bluuebunny/crossref_metadata_2025 huggingface dataset:
Über ein Barium-Lanthanoid-Oxozinkat-Platinat(IV): Ba17Yb16Zn8Pt4O57
Authors: Rabbow Ch. , Sfreddo O. , Müller-Buschbaum Hk.
Published: February 2015

Reactions of BaCO3, ZnO and Yb2O3 mixtures at temperatures up to 1300 °C using plati­num crucibles led to yellow needles of Ba17Y b16Zn8Pt4O57. The compound crystallizes with a hitherto unknown tetragonal crystal structure, space group C5
4h-I4/m, a = 22.731(1), c = 5.682(1) Å , Z = 2. The crystal structure is characterized by PtO6 octahedra and tetragonal ZnO5 pyramids. Yb3+ shows a mono-capped trigonal prismatic coordination and Ba2+ several different coordination environments (C .N = 9 to 10, by O2-). The relationship to the Ba5Ln8M4O21 type is discussed.
Zur Kenntnis der Tief-und Hochtemperaturform eines Oxidarsenats des Zinks: ZnOZn3(AsO4)2
Authors: Frerichs D. , Park C.H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of the low (t-) and high (h-) temperature form of ZnOZn3(AsO4)2 have been prepared by flux and by CO2-LASER techniques respectively. Both compounds crystal­lizes monoclinic, space group C5
2h-P21/n with the lattice parameters t-ZnOZn3(AsO4)2: a = 9.807(3), b = 8.180(2), c = 9.967(2) Å , β = 116.53(2)°, Z = 4 and h -ZnOZn3(AsO4)2: a = 9.743(3), b = 8.163(8), c = 17.933(2) Å , β = 91.55(2)°, Z = 8. Similarities and differences of the crystal structures will be discussed.
Photoredox Decomposition of [Cobalamin-μ-NC-FenII(CN)5]3- Induced by Metal-to-Metal Charge Transfer Excitation
Authors: Kunkely H. , Vogler A.
Published: February 2015

In the presence of oxygen aqueous solutions of the binuclear complex [cobalamin-μ-NC-Fe(CN)5]3- undergo a redox photolysis (ø ~ 2 x 10-3 at λirr = 405 nm) which yields aquocoba-lamin and [Fe(CN)6]3- It is suggested that this photoreaction is induced by direct metal-to-metal charge transfer (MMCT) excitation. On the contrary, [cobalamin-μ-NC-Ru(CN)5]3- is photo-inert because a reactive MMCT state is not accessible.
Quaternary Thorium Transition Metal Pnictide Oxides: ThCu1-xPO, ThCuAsO, and Th2Ni3-xP3O
Authors: Albering Jörg H. , Jeitschko Wolfgang
Published: February 2015

The new compounds ThCu1-xPO and ThCuAsO with ZrCuSiAs-type structure were pre­pared in well crystallized form by chemical vapor transport reactions. Th2Ni3-xP3O with a new structure type was obtained by reaction of ThO2 with the other elemental components in an alumina crucible at high temperatures. The crystal structures of the three compounds were determined from single-crystal X-ray data. ThCu1-xPO: P4/nmm, a = 389.43(4), c -828.3(1) pm, R = 0.024 for 13 variable parameters and 338 structure factors; ThCuAsO: P4/ nmm, a = 396.14(5), c = 844.0(1) pm, R = 0.028 (13 variables and 379 F values); Th2Ni3-xP3O : P4/nmm, a = 394.62(4), c = 1723.2(3) pm, R = 0.018 (27 variables and 374 F values). The refinement of the occupancy parameters revealed significant deviations from the ideal values for the transition metal sites for two compounds resulting in the exact compositions ThCu0.938(4)PO and Th2Ni2.45(1)P3O . Magnetic susceptibility measurements indicate Pauli paramagnetism for ThCu1-xPO . The crystal structures of these compounds are closely related. They belong to a large family of tetragonal structures of which the ThCr2Si2-and the PbFCl-type structures are well known examples.
Die Kristallstruktur von [Mn(CH3CN)6][MnI4]
Authors: Weller Frank , Mai Hans-Joachim , Dehnicke Kurt
Published: February 2015

[Mn(CH3CN)6][MnI4] crystallizes from acetonitrile solutions of Mnl2 as yellow single crystals which were characterized by their IR spectrum and by a crystal-structure analysis. Space group P21/n, Z = 4, structure solution with 3742 observed unique reflections with Fo >5σ(Fo), R = 0.050. Lattice dim ensions at 20°C: a = 1258.0(5), b = 1244.7(2), c = 1753.3(6) pm, β = 92.22(3)°. The compound forms octahedral cations [Mn(CH3CN)6]2+ with site symmetry Ci with average Mn-N bond lengths of 222.3 pm and te­trahedral anions [Mnl4]2- without symmetry with average bond lengths MnI of 271.3 pm.
Structure of Chloro(cyclopentadienone)- (cyclopentadienyl)ruthenium and its Cytotoxic Activity
Authors: Yamazaki Yoshimitsu , Goto Midori , Kageyama Yu-ichi , Tomohiro Takenori , Okuno Hiroaki
Published: February 2015

The structure of Ru(cpO)(cp)Cl complex (3), which was precipitated from aqueous solutions of Ru(cp)2Cl+PF6
- (1), was determined by X-ray crystallographic analysis. The Ru-halogen bond distance was shorter and the dihedral angle be­ tween the rings was larger than the values re­ ported for the corresponding Br analogue, Ru(cpO)(cp)Br (4). The complex 3 (IC50 109 μM) was more cytotoxic than 1 (IC50 163 μM) against mouse sarcoma S180 cells, but less toxic than 4 (IC50 72 μM).
Pb6(AsO4)[B(AsO4)4] - ein neuartiger Kristallstrukturtyp im System PbO/B2O3/As2O5 mit einem Beitrag über Pb(BAsO5)/Pb6(AsO4)[B(AsO4)4] - a New Crystal Structure Type in the System PbO/B2O3/As2O5 with Remarks about Pb(BAsO5)
Authors: Park Cheong-Hwa , Bluhm Karsten
Published: February 2015

Single crystals of Pb6(AsO4)[B(AsO4)4] (I) and Pb(BAsO5) (II) were obtained by melting B2O3, As2O5 and PbO at 800 °C. X-ray investigation led to the space group (I): S4
1 -P4̄ (Nr. 81) with a = 715.4(1), c = 976.2(3) pm, Z = 1 and (II): C3
2 -P31 (Nr. 144) with a = 712.2(1), c = 693.5(2) pm, Z = 3. While (II) is isotypic to the Stillwellite structure, Pb6(AsO4)[B(AsO4)4] represents a completely novel type of crystal structure. Boron and arsenic are tetrahedrally coordinated by oxygen. These polyhedra form two kinds of isolated anions: AsO4
3- and B(AsO4)4
9-. Lead is eightfold coordinated by oxygen.
Zur Synthese und Kristallstruktur von Dibariumkaliumtrizinkborat Ba2KZn3(B3O6)(B6O13)/Synthesis and Crystal Structure of Di-barium Potassium Tri-zinc Borate Ba2KZn3(B3O6)(B6O13)
Authors: Busche Silke , Bluhm Karsten
Published: February 2015

