Bildung eines Kupfer-Nitratokomplexes aus einem Azidokomplex und Ozon. Die Kristallstruktur von (PPh4)2[CuCl(NO3)3] · CH2Cl2/ Formation of a Copper Nitrato Complex from an Azido Complex. Crystal Structure of (PPh4)2[CuCl(NO3)3] · CH2Cl2

1992 ◽  
Vol 47 (1) ◽  
pp. 31-34 ◽  
Author(s):  
Karin Ruhlandt-Senge ◽  
Alfred D. Bacher ◽  
Ulrich Müller

(PPh4)2[CuCl(NO3)3] · CH2Cl2 is formed when ozone reacts with (PPh4)2[Cu2(N3)6] in dichloromethane. Its crystal structure was determined by X-ray diffraction. Crystal data: a = 1113(1), b = 1156(1), c = 1965(2) pm , α = 101.02(1), β = 93.74(1), γ = 104.05(2)° at 130 K, space group P1̄, Z = 2, R = 0.057 for 3951 observed reflexions. The structure contains CH2Cl2 molecules and PPh4+ and [CuCl(NO3)3]2- ions, with copper having coordination number 5. One nitrate ligand acts as a bidentate chelating unit, and the other two as monodentate ligands.

1986 ◽  
Vol 41 (7) ◽  
pp. 825-830 ◽  
Author(s):  
Hans-Günter Hauck ◽  
Wolfgang Willing ◽  
Ulrich Müller ◽  
Kurt Dehnicke

AbstractThe thionitrosyl-halothionitrene com pounds (PPh4)2[ReX4(NS)(NSX)]·2 CH2X2, X = Cl or Br, are obtained by nucleophilic ring cleavage of the Re(N2S2) rings of complexes [ReX4(N2S2)]⊖ with PPh4X in CH2X2. (AsPh4)2[ReCl4(NS)(NSCl)] · CH2Cl2 can also be obtained by the reaction of [ReCl4(NSCl)(POCl3)] with S(NSiMe3)2 and subsequent addition of AsPh4Cl. The pyridine complex [ReBr2(NS)(NSBr)(NC5H5)2] · CH2Br2 forms by bromination of the corresponding chloro compound with Me3SiBr. The IR spectra are reported. The crystal structure of (PPh4)2[ReBr4(NS)(NSBr)] · CH2Br2 was determ ined by X-ray diffraction (4158 independent observed reflexions, R = 0.059). Crystal data: a = 1039.7, b - 1232.5, c - 2158.4 pm, α = 81.59, β = 87.05, γ = 77.06°, Z = 2, space group P1̄. The compound consists of PPh4⊕ ions, CH2Br2 molecules, and anions [ReBr4(NS)(NSBr)]2⊖ in which the rhenium atoms are coordinated by four bromine atoms, one thionitrosyl and one brom othionitrene group. The latter have cis arrangement and ReN bond lengths of 186 pm. W hereas the thionitrosyl group is nearly linear, the R = N = SBr group has an ReNS angle of 165°.


1992 ◽  
Vol 47 (8) ◽  
pp. 1075-1078 ◽  
Author(s):  
Karin Ruhlandt-Senge ◽  
Ulrich Müller

When hexymethylbenzene-cyclopentadienyl-iron reacts with ozone in dichloromethane, the title compound is one of the products. Its crystal structure was determined by X-ray diffraction (R = 0.145 for 1412 unique reflexions). Crystal data: a = 1815.1(8), b = 1314.8(5), c = 1823.0(8) pm, space group Pbca, Z = 8. The sandwich-like [η6-C6Me6Fe-η5-C5H5]+ ions exhibit large thermal motions, and the CH2C12 molecules are disordered in two orientations. The novel [Fe2Cl6]2- ion has the structure of two tetrahedra sharing an edge. Its IR spectrum is reported.


1985 ◽  
Vol 40 (3) ◽  
pp. 443-446 ◽  
Author(s):  
Udo Demant ◽  
Elke Conradi ◽  
Ulrich Müller ◽  
Kurt Dehnicke

[HC(NH2)2]3FeCl6 was obtained together with other products from the reaction of S4N4 with HCl in H2CCl2 in the presence of FeCl3. Its crystal structure was determined from X-ray diffraction data (473 independent observed reflexions, R = 0.047). Lattice constants: a = 961.6, c = 876.4 pm; tetragonal, space group P42/m, Z = 2. Of the two crystallographically independent formamidinium ions HC(NH2)2⊕, one exhibits positional disorder; the other one has C-N bond lengths of 128 pm. The FeCl63⊖ ions have symmetry C2h, but the deviation from Oh is small.


1992 ◽  
Vol 47 (8) ◽  
pp. 1063-1066 ◽  
Author(s):  
Alfred-Dirk Bacher ◽  
Ulrich Müller

[Na(15-crown-5)]2S6 was obtained from Na2S4 und 15-crown-5 in acetonitrile. Its crystal structure was determined by X-ray diffraction with 2968 observed reflexions, R = 0.119. Crystal data: a = 861.4(9), b = 1006(1), c = 2097(1) pm, α = 89.7(1), β = 100.20(8), γ = 114.6(1)°, Ζ = 2, space group Ρ 1̄. The chain-like S62- ion has transoid conformations, each of its terminal atoms is in contact with one Na+ ion which in turn is coordinated with one crown ether molecule.


