bluuebunny/crossref_metadata_2025 huggingface dataset:
Preparation and Crystal Structure of EuAgGe
Authors: Pöttgen Rainer
Published: February 2015

The title compound was prepared by the reaction of the elemental components in a tantalum tube. EuAgGe (single crystal. X-ray, Imma, a = 467.0(1), b = 740.0(1), c = 798.1(1) pm, V = 0.2758(1) nm3, Z = 4, wR2 = 0.0371, 474 F2 values and 13 variables) crystallizes with the orthorhombic structure of CeCu2. The europium atoms occupy the cerium positions, while the silver and germanium atoms are randomly distributed on the copper positions. The crystal structure of EuAgGe is discussed together with the structures of EuAg2 and EuAuGe.
A Fluorine-Containing Cryptand for the Complexation of Anions and the Utility of 19F NMR Spectroscopy for the Determination of Host-Guest Association
Authors: Plenio Herbert , Diodone Ralph
Published: February 2015

The first fluorine-containing cryptand F3-TREN 4 for the complexation of anions was prepared in the 3 + 2-condensation reaction of 2-fluoro-1,3-phthalaldehyde 3 with tris(2-aminoethyl) amine and subsequent reduction with NaBH4. Upon incorporation of anionic guests 4 ·6HClO4 experiences shifts of its 19F NMR resonances and thus demonstrates the advantages of studying host-guest association by 19F NMR spectroscopy.
Amphiphilic Carbohydrate-Based Mesogens, 11 Synthesis of Mesogenic 1-AIkylthio-1-deoxy-D-galactitols by Glycoside Reduction
Authors: Dahlhoff Wilhelm V. , Radkowski Karin , Riehl Klaus , Zugenmaier Peter
Published: February 2015

Alkyl-1-thio-α/β-D-gaIactopyranosides (hexyl-dodecyl, 1a - g ) have been O-diethylborylated and then reduced with tetraethyldiboranes(6) in the presence of 9-methylsulfonyloxy- 9-borabicyclo[3.3.1]nonane (MSBBN) catalyst to give 1-alkylthio-1-deoxy-D-galactitols 3a -g after deprotection. 3 exhibit the smectic A liquid crystalline phase on melting.
Arthogalin, a Cyclic Depsipeptide from the Lichen Arthothelium galapagoense
Authors: Huneck S. , Himmelreich U. , Nicholson G.
Published: February 2015

The structure and stereochemistry of arthogalin from the liehen Arthothelium galapagoense has been elucidated as the cyclic depsipeptide 1′.
Tetraphenylphosphoniumtris( tetrasulfido)stannat, (PPh4)2[Sn(S4)3] / Tetraphenylphosphonium Tris-tetrasulfidostannate, (PPh4)2[Sn(S4)3]
Authors: Bubenheim Wilfried , Müller Ulrich
Published: February 2015

PPh4[SnCl3] reacts with Na2S4 in acetonitrile to give the title compound as one of the products. Its crystal structure was determined by X-ray diffraction (R = 0.071 for 3288 reflexions). Crystal data: monoclinic, P21/C, Z = 4, a = 1301.2(3), b = 1139.1(2), c = 3476.2(7) pm, β = 97.82(3)°· (PPh4)2[Sn(S4)3] is isotypic with (PPh4)2[Sn(Se4)3] and contains [Sn(S4)3]2- ions in which three tetrasulfido groups are chelating an octahedrally coordinated tin atom.
Photochemistry of Aqueous Tetrathioantimonate(V)
Authors: Kunkely H. , Vogler A.
Published: February 2015