Single crystals of the new compound Ba2KZn3(B3O6)(B6O13) were obtained by using a B2O3 flux technique; they crystallize in an as yet unknown structure type. X-ray investigations led to the space group Ci
1-P1̄ (Nr.2) with lattice parameters a = 705.2(2), b = 712.5(2), c = 1880.3(6), a = 93.43(3)°, β = 90.72(2)°, γ = 119.57(2)°, Z = 2. The structure contains (B3O6)3--rings and a new discrete (B6O13)8- anion, which is composed of two BO4 and two B2O5 units. Zn2+ is tetrahedrally coordinated by oxygen and two out of three tenfold coordinated Ba-sites are statistically occupied by Ba2+ and K+.
Zur Kenntnis zweier Formen des Zinkorthoarsenates: α-Zn3(AsO4)2 und β-Zn3(AsO4)2/On Two Forms of Zinc Orthoarsenate: α -Zn3(AsO4)2 and β-Zn3(AsO4)2
Authors: Frerichs D. , Park C. H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of two forms of zinc orthoarsenate (α-Zn3(AsO4)2 (I) and β-Zn3(AsO4)2 (II)) have been prepared by flux techniques. Both compounds crystallize monoclinically, space groups (I): C2h
5-P21/c, (II): C2h
5-P21/n, with the lattice parameters (I): a = 6.306(2), b = 8.652(2), c =1.321(4) Å, β = 92.25(5) °, Z = 4 and (II): a = 5.281(1), b = 8.494(2), c = 7.726(3) Å, β = 96.39(3)°, Z = 2. α-Zn3(AsO4)2 is isotypic to I-Cu3(AsO4)2 and β-Zn3(AsO4)2 to γ-Zn3(PO4)2. Similarities and differences of the crystal structures are discussed.
Notizen:1,3-Dimethoxy-6H- benzo[b]naphtho[1,2-d]pyran-6-thione, a Thionolactone-Bridged Axially Prostereogenic Biaryl
Authors: Peters Karl , Peters Eva-Maria , Bringmann Gerhard , Schupp Olaf
Published: February 2015

The title compound was prepared from the cor­responding “ordinary” oxolactone bridged biaryl using Lawesson’s reagent. It crystallizes from dichloromethane / petroleum ether in the mono­clinic system, space group P21/a; a = 1115.7(2),b = 1383.9(2), c = 1042.0(1) pm and β = 106.67(1)°.
Weitere Verbindungen mit isolierten quadratischen PdO4-Polygonen: BaPdLn2O5 (Ln=Eu, Gd, Dy, Ho) / Compounds Containing Isolated Square Planar PdO4 Polygons: BaPdLn2O5 (Ln=Eu, Gd, Dy, Ho)
Authors: Müller-Buschbaum Hk. , Wulff L.
Published: February 2015

New compounds of the composition BaPdLn2O5 (Ln = Eu, Gd, Dy, Ho) have been prepared by crystallization from flux. They crystallize isotypic to BaPtLn2O5, space group D5
4h-P4/ mbm. Eu: a = 6.6359(6), c = 5.885(3) Å ; Gd: a = 6.608(3), c = 5.873(3) Å ; Dy: a = 6.5431(7), c = 5.8574(8) Å ; Ho: a = 6.522(4), c = 5.855(5) A , Z = 2. The crystal structure is characterized by isolated planar PdO4 polygons incorporated into a framework of edge-and corner-sharing doubly capped BaO8 cubes and edge-and face-sharing LnO6 prisms.
Mit Bor besetzte kondensierte Cluster in Ta5G e3By (y ≈ 0,7) / Boron Occupied Condensed Clusters in Ta5Ge3By (y ≈ 0.7)
Authors: Peters E. , Müller-Buschbaum Hk.
Published: February 2015

Tantalum, Germanium, Cluster Bronze coloured, rod-shaped crystals of Ta5Ge3By have been prepared by CO2-LASER-techniques. X-ray-methods confirm the well known hexagonal Mn5Si3 type, space-group D3
6h-P63/mcm, a = 7.6276(6) and c = 5.2781(9) Å . The Ta6-clusters are centred by boron atoms.
Zur Kenntnis des ersten Alkalimetall-Cadmium-Halogeno-Oxovanadats: K4CdV5O15Cl / On the First Alkaline-Cadmium-Vanadium Oxide Halide: K4CdV5O15Cl
Authors: Münchau S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of K4CdV5O15Cl have been prepared by crystallization from melts. The yellow crystals show tetragonal symmetry, space group C1
4-P4, a = 9.097(1), c = 5.331(2) Å, Z = 1. K4CdV5O15Cl belongs to the K4CuV5O3Cl type. V (l) forms V2O7 double tetrahedra connected by square V(2)O5 pyramids and CdO4Cl2 octahedra. The crystal structure is dis­cussed with respect to the isotypic compound K4CuV5O15Cl considering a short V(2)-O distance indicative of a vanadinyl group.
1.3.5.7-Tetra-tert-butyl-3.7-dichlor-2.4.6.8.9-pentaaza-1.3.5.7- tetrasilabicyclo[3.3.1.]nonan - Synthese und Kristallstruktur / 1.3.5.7-Tetra-tert-butyl-3.7-dichloro-2.4.6.8.9-pentaaza-1.3.5.7- tetrasilabicyclo[3.3.1.]nonane - Syntheses und Crystal Structure
Authors: Rakebrandt Hans-J. , Klingebiel Uwe , Noltemeyer Mathias , Zak Zdirad
Published: February 2015

The reaction of tert-butyltrichlorosilane with an excess of ammonia leads to the formation of a tetrasilabicyclo[3.3.1.]nonane, an NH-bridged cyclotetrasilazane. The crystal structure of the compound (Me3CSi)4Cl2(NH)5 is described.
New Preparative Methods for the Halides of Titanium(II) and Vanadium(II): Reduction of Titanium(IV) Halides with Sodium and Oxidation of Bis(mesitylene)vanadium(0)
Authors: Calderazzo Fausto , Benedetto Giuseppe E. De , Engler Ulli , Ferri Isabella , Pampaloni Guido , Wagner Trixie
Published: February 2015

TiCl4(THF)2 reacts with two equivalents of sodium in THF to afford the soluble TiCl2(THF)n (1), which has been characterized analytically and by spectroscopic and magnetic measurements. By redox reactions. TiCl2(THF)n gives TiCl2(9,10-C10H8O2) (2), or TiCl2(benzoate)2 .(3), with 9,10-phenanthrenequinone or dibenzoylperoxide in toluene, respectively. By operating in 1,2-dimethoxyethane (DME), Na(DME)1.5[TiCl4(DME)] (4), or NaTiCl3(DME)2 have been isolated from the reaction of TiCl4(DME) with one or two equivalents of sodium, respectively. From 4, by cation exchange, PPN[TiCl4(DME)] [PPN = bis(triphenylphosphine)iminium] (5), has been obtained and characterized analytically, spectroscopically and by X-ray diffraction methods. Crystal data: C40HCl4NO2P2Ti. MW = 818.4, space group: Pna21 (N° 33). a = 14.445(2), b = 15.690(2), c = 17.544(2) Å . V = 3976(2) Å3, Z = 4, F(000) = 1692, R = 0.041, Rw = 0.0420. The titanium(III) atom in the anion has the expected cis-octahedral, slightly distorted, geometry. By reaction of TiBr4(DME)0.5 with sodium in DME, TiBr3(DME)1.5 .1.5 DM E (7), is the product. Bis(mesitylene)vanadium(0), Vmes2, reacts with two equivalents of CPh3Cl in DME, to give VCl2(DME)n.
Die Kristallstrukturen der Dysprosium-Komplexe [DyCl3(DME)2] und [DyCl2(THF)5]+[DyCl4(THF)2]- / Crystal Structures of the Dysprosium Complexes [DyCl3(DME)2] and [DyCl2(THF)5]+[DyCl4(THF)2]-
Authors: Anfang Stefan , Dehnicke Kurt , Magull Jörg
Published: February 2015