1987 ◽  
Vol 42 (7) ◽  
pp. 828-834 ◽  
Author(s):  
W. Frank ◽  
B. Dincher

Abstract The crystalline compounds [(CH3C6H5)2Hg,][AlCl4]2 (1), [(1,2-(CH3)2C6H4)2Hg2][AlCl4]2(2), [(1,3,5-(CH3)3C6H3)2Hg2][AlCl4]2 (3), [1,2,4,5-(CH3)4C6H2Hg2][AlCl4]2 (4) and [((CH3)6C6)2Hg2][AlCl4]2-CH3C6H5 (5) have been prepared from mercury(I)chloride, aluminium trichloride and the corresponding arenes and characterized by elem ental analysis. The crystal structure of 5 has been determ ined from single crystal X-ray diffraction data and refined to R - 0.093 for 3269 unique reflections. Crystal data: monoclinic, space group P21/c, a = 2116(1), b = 1095.1(7), c = 1880(1) pm, β - 104,9(1)°, Z = 4. Each atom of a central Hg2 unit (Hg -Hg distance 251.5 pm) is asymmetrically complexed by hexamethylbenzene, the Hg - Carene distances being in the range from 241 to 340 pm. Two distorted AlCl4 tetrahedra complete a “molecular” [arene2Hg2][AlCl4]2 unit. The shortest Hg-Cl distances are 310 and 312 pm, respectively.


1992 ◽  
Vol 47 (5) ◽  
pp. 702-705 ◽  
Author(s):  
Alfred D. Bacher ◽  
Irina Sens ◽  
Ulrich Müller

(NEt4)2S5 was prepared from NEt4Cl and Na2S4 in ethanol. Its reaction with boiling acetonitrile yielded tetraethylammonium tetrathiooxalate. (NEt4)2[C2S4] was also obtained by heating (NEt4)2S5 with tetraethylammonium dithioacetate in ethanol. Benzyltriethylammonium tetrathiooxalate, (NEt3Bz)2[C2S4]· 2 toluene, crystallized after NEt3BzCl and Na2S4 were heated in acetonitrile on subsequent addition of toluene. The crystal structure of (NEt4)2[C2S4] was determined by X-ray diffraction (454 independent observed reflexions, R = 0.047). Crystal data: tetragonal, a = 871.2(1) pm, c = 1566.0(3) pm, space group P42/nmc, Z = 2. The [C2S4]2- ion has point symmetry 4m2 (D2d), i.e. the dihedral angle between the two CS2 groups is 90°. The ethyl groups of the NEt4+ ions are disordered in two orientations.


1992 ◽  
Vol 47 (6) ◽  
pp. 819-822 ◽  
Author(s):  
Irina Sens ◽  
Alfred Dirk Bacher ◽  
Ulrich Müller

NaNEt4S4 was obtained from an equimolar solution of Na2S4 and NEt4Cl in ethanol. Its crystal structure was determined by X-ray diffraction with 4175 observed unique reflexions, R = 0.044. Crystal data: a = 713.4(4), b = 1744.5(9), c = 1204.0(5) pm, β = 105.8(3)°, space group P21/n, Ζ = 4. In the structure, chains consisting of Na+ and S42− ions run in the a direction, every Na+ being coordinated by four terminal S atoms of S42− ions (two terminal, one chelating). The chains are separated by the NEt4+ ions.


1985 ◽  
Vol 40 (12) ◽  
pp. 1672-1676 ◽  
Author(s):  
Dieter Fenske ◽  
Udo Demant ◽  
Kurt Dehnicke

Abstract Ruthenium trichloride, obtained from its hydrate with thionyl chloride, reacts with excess trichloronitrom ethane yielding polymer [Ru(NO)Cl3]; by addition of triphenylmethylphosphonium chloride in dichlorom ethane (PPh3Me)2[Ru(NO)Cl4]2 · 2 CH2Cl2 is obtained, the IR spectrum of which is reported and assigned. Its crystal structure was determined with X-ray diffraction data (6404 independent observed reflexions, R = 0.068). Crystal data at -90 °C: a = 1145, b = 1591, c = 1406 pm, β = 96,0°, Z = 2, space group P21/C. The structure consists of PPh3Me⊕ cations, centrosymmetric anions [Ru(NO)Cl4]22⊖ nearly fulfilling C2h symmetry, and CH2Cl2 molecules. In the anions the Ru atoms are linked via chloro bridges; the nitrosyl groups occupy axial positions with bond distances RuN of 175 and NO of 113 pm, bond angle RuNO 172.7°.


1985 ◽  
Vol 40 (11) ◽  
pp. 1457-1462 ◽  
Author(s):  
Jürgen Hanich ◽  
Wolfgang Willing ◽  
Ulrich Müller ◽  
Kurt Dehnicke

VBr2(N3S2) was synthesized by reaction of VCl2(N3S2) with Me3SiBr. It reacts with PPh4Br in dibromomethane solution to form (PPh4)2[VBr3(N3S2)]2. The compounds were characterized by their IR and 51V NMR spectra. The crystal structure of VBr2(N3S2) was determined by X-ray diffraction (2060 reflexions. R = 0.114). Crystal data: triclinic, space group P1̄, a = 586.4, b = 794.2, c = 744.6 pm. α - 89.25, β - 108.58, γ = 99.67°. Z = 2. The vanadium atoms form planar, six-membered rings wjith the N3S2 groups, with short VN distances (172 and 185 pm). Bromine- bridged dimers are associated via V−N links to form chains in a similar way as in some tetrahalides. The structure is similar to that of VCl2(N3S2), but the chains are rotated by 17° along their axes.


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