The electronic spectrum of [SbS4]3- in 10-3 M NaOH displays an absorption band at λmax = 285 nm which is assigned to a ligand-to-metal charge transfer (LMCT) transition. Upon LMCT excitation [SbS4]3- undergoes an intramolecular redox reaction with the formation of [SbS3]3- and elemental sulfur (φ = 0.11 at λirr = 333 nm).
Synthese und Kristallstruktur einer mit dem Johillerit verwandten Verbindung CdCu1,5Mg1,5Pb0,5O12 / Synthesis and Crystal Structure of a Johillerite Related Compound CdCu1,5Mg1,5Pb0,5O12
Authors: Münchau S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of CdCu1.5Mg1.5Pb0.5V3O12 have been prepared in closed steel tubes using V2O5 as a flux. The orange crystals show monoclinic symmetry, space group C6
2h-C2/c, a = 12.417(5), b = 12.983(6), c = 6.911(3) Å , β = 113.02(1)°, Z = 4. CdCu1.5Mg1.5Pb0.5V3O12 reveals a relationship to the Johillerite type, but it is characterized by an additional point position for cadmium, situated between the square planar CuO4 polygons of the Johillerite structure.
Kristallstrukturuntersuchung an einem bismuthaltigen Hollandit: Bi1.9CU4V4O16 / Crystal Structure Investigation of the Bismuth Containing Hollandite: Bi1.9Cu4V4O16
Authors: Feldmann J. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Bi1.9Cu4V4O16 have been prepared by quenching of CO2-LASER heated samples. They were investigated by X-ray techniques. The compound crystallizes with tetragonal symmetry, space group C5
4h-I4 /m , a = 9.945(2) Å , c = 2.915(3) Å, Z = 1, and is isotypic to the mineral Hollandite. Bi1.9Cu4V4O16 is the first Hollandite with a statistical distribution of vanadium and copper in the network of octahedra. Calculations of the Coulomb terms of lattice energy led to a distance of bismuth to the lone pair of 1.07 Å. Considering the lone pair as part of the coordination sphere of Bi3+ a square pyramidal polyhedron is obtained.
Ein Titan-Tantaloxid mit TiII: Ti0,33 Ta0,67O2 (TiTa2O6) / A Titanium Tantalum Oxide of TiII: Ti0,33 Ta0,67O2 (TiTa2O6)
Authors: Peters E. , Müller-Buschbaum Hk.
Published: February 2015

Black single crystals of Ti0.33Ta0.67O2 have been prepared by CO2-LASER techniques heating a mixture of TiO and Ta2O5 to T > 2000 °C. The titanium tantalum oxide crystallizes with tetragonal symmetry, space group D14
4h -P42/mnm, lattice constants a = 4.7344(6) Å c = 3.0504(2) Å, Z = 2. Ti0.33Ta0.67O2 represents the compound TiTa2O6 with rutile structure because of the statistical distribution of Ti2+ and Ta5+. The composition of rutile-type compounds is discussed in more general terms.
EuPdGe - a New Germanide with EuNiGe Type Structure
Authors: Pöttgen Rainer
Published: February 2015

The title compound was prepared from the elemental components in a tantalum tube at 1070 K and investigated by X-ray diffraction of both powder as well as single crystals. The crystal structure was refined from four-circle diffractometer data: P21/n, a = 618.1(1), b = 613.6(1), c = 743.9(1) pm, β = 109.40(1)°, V = 0.2661(1) nm3, Z = 4, wR2 = 0.0536 for 1564 F2 values and 29 variables. EuPdGe crystallizes with the EuNiGe type structure. Both Pd and Ge atoms in EuPdGe have three germanium or palladium neighbors, respectively. They form two-dimensionally infinite [PdGe] polyanions which consist of corrugated 4.82 nets. These polyanions are separated by the europium atoms.
Komplexe Alkalimetall-carbonat-hydrogencarbonate mit fünffach koordiniertem Zink: NaA2{Zn2[H(CO3)2](CO3)2(H2O)2} mit A = K, Rb / Complex Alkalimetal-carbonates-hydrogencarbonates with Penta-Coordinated Zinc: NaA2{Zn2[H(CO3)2](CO3)2(H2O)2] with A = K, Rb
Authors: Zheng Yue Qing , Adam Arnold
Published: February 2015

The new alkalimetal-hydrogenbis(carbonato)-bis(carbonato)complexes with penta-coordinated zinc atoms, NaA2{Zn2[H(CO3)2](CO3)2(H2O)2} with A = Kor Rb, crystallize in the monoclinic system, P21/n (no. 14), Z = 2 with a = 1057,9(1), b = 1102,2(1), c = 514,9(1) pm, β = 92,94(1)°, VEZ = 599,6(2) · 106 pm3, R = 0,052, Rw = 0,029 for the potassium compound and with a = 1068,2(2), b = 1131,6(4), c = 518,6(1) pm, β = 92,07(1)°, VEZ = 626,4(4)·106 pm3, R = 0,050, Rw = 0,028 for the rubidium compound. These compounds are the first to be structurally characterized with a simultaneous presence of discrete [H(CO3)2]3-and CO3
2- anions.