[DyCl3(DME)2] (DME = 1,2-dimethoxyethane) has been prepared from the known tetrahy-drofuran complex [Dy2Cl6(THF)7] in boiling DME. Both complexes were characterized by structure determinations. [DyCl3(DME)2]: Space group P21/c, Z = 4, lattice dimensions at -70 °C: a = 1141.9(6), b = 884.2(4), c = 1558.3(6) pm, β = 104.83(4)°. The complex has a molecular structure with a distorted pentagonal bipyramidal geometry in which the oxygen atoms of the chelating DME molecules and one chlorine atom occupy the pentagonal plane. [DyCl2(THF)5]+[DyCl4(THF)2]-: Space group C2/c, Z = 4, lattice dimensions at -70 °C: a -1241.4(9), b = 1139.4(6), c = 2735.1(19) pm, β = 91.19(4)°. The complex contains a seven-coordinate cation with axial chloride ligands in a pentagonal bipyramidal structure and a six-coordinate anion with a trans octahedral geometry.
Darstellung, Schwingungsspektren und Normalkoordinatenanalyse der 10B-und 11B-Isotopomeren von [B2(NCS)6]2- sowie Kristallstruktur von (Ph3P=N=PPh3)2[B2(NCS)6] / Preparation, Vibrational Spectra and Normal Coordinate Analysis of the 10B and 11B Isotopomers of [B2(NCS)6]2- and Crystal Structure of (Ph3P=N=PPh3)2[B2(NCS)6]
Authors: Preetz W. , Steuer B.
Published: February 2015

By reaction of [B6H6]2- with a solution of (SCN)2 in dichloromethane in the presence of solid KOH the hexaisothiocyanatodiborate anion [B2(NCS)6]2- is formed and can be isolated by fractionated crystallization. The crystal structure of (PNP)2[B2(NCS)6] has been determined by single crystal X-ray diffraction analysis; triclinic space group P1̄ with a=12,282(5), b=12,416(5), c=14,155(5)Å, a=68,36(5), β=70,59(5), γ=80,93(5)°.The [B2(NCS)6]2- anion reveals a staggered conformation with nearly local D3d symmetry and a B-B bond length of 1,73(2) Å. Using the crystallographic data a normal coordinate analysis has been performed. With a set of 12 force constants (e.g. fd(BB)=3,62, fd(BN)=4,21 mdyn/Å) a good agreement between observed and calculated frequencies for the 10B and 11B isotopomers has been achieved. The potential energy distribution on the force constants reveals strong vibrational couplings within the B2N6 framework.
Metallkomplexe mit biologisch wichtigen Liganden, LXXXIII [1]. Palladium(II)-und Platin(II)-Komplexe mit 2-Hydroxyiminocarboxylaten und ihren Derivaten / Metal Complexes of Biologically Im portant Ligands, LXXXIII [1], Palladium(II) and Platinum (II) Complexes of 2-Hydroxyiminocarboxylates and their Derivatives
Authors: Lampeka Rostislav , Wanje Herbert , Bec Wolfgang
Published: February 2015

Palladium(II), Platinum(II), 2-Hydroxyiminocarboxylate, Oximes of Pyruvoyl a-Amino Acids The synthesis and spectroscopic properties of palladium(II) and platinum (II) chelate com­ plexes with carboxylates of 2-hydroxyiminopropionic, 2-hydroxyimino-3-phenylpropionic acids, with the amide and N-methylamide of 2-hydroxyiminopropionic acid, and with oximes of pyruvoylglycine and pyruvoyl-L-phenylalanine are reported.
Metallkomplexe mit biologisch wichtigen Liganden, LXXXY [1] Koordinationsverbindungen von Cobalt(III), Iridium(III), Ruthenium(II) und Palladium(II) mit Isoxazol-und Isoxazolin-3-carboxylaten / Metal Complexes of Biologically Important Ligands, LXXXV [1] Coordination Compounds of Cobalt(III), Iridium (III), Ruthenium (II) and Palladium(II) with Isoxazole-and Isoxazoline-3-carboxylates
Authors: Lampeka Rostislav , Mihan Shahram , Beck Wolfgang
Published: February 2015

Chelate complexes of 5-phenyl-isoxazole-3-carboxylate (L1) and 5-phenyl-isoxazoline-3-carboxylate (L2) ligands were prepared: Pd(L1)2. Cp*(Cl)Ir(L1), (p-cymene)(Cl)Ru(L1), Pd(L2)2, (Et3P)(Cl)Pd(L2),

, Cp*(I)Co(L2), Cp*(Cl)Ir(L2) (10), and (p-cymene)(Cl)Ru(L2) (Cp* = C5Me5). The structure of 10 was determined by X-ray diffraction.
Die Kristallstruktur von [(THF)2Li(μ2-Cl)2TiCl2(THF)2] / Crystal Structure of [(THF)2Li(μ2-Cl)2TiCl2(THF)2]
Authors: Neumüller Bernhard , Heshmatpou Felora , Dehnicke Kurt
Published: February 2015

The crystal structure of the title com pound has been determined by X-ray methods. Space group C2/c, Z = 4, lattice dimensions at -80 °C: a = 1343.8(2), b = 1031.6(1), c = 1669.4(1) pm, β = 96.47(1)°. The compound forms an ion pair in which the lithium atom is coordinated in a distorted tetrahedral geometry by two THF molecules and by two chlorine atoms. The halide atoms have a μ2-bridging function, coordinating the lithium and the titanium center. The titanium atom possesses a distorted octahedral environment with two THF ligands in trans-position.
Darstellung, 11B-NMR-Spektren, Schwingungsspektren und Normalkoordinatenanalyse von conjuncto-Bis-hexahydro-closo-hexaborat, [B6H6-B6H6]2-, sowie Kristallstruktur von [P(C6H5)4]2-conjuncto-[B6H6-B6H6] / Preparation, 11B NMR Spectra, Vibrational Spectra and Normal Coordinate Analysis of conjuncto-Bis-hexahydro-closo-hexaborate, [B6H6-B6H6]2-, and the Crystal Structure of [ P(C6H5)4]2-conjuncto-[B6H6-B6H6]
Authors: Bublitz D. , Franken A. , Preetz W. , Thomsen H.
Published: February 2015

