14), Z = 4, a = 943.2(3) pm, b = 2510.6(7) pm, c = 1325.1(6) pm, β = 98.21(3)°).     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).     

Fluoroplatinate(IV) der Lanthaniden LnF[PtF6]. (Ln = Pr,Sm, Gd,Tb, Dy,Ho, Er)

Fluoroplatinates(IV) of the Lanthanides LnF[PtF₆] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er) For the first time fluorides LnF[PtF₆] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er), all yellow have been obtained. From single crystal data they crystallize monoclinic, space group P2₁/n?C (No. 14), Z = 4, Pr: a = 1 125.77(19) pm, b = 559.04(7) pm, c = 910.27(17) pm, β = 107.29(1)°; Sm: a = 1 114.63(31) pm, b = 552.70(12) pm, c = 898.02(20) pm, β = 107.24(2)°; Gd: a = 1 112.12(15) pm, b = 551.22(7) pm, c = 891.99(11) pm, β = 107.09(1)°; Tb (Powder data): a = 1 108.88(20) pm, b = 552.71(9) pm, c = 889.56(16) pm, β = 107.30(1)°; Dy: a = 1 100.28(23) pm, b = 547.77(8) pm, c = 882.41(13) pm, β = 107.32(1); Ho: a = 1 099.11(16) pm, b = 546.16(7) pm, c = 879.45(15) pm, β = 107.34(1)°; Er: a = 1 095.10(16) pm, b = 544.82(10) pm, c = 874.85(14) pm, β = 107.37(1)°.     

Über Na2PrO3 und Na2TbO3

On Na₂PrO₃ and Na₂TbO₃ Using an exchange reaction of Na₂O with Li₈TbO₆ (Na : Tb = 2.1 : 1; au-tube; 750°C, 30 d) yellow-orange colored single crystals of Na₂TbO₃ could be prepared for the first time. Na₂TbO₃ crystallizes monoclinic in C2/c (Z = 8; a = 576.92(6), b = 1001.27(9), c = 1117.91(14) pm, β = 99.98(1)°). According to four-circle data the Li₂SnO₃-type of structure is adopted (PW 1100, MoKα , 1935 I₀ (hkl), R = 4.86%, R_w = 3.63% for all 928 unique reflexions). By a similar exchange reaction of Na₂O with Li₈PrO₆ for the first time single crystals of Na₂PrO₃ could be prepared, too (Na : Pr = 2.2 : 1; au-tube; 700°C; 23 d). The structure determination reveils that there is a variant of the NaCl-type of structure, which ressembles to the Li₂SnO₃-type of structure (PW 1100, MoKα , 2199 I₀ (hkl)), R = 8.88%, R_w = 5.21% for all 947 unique reflexions; C2/c, Z = 8, a = 678.78(5), b = 977.47(7), c = 1080.38(9) pm, β = 108,4(1)°. In contrast to Na₂TbO₃ there are no layers according to NaO(Na_1/3Tb_2/3)O. All octahedral intersticies are occupied systematically with Pr⁴⁺ and Na⁺ : (Na_2/3Pr_1/3)O(Na_2/3Pr_1/3)O.     

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.     

Phosphaniminato-Komplexe von Titan(IV) und Titan(III). Die Kristallstrukturen von [TiCl2(OMe)(NPPh3)]2, [TiBr2(NPPh3)]2 · 3 C7H8 sowie von [Ph3PNH2]Br · CH2Cl2

Phosphorane Iminato Complexes of Titanium(IV) and Titanium(III). The Crystal Structures of [TiCl₂(OMe)(NPPh₃)]₂, [TiBr₂(NPPh₃)]₂ · 3C₇H₈, and [Ph₃PNH₂]Br · CH₂Cl₂ TiCl₃(NPPh₃) reacts with a solution of methyllithium in diethyl ether in the presence of lithiummethylate forming yellow [TiCl₂(OMe)(NPPh₃)]₂. On reaction with benzyl magnesium bromide TiCl₃(NPPh₃) in diethyl ether is converted into green [TiBr₂(NPPh₃)]₂ under reduction and ligand exchange. [TiBr₂(NPPh₃)]₂ crystallizes from toluene with three molecules C₇H₈. [Ph₃PNH₂]Br · CH₂Cl₂ originates as a side product of this reaction. The products are characterized by their i.r. spectra and by crystal structure analyses. [TiCl₂(OMe)(NPPh₃)]₂ . Space group P1 , Z = 2, structure solution with 2909 independent reflections, R = 0.063. Lattice dimensions at 20°C: a = 1005.1, b = 1044.5, c = 1068.6 pm, α = 66.98°, β = 89.35°, γ = 80.24°. The compound forms centrosymmetric dimeric molecules with μ₂-OMe bridges and five-fold coordinated titanium atoms. The (NPPh₃^?) ligand is terminally connected with a Ti = N distance of 174.8 pm and with a TiNP bond angle of 165.3°. [TiBr₂(NPPh₃)]₂ · 3 C₇H₈ . Space group P1 , Z = 2, structure solution with 5548 independent reflections, R = 0.053. Lattice dimensions at ?70°C: a = 983.3, b = 1162.7, c = 1376.5 pm, α = 100.53°, β = 110.30°, γ = 105.24°. The compound forms centrosymmetric dimeric molecules with μ₂-NPPh₃ bridges and tetrahedral coordination at the titanium atoms. With 195.9 pm the Ti–N bonds correspond with single bonds. The Ti …? Ti distance of 260.0 pm is exceptionally short. [Ph₃PNH₂]Br · CH₂Cl₂ . Space group P1 , Z = 1, structure solution with 3091 independent reflections, R = 0.049. Lattice dimensions at 20°C: a = 909.4, b = 1004.4, c = 1158.5 pm, α = 108.09°, β = 94.67°, γ = 91.92°. The bromide ions are bonded to a one-dimensional infinite network via hydrogen bridge bonds of the cation and of the dichloromethane.