The crystal structure of the isostructural compounds contains two-dimensional infinite {Zn2[H(CO3)2](CO3)2(H2O)2} layers parallel [1 0 1] with zinc coordinated in a slightly distorted trigonal-bipyramidal geometry. The layers are held together by hydrogen bonds from water molecules to oxygen atoms of the carbonato groups in adjacent layers. Potassium or rubidium atoms are located between the layers, and sodium atoms in smaller vacancies within the layers. The hydrogen bond of the [H(CO3)2]3- anion is very short, O···O: 247,4(2) pm (K) and 246,9(5) pm (Rb). The carbonate groups in both compounds exhibit significant deviations from D3h symmetry in accordance with the vibrational modes observed in the IR spectra. The thermal behaviour of the potassium compound is also reported.
Synthesis, Properties and Crystal Structure of Di(phthalocyaninato)lanthanum(III), a Partially Oxidized Semiconductor
Authors: Ostendorp Guido , Homborg Heiner
Published: February 2015

[La(Pc)2] · CH2Cl2 is prepared by anodic oxidation of (nBu4N)[La(Pc2-)2] as slightly soluble black needles crystallizing in the orthorhombic space group Pnma with a = 28.365(5). b = 22.935(3). c = 8.026(3) Å, Z = 4. The La atom is in the center of an antiprismatic coordination polyhedron formed by the eight isoindole N atoms of the two staggered Pc ligands. The mean value of the La -Niso bond distance is 2.51 Å. One Pc ligand is quasi planar, the other is convex. The electronic absorption spectra and IR and resonance Raman spectra of the partially oxidized LaIII diphthalocyanine are reported and compared with those of the protonated complex H[La(Pc2-)2].
Phosphanimin-Komplexe von Mangan(II)halogeniden. Die Kristallstrukturen von [MnCl2(Me3SiNPEt3)]2, [Mnl2(Me3SiNPEt3)2] und [MnI2(Me2Si(NPEt3)2)] / Phosphaneimine Complexes of Manganese(II)halides. The Crystal Structures of [MnCl2(Me3SiNPEt3)]2, [Mnl2(Me3SiNPEt3)2] and [MnI2(Me2Si(NPEt3)2)]
Authors: Mai Hans-Joachim , Wocadlo Sigrid , Massa Werner , Weller Frank , Dehnicke Kurt , Maichle-Mössmer Cäcilia , Strähle Joachim
Published: February 2015

The phosphaneimine complexes [MnCl2(Me3SiNPEt3)]2 (1) and [MnI2(Me3SiNPEt3)2] (2) have been prepared by the reaction of Me3SiNPEt3 with MnCl2 and Mnl2, respectively. Thermal decomposition of 2 leads to the chelate complex [MnI2(Me2Si(NPEt3)2)] (3) by cleaving SiMe4. The complexes are characterized by IR spectroscopy and by crystal structure determinations.

1: Space group P21/c, Z = 4, structure solution with 5062 observed unique reflections, R = 0.047. Lattice dimensions at -55 °C: a = 1175.8(5), b = 1634.5(2), c = 1740.2(8), β = 99.58(2)°. 1 forms dimeric molecules via chloro bridges and a cis-arrangement of the Me3SiNPEt3 donor molecules with Mn-N bond lengths of 210.4(5) and 208.2(4) pm.

2: Space group P 41212, Z = 4, structure refinement with 1633 independent reflections, 1072 observed unique reflections, R = 0.053. Lattice dimensions at -60 °C: a = b = 949.5(1), c = 3345.2(7) pm. 2 forms monomeric molecules with tetrahedrally coordinated Mn atoms and Mn-N bond lengths of 220.7(13) pm.