By reaction of [B6H6]2- with dibenzoylperoxide in dichloromethane conjuncto-[B6H6- B6H6]2- is formed. The product could be separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [P(C6H5)4]2 -conjuncto- [B6H6-B6H6] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1̄ with a = 10.8315(10), b = 11,2422( 12), c = 20.340(2) Å, α = 91.278° (9), β = 90.178° (9), γ = 105.662°(9). The 11B NMR spectrum reveals three signals with the intensity ratio 1:1:4, for two equivalent moieties of the conjuncto molecule ion with local C4v symmetry. The IR and Raman spectra of the deprotonated Cs salts of the 10B, 11B and their respective D isotopomers of conjuncto-[B6H5-B6H5]4- exhibit characteristic shifts. Using averaged crystallographic data and assuming idealized D4h symmetry, normal coordinate analyses have been performed based on a modified valence force field. With a set of eleven force constants (e.g. fd(BB)conjuncto = 2.9, fd(BB)cage = 1.6 mdyn/Å) very good agreement between observed and calculated frequencies has been achieved. From strong vibrational coupling with the B6 clusters two vibrations result for the conjuncto B-B bond at 1142/1198 and 292/304cm-1 for 11B/10B species, respectively. They can be assigned as anti-phase and in-phase motions of the conjuncto B atoms related to the equatorial B4 planes.
Zur Synthese und Kristallstruktur von Bariumboroarsenat Ba(BAsO5) mit einem Beitrag über Bariumorthoarsenat Ba3(AsO4)2 / Synthesis and Crystal Structure of Barium Boroarsenate Ba(BAsO5) with a Contribution on Barium Orthoarsenate Ba3(AsO4)2
Authors: Park Cheong-Hwa , Bluhm Karsten
Published: February 2015

Single crystals of Ba(BAsO5) (I) and Ba3(AsO4)2 (II) were obtained by melting B2O3, arsenic pentoxide and BaO at 1100°C. Both compounds crystallize trigonally, space groups (I): C3
2 - P31 (Nr. 144), (II): D3d
5 - R3̄m (Nr. 166), with the lattice parameters (I): a = 726.7(1), c = 710.6(1) pm, Z = 3 and (II): a = 576.7(1), c = 2116.3(2) pm, Z = 3. Ba(BAsO5) is isotypic to Pb(BAsO5) (Stillwellite structure) and Ba3(AsO4)2 to Ba3(PO4)2. The structure of Ba(BAsO5) is characterized by helical chains of rings of two borate tetrahedra and one arsenate tetrahedron. Barium is tenfold coordinated by oxygen. A rod-like sequence of coordination polyhedra, AsO4
- Ba(2)O10-Ba(1)O12-Ba(2)O10-AsO4 is characteristic in the crystal structure of Ba3(AsO4)2.
Darstellung und 11B-NMR-Spektrum von Heptabromo-closo-heptaborat, [B7Br7]2- sowie Kristallstruktur von [(C5H5N)2CH2][B7Br7] / Preparation and 11B NMR Spectrum of Heptabromo-closo-heptaborate, [B7Br7]2-, and the Crystal Structure of [(C5H5N)2CH2][B7Br7]
Authors: Franken A. , Thomsen H. , P reetz W.
Published: February 2015

By reaction of conjuncto-[B6H6-B6H6]2- in alkaline solution with excess bromine the heptabromo-closo-heptaborate, [B7Br7]2 is formed. The crystal structure of [(CsH3N)2CH2][B7Br7] has been determined by single crystal X-ray diffraction analysis (monoclinic, space group P21/a with a = 15.0843(14), b = 9.8882(14), c = 17.057(2) Å, β = 114.039°(7)). In accordance with the D5h point symmetry, the anion shows two singlets at -23.3 and -0.1 ppm with the intensity ratio 2:5 in its 11B NMR spectrum.
Hochdruckreaktionen quaternärer Chalkogenide mit Schichtstruktur / High-Pressure Reactions of Quaternary Layered Chalcogenides
Authors: Berand N. , Haeuseler H. , Range K.-J.
Published: February 2015

The layered chalcogenides CoGa1.7Ti0.3S4, CoGa1.7V0.3, CoGa1.6Cr0.4S4, CoGaInS4, MnGa1.5Cr0.5S4, MnGa1.4Sc0.6S4, MnGa0.8In1.2S4, MnIn2S1.6Se2.4 and CdIn2S2.1 Se1.9 have been investigated under high-pressure - high-temperature conditions (p ≤ 60 kbar, T ≤ 1600°C). MnIn2S1.6Se2.4 and CdIn2S2.1,S1.9 show a phase transition to spinel-type compounds (a = 11.022(2) and a = 11.059(1) Å, respectively). MnGa0.8In1.2S4 forms a high-pressure polymorph with an olivine-type structure (a = 12. 856(3), b = 7.500(3), c = 6.128(2)Å. All other compounds decompose under the conditions applied. The results of a Rietveld structure refinement for the two high-pressure spinels are presented
Ligand Influences on the Supramolecular Chemistry of Simple Gold(I) Complexes: Mononuclear (Isonitrile)gold(I) Complexes
Authors: Schneider Wolfgang , Angermaier Klaus , Sladek Alexander , Schmidbaur Hubert
Published: February 2015

A series of (isonitrile)gold(I) complexes has been synthesized: (MeNC)AuX (X = Cl la, I lc), (t-BuNC)AuBr 2b. (PhNC)AuX (X = Cl 3a. Br 3b. I 3c. SCN 3d), (MesNC)AuCl 4a [mes=mesityl], and (MeOC(O)CH2NC)AuX (X = Cl 5a. Br 5b. I 5c. SCN 5d). The chlorides were prepared by the reaction of (Me2S)AuCl with equimolar amounts (or with an excess) of the corresponding isonitrile. The bromides, iodides and thiocyanates were obtained from the reaction of (RNC)AuCl with K+X- (X = Br, I, SCN) in the two-phase system H2O/CH2CI2. The molecular and crystal structures of la. 2b. 3a-c, 4a, and 5a-c have been determined by X-ray diffraction methods. In the solid state the molecules are aggregated through short Au-Au contacts into dimers (4a and 5c), chains (la, 2b and 3a-c) or sheets (5a and 5b). The influence of the isonitrile and halide ligands on the type and strength of the intermolecular Au-A u contacts is discussed
Synthesis of Pentaalkyl-6-bromo-2,3,4,5-tetracarba-nido-hexaboranes(6)
Authors: Wrackmeyer Bernd , Glöckle Alexandra
Published: February 2015

Peralkylated 2,3,4,5-tetracarba-mdo-hexaboranes(6) 1 react with boron tribromide, BBr3, via selective exchange of the alkyl substituent in 6-position to give the corresponding new 6- bromo derivatives 2 in quantitative yield. The 6-iodo derivatives 2(1) can be prepared in the same way using BI3. Treatment of the carbaboranes 2 with Li Et3BH leads to the 1,2,3,4,5- pentaalkyl-2,3,4,5-tetracarba-inido-hexaboranes(6) 3. 1,3,4,6-Tetraethyl-2,3,4,5-tetracarbaw do-hexaborane(6) 4 reacts with BBr3 via degradation of the carbaborane cage to give EtBBr2, and (Z)-1,4-bis [bis(dibromoboryl)]-3-hexene 5. A new bis(diethylboryl)-substituted dialkenyl(bromo)borane 8 was prepared, but attem pts failed to convert it into a 1-bromo- or 6-bromo-mdo-C4B2-carbaborane. Treatment of 1,1-dialkyl-3-diethylboryl-4-ethylstannoles 9 with a large excess of BBr3 also affords 5, whereas 6-bromo-l,3,4-triethyl-2,3,4.5-tetracarbamdo- hexaborane(6) 11 was isolated in low yield (<5%) from the reaction between 9 and BBr3 (slight excess)
Electrophilic Oxygenation with XeF2 - H2O in Hydrogen Fluoride, Part 1. Oxygenation of [C6F5Xe]+ [AsF6]- and Epoxidation of Fluorinated Cycloalkenylxenon(II) Salts
Authors: Frohn H. J. , Bardinh V. V.
Published: February 2015

XeF2 and H2O react with [C6F5Xe]+ [AsF6]- in HF without Xe-C bond cleavage under formation of the cyclohexadienone compound [3-O-1.4-CeF5Xe]+ [ AsF6]- The FC=CF moiety in this dienone is epoxidised with the same reagent. The cyclohexadiene compound [1,4-C6F7Xe]+ [AsF6]- could also be epoxidised under the same conditions.
Electrophilic Oxygenation with XeF2 - H2O in Hydrogen Fluoride, Part 2. Electrophilic Oxygenation of Pentafluorobenzene Derivatives C6F5X
Authors: Frohn H. J. , Bardin V. V.
Published: February 2015

Electrophilic oxygenation of polyfluorobenzenes C6F5X (X = F. Cl. Br. H, CF3, NH3
+, NMe3
+, OH and OCH2CF3) with XeF2 and H2O in HF leads to the formation of polyfluorinated 1,4- cyclohexadienones. Pentafluoroiodobenzene is converted into C6F5IF2 and C6F5IF4, whereas [CeF5N2]+ [NbF6]- is unreactive towards this new type of electrophilic oxygenation.
Halogenierungs- und Dissoziationsstufen eines Diphosphonio-1,2,4- triphosphoiids / Stages of Halogenation and Dissociation of a Diphosphonio-1,2,4-triphospholide
Authors: Schrödel Hans-Peter , Schmidpeter Alfred , Nöth Heinrich , Schmidt Martin
Published: February 2015

Reductive condensation of Ph3P=C(SiMe3)2 and PCl3 or PBr3 yields the ionic halides of the 3,5-bis(triphenylphosphonio)-1,2,4-triphospholide cation 5. The compounds can take up two moles of halogen X2. In the first step bis(triphenylphosphoranediyl)trihalo-1,2,4-triphos- pholanes 6 are formed. Low temperature 31P NMR spectroscopy shows them to exist in two conformeric forms. In polar solvents heterolytic dissociation of the phosphorus-halogen bond in the 4-position occurs.

The molecular structure of 5 demonstrates a cyclic delocalized bonding system. Chlorination or bromination (to give 6) effects little structural change with exception of a large increase of the PP bond length. The phosphorus-halogen bonds in 6 are very long and rather different in length. The overall situation as well as the structural details can be rationalized to result from a negative hyperconjugation between the ylidic carbon atoms and the phosphorus-halogen bonds.
Über einen Hollandit des Vanadiums: Ba0,5Bi0,9V8O16 / On a Hollandite of Vanadium: Ba0,5Bi0.9V8O16
Authors: Feldmann J. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ba0,5Bi0,9V8O16, have been prepared with CO2-LASER techniques. The compound crystallizes with tetragonal symmetry, space group C4h
5- I4/m. a = 9.943(2). c = 2.893(2) Å. Z = 1 and belongs to the Hollandite family. The two different tunnel positions are occupied by Ba2+ and Bi2+. As a result of this Ba2+ shows a cuboctahedral and Bi3+ a square pyramidal BiO4+s
2 coordination if the lone pair of bismuth is included.
Excited State Properties of Myochrysin and Auranofin
Authors: Kunkely Horst , Vogler Arnd
Published: February 2015

Myochrysin (sodium aurothiomalate hydrate) and auranofin [2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranosato-S)(triethylphospine)gold(I)] are luminescent in the solid state and in ethanol glasses at 77 K (myochrysin: λmax = 600 nm; auranofin: 618 nm). Aqueous myochrysin and auranofin in acetonitrile undergo a photodecomposition. It is assumed that the luminecence originates from a metal-centered ds excited state with partial ligand-to-metal charge transfer (LMCT) character while the photodecomposition is induced by LMCT excitation.
Zwei Metasilicate mit Vierer-Einfach-Ketten: Hochdrucksynthese und Strukturverfeinerung von Sr2(VO)2Si4O12 (Haradait) und Sr2(TiO)2Si4O12 / Two Metasilicates with Vierer Single Chains: High-Pressure Synthesis and Structure Refinement of Sr2(VO)2Si4O12 (Haradaite) and Sr2(TiO )2Si4O12
Authors: Berger Thomas , Range Klaus-Jürgen
Published: February 2015

Single crystals of Sr2(VO)2Si4O12 could be obtained by high-pressure high-temperature reaction of a SrSiO3/SiO2/V2O5 mixture in a modified Belt-type apparatus. The green crystals are orthorhombic, space group Cmcm, with a = 5.3139(3), b = 14.6281(7), c = 7.0329(4) Å and Z = 2. The structure comprises vierer single chains of SiO4 tetrahedra, the resulting Si4O12 units being connected by VO5 square pyramids. There is one short distance (V - O = 1.61 (1) Å) within the square pyramid, giving definite evidence to a (VO)2+ group with a V = O double bond.

The crystal structure of microcrystalline Sr2(TiO)2Si4O12, obtained by high-pressure hightemperature reaction of a SrSiO3/SiO2/TiO2 mixture, was refined by the Rietveld technique. The compound (Cmcm, a = 5.3530(2), b = 14.4864(7), c = 7.0817(3) Å, Z = 2) is isostructural with the vanadium compound.
Synthese und Kristallstruktur von Cl3Ti[N(SiMe2Cl)(SiMe2NH2)] / Synthesis and Crystal Structure of Cl3Ti[N(SiMe2Cl)(SiMe2N H2)]
Authors: Buheitel R. , Milius W. , Schnick W.
Published: February 2015

Cl3Ti[N(SiMe2Cl)(SiMe2NH2)] is yielded by reaction of TiCl4 with two molecules ClMe2SiNHSiMe3. A single crystal structure determination (P 21/n, a = 747.12(2), b = 1294.1(3), c = 1496.7(3) pm, β = 90.30(3)°, Z = 4) shows a planar four-membered ring Ti-N-Si-N as the central feature of the monomers formed by a weak coordinative bond of the NH2 group to the Ti atoms. The monomers are connected to give dimers via two Cl bridges linked to the Ti atoms.
Synthese von Organylphosphonigsäure-N-(N′,N′,N″,N″-tetramethyl)guanidinidfluoriden und ihre Reaktion mit Chalkogenen und Triphenylmethylazid; Darstellung und Charakterisierung von Organylchalkogeno- und Phenyltriphenylmethylimino- phosphonsäure-N-(N′,N′,N″,N″-tetramethyl)guanidinidfluoriden / Synthesis of Organophosphonous-N-(N′,N′,N″,N″-tetramethyl)guanidinide Fluorides and their Reaction with Chalcogens and Triphenylmethyl Azide; Synthesis and Characterization of Organochalcogeno- and Phenyltriphenylmethylimino-phosphonic-N-(N′,N′,N″,N″-tetramethyl)-guanidinide Fluorides
Authors: Münchenberg Jochen , Thönnessen Holger , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The organophosphonous-N-(N′,N′,N″,N″-tetramethyl)guanidinide fluorides RP(F)N=C(NMe2)2 2a (R = t-Bu) and 2b (R = Ph) were synthesized. They are readily oxidized by the urea-H2O2 1:1 adduct and by elemental sulfur, selenium and tellurium to give the compounds 4a/b, 5a/b, 6a/b and 7a/b respectively. Compound 2b undergoes a Staudinger reaction with triphenylmethyl azide to yield the phosphine imide 3. The compounds were characterized by 1H-, 13C-, 19F and 31P NMR spectroscopy, and 6a/b and 7a/b by 77Se and 125Te NMR spectroscopy. The structures of the sulfur compound 5b and the selenium compound 6a were confirmed by X-ray crystal structure analysis. Both molecules exhibit short P-N-bonds [158.9(2) pm and 159.8(3) pm] consistent with partial double bond character even though the P(:S) and the P(:Se) bonds are not longer than a normal double bond.
Notizen:Über NaBa3RuO6und NaBa3IrO6.Zwei Edelmetall-Oxometallate mit Sr4PtO6-Struktur / On NaBa3RuO6and NaBa3IrO6.Two Noble Metal Oxometallates Showing Sr4PtO6Structure
Authors: Frenzen S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of NaBa3RuO6 (I) and NaBa3IrO6 (II) have been prepared by crystallization from melts in closed silver tubes. The crystal structures were investigated by X-ray techniques. Both compounds crystallize with trigonal (rhombohedral) symmetry, space group D6
3d-R3̅c, I: a = 10.107(2), c = 11.872(2) Å, II: a = 10.128(2), c = 11.905(2) Å, Z = 6. I and II are isostructural to the Sr4PtO6 type.
Notizen: Enantioselective Catalysis, 101 [1] Synthesis and Coordination Properties of (3′S,4′S)-(+)-1,2-Bis(3′,4′-dimethoxyphospholano)benzene, a N ew Chiral Diphosphane
Authors: Brunner Henri , Net Gemma
Published: February 2015

A new bisphospholane, BDPB, derived from 1,2-bisphosphanobenzene and tartaric acid as well as the complex [Rh(COD)(BDPB)]PF6 were synthesized. The strong binding of BDPB to metals and the presence of four functional groups in the periphery of the molecule make this bisphospholane a good starting point for new expanded bisphosphanes.
Elektronentransfer und Ionenpaar-Bildung, 48 [1] Titrationen von Tetraphenyl-p-benzochinon mit Natrium- und Kaliummetall in aprotischen Lösungen / Electron Transfer and Ion Pair Formation, 48 [ 1 ] Titrations of Tetraphenyl-p-benzoquinone with Sodium and Potassium Metals in Aprotic Solutions
Authors: Bock Hans , Kleine Markus
Published: February 2015

UV/VIS and ESR spectra of electron transfer reaction products in aprotic (cH⊕ < 0,1 ppm) solution can be measured in an especially designed and sealed glass apparatus and provide information on unknown facets of the microscopic pathway through the network of interdependent equilibria. For tetraphenyl-p-benzoquinone in tetrahydrofuran, single-electron reduction by a sodium metal mirror produces a red solution and, unexpectedly, after addition of 2.2.2. cryptand, contact with a potassium metal mirror generates a green (!) one. For both, ESR/ENDOR spectra prove the presence of tetraphenyl-p-benzoquinone radical anion. UV/VIS measurements provide the clue: In the equilibrium revealed by repetetive spectra recording, M·⊖
solv + Me⊕
solv ⇄ [M·⊖···Me⊖]solv, the radical anion is green (vm = 16900 cm-1) and the contact ion pair red (vm=18900 cm-1 ). On ion pair formation, therefore, the excitation energy of the radical anion increases by 0.25 eV.
Ti2Ni2In, Zr2Co2In, and Zr2Pd2In - Intermetallic Compounds with Ordered U3Si2 and Zr3Al2 Type Structure
Authors: Pöttgen Rainer , Kotzyba Gunter
Published: February 2015

Ti2Ni2ln, Zr2Co2ln, and Zr2Pd2In were synthesized by reacting the elements in an arcmelting furnace and subsequent annealing at 1070 K. The compounds were investigated by X-ray diffraction on both powders as well as single crystals. Zr2Co2 adopts the ordered U3Si2 type structure: P4/mbm, a = 720.54(7), c = 331.59(4) pm. The structure consists of planar [Co2ln] layers with CO2 dumb-bells which are separated by the zirconium atoms. Ti2Ni2ln and Zr2Pd2ln crystallize with the ordered Zr3Al2 b type structure (space group P42/mnm), a superstructure of U3Si2: a = 694.3(2), c = 623.2(2) pm for Ti2Ni2In and a = 746.0(1), c = 686.1(1) pm for Zr2Pd2ln. The Ni2 and Pd2 dumb-bells in the Ni2ln and Pd2ln layers of Ti2Ni2In and Zr2Pd2In are shifted from the mirror planes of the subcell resulting in puckered layers with weak interlayer Ni-Ni and Pd-Pd contacts, respectively. The indium atoms in these compounds occupy [Ti8] and [Zr8] square prisms while the transition metal atoms are surrounded by [Ti6] and [Zr6] trigonal prisms. These structural fragments are derived from the CsCl and AlB2 type structures. Chemical bonding in these intermetallic compounds is briefly discussed. Magnetic susceptibility measurements of compact polycrystalline samples indicate Pauli paramagnetism.
1,3,4,5-Tetramethyl-2-methylenimidazolin - ein Olefin mit Ylid-artigen Eigenschaften [1] / 1,3,4,5-Tetramethyl-2-methylenimidazoline - an Olefin with Ylidic Properties [1]
Authors: Kuhna Norbert , Bohnena Hans , Henkel Gerald , Kreutzberg Jörg
Published: February 2015

A facile synthesis of l,3,4,5-tetramethyl-2-methylenimidazoline 5 (Im) starting from the pentamethylimidazolium ion (8) and KH is described. Boranes react with 5 to give the adducts ImBHi3 (11) and ImBF3 (18). With Mel and CH3C(O)Cl the imidazolium salts ImMe+ (19) and ImC(O)Me+ (20) are obtained. CS2 gives the zwitterionic compound ImCS2 (24) which is transformed into the cationic thiocarboxylic ester ImC(S)SCH2Cl+ on treatment with CH2Cl2. Reaction with chlorotrimethylsilane gives the imidazolium ion ImSiMe+
3 (26) which may be transferred into the disilylated imidazolium ion 28 via deprotonation and subsequent silylation, the silylated olefin 27 being the intermediate. Similarly, the cations ImSiR2Cl+ (29; R = Me, Ph) are obtained from 5 and the silanes R2SiCl2. The neutral adduct ImSnPh2Cl2 (32) is formed in the reaction of 5 with Ph2SnCl2. Iodine reacts with 5 to give the charge-transfer adduct Iml2 (35), which can be further transferred into the imidazolium salt Iml+I-
3 (36).
Elementorganische Verbindungen mit o-Phenylenresten, XXVIII [1] Charge-transfer-Komplexe von 2,3,7,8-Tetraalkoxy-chalkogenanthrenen mit 7,7,8,8-Tetracyan-2,3,5,6-tetrafluor-chinodimethan / Organometalloidal Compounds with o-Phenylene Substituents, Part XXVIII [1] Charge-Transfer Complexes of 2,3,7,8-Tetraalkoxy-chalcogenanthrenes wjth 7,7,8,8-Tetracyano-2,3,5,6-tetrafluoro-quinodimethane
Authors: Friederichs Stephan , Kudnig Jens , Klar Günter
Published: February 2015

2,3,7,8-Tetramethoxythianthrene and -selenanthrene, as well as -tetraethoxythianthrene give isostructural 1:1 charge-transfer complexes with 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane. In the columnar crystal structures there are alternating donor and acceptor molecules. The chalcogenanthrene molecules which are folded at their E···E axes in the pure state, are planar in the complexes indicating a charge-transfer according to [donor]+ [acceptor]- . Consecutive molecules of the stacks are arranged in such a way that an optimum overlap of the HOMO of the donor and the LUMO of the acceptor, both of which are of π-type character according to MNDO calculations, is secured.
Strukturelle Unterschiede von Ruthenium(III)-Chelaten mit SN- und SO -Liganden. Strukturen von Tris(1-phenyl-3-methyl-4-phenylhydrazono-5-thionato)ruthenium (III) und Tris(thiodibenzovlm ethanato)ruthenium( III) / Structural Differences of Ruthenium (III) Chelates with SN- and SO-Ligands. Crystal Structures of Tris(1-phenyl-3-methyl-4-phenyl-hydrazono-5-thionato)- ruthenium (III) and Tris(thiodibenzoylmethanato)ruthenium (III)
Authors: Hinsche G. , Uhlemann E. , Weller F.
Published: February 2015

Both complexes were synthesized and characterized by X-ray analysis.They have a distorted octahedral structure. In the first case a meridional arrangement of ligands was found whereas the compound with thiodibenzoylmethane has a facial structure. Crystal data: C48H39N12RuS3: a = 1400,9(3)pm , b = 1839,3(4) pm , c = 1969,9(4) pm, β = 109,65(3°); space group: P2(1)/c , Z = 4, C45H33O3RuS3: a = 1013,2(2) pm, b = 1762,7(4) pm, c = 2151,5(4) pm; β = 100,11(3°), space group: P2(1)/n, Z = 4.
Zur Kristallchemie ungeladener Phosphazen-Basen, I [1] Strukturen zweier Hydrate und eines Acetats von Tris(dimethylamino)methyliminophosphoran / Crystal Chemistry of Uncharged Phosphazene Bases, I [1] Structures of Two Hydrates and an Acetate of Tris(dimethylamino) methyliminophosphorane
Authors: Hartmann Frank , Mootz Dietrich , Schwesinger Reinhard
Published: February 2015

Two hydrates and an acetate of the uncharged, very strong phosphazene base tris(dimethylamino)methyliminophosphorane, (Me2N)3P=NMe (for short Me-P1), have been characterized by their crystal structures. A monohydrate, Me-P1 · H2O , mp. 3°C, is monoclinic with space group P21/n and Z = 4 formula units per unit cell of dimensions a = 8.585, b = 11.107, c = 13.083 Å, and β = 97.76° at -30°C. Another hydrate, Me-P1 · 1.75 H2O, mp. - 11°C. is triclinic with P1̅, Z = 4, a = 7.924, b = 11.768, c = 14.257 Å, α = 89.70°,β = 86.30°, and 7 = 86.54° at -100°C. An acetate, Me-P1 · CH3COOH, mp. 88°C, is also triclinic with P1̅, Z = 2, a = 7.558, b = 8.193, c = 11.431 A, a = 93.60°, β = 96.52°, and γ = 92.12° at-100°C. In the hydrate Me-P1 · H2O , a centrosymmetric dimer of the formula unit is formed by O-H···N hydrogen bonds arranged in a four-membered ring. In the hydrate Me-P1 · 1.75 H2O , two rings of this kind are linked by additional water molecules into an infinite chain each. Both hydrate structures are those of molecular adducts, in spite of the great strength of the base. By contrast, the structure of the acetate Me-P1 · CH3COOH is clearly ionic, with an ion pair being formed by a bifurcated (three-center) hydrogen bond N-H(···O)2 from the protonated N atom of the base cation to both O atoms of one and the same acid anion.
Strukturen ladungsgestörter oder räumlich überfüllter Moleküle, 108 [1] Strukturänderungen bei der Zweifach-Reduktion von Tetraphenyl-p-chinodimethan zu seinem Dianion / Structures of Charge-Perturbed or Sterically Overcrowded Molecules, 108 [1] Structural Changes of Tetraphenyl-p-quinodim ethane on Twofold Reduction to its Dianion
Authors: Bock Hans , Arad Claudia , Näther Christian , Göbel Ilka , John Andreas
Published: February 2015

The two-electron reduction of tetraphenyl-p-quinodimethane M via its radical anion M⊖ to its dianion M⊖⊖ is explored both by cyclovoltammetry and ESR/ENDOR spectroscopy. Contact of the diglyme solution with added 15-crown-5 under aprotic conditions with a sodium metal mirror yields black crystals of a solvent-separated contact ion triple [M⊖⊖][Na⊕(OCH2CH2)5(H3CO(CH2CH2O)2CH3)]2. The two-electron-insertion into the pquinodimethane derivative R2C⊖=C(HC=CH)2C=CR2 changes its structure drastically to that of a twofold carbanion substituted benzene, R2C⊖ -(C6H4)- ⊖CR2. MNDO calculations provide a rationale for both the tremendous solvation of a Na⊕ center coordinated to seven oxygen centers of 15-crown-5 and of one diglyme molecule and the structural changes as well as the charge distribution in the unique Tetraphenyl-p-quinodimethane dianion (H5C6)2C⊖-(C6H4)- ⊖C(C6H5)2, in which the two negative charges are largely localized at the carbanion center of the benzene -substituents.
Struktur von C2Cl6N4P2, dem Reaktionsprodukt von Dicyandiamid mit PCl5 / Structure of C 2Cl6N4P2, the Reaction Product of Dicyandiamide with PCl5
Authors: Belaj Ferdinand
Published: February 2015

The reaction product of dicyanodiamide with PC15 (1:2) is 2,2,4-trichloro-2,2-dihydro- 6-trichlorophosphazeno-1.3,5,2λ5-triazaphosphorine and not 2.4,6-trichloro-2,2-dihydro-2- trichlorophosphazeno-1,3,5,2λ5-triazaphosphorine as reported in the literature. This is confirmed by an X-ray structure determination at 90K: Space group P 21/c, a = 17.258(5), b = 9.664(3), c = 15.070(4) Å, β = 114.05(2)°, Z = 8, R = 3.99%. Both molecules of the asymmetric unit show about the same conformation with approximate Cs-m - symmetry as was also obtained by semi-empirical MNDO calculations. The thermal motion analysis establishes that the molecules cannot be described as ′rigid bodies′, and that the easy deformability of the exocyclic C-N-P angles allows the ′rigid′ NPCl3 tetrahedra to perform almost isotropic librations.
Spezielle Alkylammoniumhexachlorometallate, II [1] Synthese und Kristallstruktur von Bis(1,2-diammoniopropan)hexachlororhodat(III)-chlorid, [H3N-CH(CH3)-CH2-NH3]2[RhCl6]Cl/ Alkylammonium Hexachlorometallates, II [1] Synthesis, and Crystal Structure of Bis(1,2-diammoniopropane) Hexachlororhodate(III) Chloride, (H3N-CH(CH3)-CH2-NH3]-[RhCl6]Cl
Authors: Frank Walter , Reiß Guido J.
Published: February 2015

Bis(1,2-diammoniopropane) hexachlororhodate(III) chloride, [H3N-CH(CH3)-CH2-NH3]2 [RhCl6]Cl (1) has been obtained by the reaction of rhodium(III) chloride with rac-1,2- diammoniopropane dihydrochloride in hydrochloric acid solution. The quasi-ternary compound, which crystallizes in the orthorhombic space group Pbca (a - 11.0007(13) Å, b = 22.181(2) A, c = 14.638(2) A, V = 3571.7(7) Å3, \ T = -120 °C, Z - 8) contains two crystallographically independent 1,2-diammoniopropane ions beside one hexachlororhodate and one chloride ion. One of the cations shows a R/S-S/R-disorder of enantiomeric pairs in the centrosymmetric crystal lattice. The packing scheme is determined by a complex framework of hydrogen bonds.
Intercalation Compounds of Large Organic Molecular Cations in the Layered Dichalcogenide 2H-TaS2
Authors: Hauptmann Anja , Lerf Anton , Biberacher Werner
Published: February 2015

We report on the first successful intercalation of organic cations in large crystals of 2H-TaS2 by electrochemical methods. The following species have been intercalated: Tetramethylammonium, methylviologen and methylene blue. Whereas the first species can be intercalated in chemical equilibrium like the hydrated metal ions, the intercalation of the other two more complex cations is accompanied by side reactions. The most complex system is methylene blue/TaS2 where we observe three different phases depending on the preparation conditions. The electrical resistivity as a function of temperature has been measured by a 4-point ac method on single crystals immediately after intercalation. All samples are superconductors, some of them having a transition temperature to the superconducting state Tc of 4.9 K, which is quite high for organic molecule intercalation compounds of 2H-TaS2. The anomaly of the resistivity at 77 K in the empty host lattice is suppressed in all of the intercalated samples even at the very low charge transfer of n = 0.06.
Iodbenzol als Lewis-Säure: Synthese und Kristallstrukturen von PPh4[Cl-I-C6H5] und PPh4[Br-I-C6H5] / Iodobenzene as Lewis-Acid: Synthesis and Crystal Structures of PPh4[Cl-I-C6H5] and PPh4[Br-I-C6H 5]
Authors: Ghassemzadeh Mitra , Magull Jörg , Fenske Dieter , Dehnicke Kurt
Published: February 2015

The donor-acceptor complexes [X-I-C6H5]− with X− = Cl− and Br− have been prepared as tetraphenylphosphonium salts from iodobenzene and PPh4X in acetonitrile solutions. They form colourless single crystals, which were characterized by crystal structure determinations.

PPh4[Cl-I-C6H5]: Space group P21/c, Z = 4. Lattice dimensions at -70°C: a = 1301.1(5), b= 1457.0(5), c = 1478.8(5) pm, β = 114.17(3)°.

PPh4[Br-I-C6H5]: Space group P21/n, Z = 4. Lattice dimensions at 20°C: a = 1354.9(1), b= 1480.1(2), c = 1375.5(1) pm, β = 106.13(2)°.

The halide ions are coordinate at the iodine atom of the iodobenzene molecule in a linear arrangement [X-I-C6H5]− with bond lengths Cl-I of 327.9 and Br-I of 347.2 pm.
Herstellung von CuTa2O6 - von der Trirutil- zur Perowskit-Struktur / Preparation of CuTa2O6 - from the Trirutile to the Perovskite Structure
Authors: Krabbes I. , Langbein H.
Published: February 2015

A new trirutile MTa2O6 was synthesized by thermal decomposition of a freeze dried Cu- Ta-oxalate precursor. Its formation takes place preferentially starting from Cu-rich precursor compositions. Above 1000°C decomposition leads to the already known perovskite like structure with a composition Cu1.05Ta1.98O6 . The degree of the orthorhombic distortion of the perovskite unit cell depends on the conditions during the cooling process after perovskite formation.
Zur Reaktion von Trialkylphosphiten mit dem Titanocen-Komplex des 4,5-Dimercapto-1,3-dithiol-2-ons / Reaction of Trialkyl Phosphites with the Titanocene Complex of 4,5-Dimercapto-1,3-dithiole-2-one
Authors: Hartke Klaus , Rauschen Frank
Published: February 2015

The titanocene complex 1b reacts with triethyl and trimethyl phosphite to yield the phosphonoesters 3a,b, which exist in solution as a mixture of two interconvertable conformers. The titanocene complex la is alkylated by trimethyloxonium tetrafluoroborate to form the 1,3-dithiolium tetrafluoroborate 10. The latter interacts with 9 (the lithium salt of 3a) merely by proton transfer restoring 3a. 9 condenses with aldehydes and ketones in a Horner- Wadsworth-Emmons reaction to give the titanocene complexes 16 as main products and the 4.5-bis(ethylthio)-1,3-dithiole-2-ylidene compounds 17 as byproducts.
Structural Assembly of Rigid Hydroxycarboxylic Acid Frameworks - Solid State Structures of Two Substituted 6-Hydroxy-trans-3-hexenoic Acids
Authors: Berlekamp Martin , Erker Gerhard , Fröhlich Roland
Published: February 2015

5-(1-H ydroxycyclohexyl)-trans -3-pentenoic acid (2a) and 5 -(2 -hydroxy-2 -indanyl)-trans-3-pentenoic acid (2b) both exhibit associated structures in the solid state that contain strictly alternating repetitive -OH / HO2C- hydrogen bonded arrays. The (2a)„ structure is helical, whereas the association of 2b leads to a three dimensional assembly of tube-like (2b)„ structures. In contrast, the related sterically shielded 6,6-diphenyl-6-hydroxy-trans -3-hexenoic acid (2c) exhibits only a conventional carboxylic acid dimer structure in the solid state.
Ein zweikerniger Vanadium(V)-Komplex mit (μ1)- und (μ-μ2:μ2)-gebundenen Hydrazido(2-)-Liganden / A Dinuclear Vanadium(V) Com plex with (μ1)- and (μ-μ2:μ2)-Bonded Hydrazido(2-) Ligands
Authors: Kopka Klaus , Mattes Rainer
Published: February 2015

The title complex was obtained by reaction of guanidinium dioxodipicolinatovanadate(V) and N-methyl-N-phenylhydrazine. According to the single crystal structure analysis the dinuclear anion [(μ-PhNNH)(μ-OCH3){(MePhNN(dipic)V)}2]- with sevenfold coordinated metal centers contains two types of hydrazido ligands. The ligand [MePhNN]2- is terminally bonded, and the VNN unit is linear with extensive electron delocalisation. The V-N and N-N bond lengths are 167.9(5) and 131.9(6) pm, respectively. The bonding of the bridging ligand is of the hitherto unknown μ-μ2:μ2 type, with V-N and N-N bond lengths of 202.5(5) and 136.5(5) pm, respectively. The V(N2)V moiety is not planar. The compound was also characterized by 1H and 51V NMR spectroscopy.