3: Space group P21/c, Z = 4, structure refinement with 8419 independent reflections, 4584 observed unique reflections, R = 0.047. Lattice dimensions at 20 °C: a = 1343.3(1), b = 2508.2(2), c = 1535.1(1) pm, β = 91.742(5)°. 3 forms monomeric molecules with the [Me2Si(NPEt3)2] ligand bound in a chelating fashion with Mn-N bond lengths of 212.9 pm in average.
Ubergangsmetallkomplexe mit Schwefelliganden, CIX. Synthese und Reaktivität von meso-[Ru(L)('buS5')]-Komplexen mit L = NO+, CO, PR3 (R = Me, Ph, Cy), pyr, CN-, N2H4, NH2NHR (R = Me, Ph), NH2NMe2, NH3, NH2Ph, NHEt2 ('buS5' - H2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)di-ethylsulfid) / Transition Metal Complexes with Sulfur Ligands, CIX. Synthesis and Reactivity of meso-[Ru(L)('buS5')] Complexes with L = NO+, CO, PR3 (R = Me, Ph, Cy), pyr, CN-, N2H4, NH2NHR (R = Me, Ph), NH2NMe2, NH3, NH2Ph, NHEt2 ( 'buS5' - H2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide)
Authors: Sellmann Dieter , Rohm Christine , Moll Matthias , Knoch Falk
Published: February 2015

In a search of transition metal complexes with sulfur dominated coordination spheres and free coordination sites for the binding of small molecules, [Ru(L)('buS5')] complexes with the sterically demanding pentadentate thioether-thiolate ligand 'buS5'2- ( 'buS5'2- = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide(2-)) have been synthesized.

Reaction of [RuCl3(NO)(PPh3)2] with 3,5-di(t-butyl)benzene-1,2-dithiolate, ′buS2'2-, yields the 16 electron complex [Ru(NO )('buS2')2]- which is isolated as the NBu4
+-salt, 1. According to the NMR spectra, 1 contains a two-fold axis or a mirror plane. Alkylation of 1 with bis(β-bromethyl)sulfide under reflux leads stereoselectively to meso-[Ru(NO)('buS5')]Br, [2]Br. Reaction of [2]Br with LiBEt3H yields the barely soluble binuclear complex [Ru('buS5')]2, 3, with [Ru('buS5')Ru(NO)('buS2')('buS2'- C2H4SH)], 4, as a by-product. 4 ·THF, 4a, has been characterized by X-ray structure analysis.

Reactions of 3 with σ-π- and σ-ligands yield mononuclear meso-[Ru(L)('buS5')] complexes which have been isolated and characterized with L = CO, PMe3, PPh3, PCy3, pyr, CN-, 5 - 10, NH2NHPh, NH2NHMe, NH2NMe2, NH2Ph und NHEt2, 13-17. Complexes 5 -10 are stable compounds. Complexes 13-17, however, are sensitive towards oxidation and/or substitution. Coordination of L = N2H4 and NH3 to 3 leads to insoluble [Ru(L)('buS5')]x complexes.
In2.24(NCN)3 and NaIn(NCN)2: Synthesis and Crystal Structures of New Main Group Metal Cyanamides
Authors: Dronskowski Richard
Published: February 2015

Single crystals of In2.24(NCN)3 and NaIn(N CN)2 can be synthesized from a reaction between InBr and NaCN at 400 °C, followed by chemical transport at 400-500 °C. The X-ray crystal structure determinations of In2.24(NCN)3 (rhombohedral R3̄c, a = 606.09(4), c = 2884.4(2) pm, Z = 6) and NaIn(NCN)2 (orthorhombic Cmcm, a = 961.30(6), b = 716.84(5), c = 603.65(4) pm, Z = 4) reveal ionic layer structures built from sheets of cationic and anionic (cyanamide) motifs. While NaIn(NCN)2 contains In3+ and Na+ ions, In2.24(NCN)3 is a mixedvalence compound, incorporating a monovalent In+ ion besides trivalent indium. The NCN2- units of both In2.24(NCN)3 and NaIn(NCN)2 reflect perfect D∞h point group symmetry within the limits of experimental accuracy. Furthermore, an evaluation of all presently available crystallographic data on metal cyanamide crystal structures manifests that there is no evidence for a non-centrosymmetric description of any of these. Likewise, we propose an alternative centrosymmetric structural model for lead cyanamide, PbNCN, and question the evidence of the unsymmetrical, non-D∞h shaped cyanamide anion in the latter structure.
Koordinationschemie π-gebundener Cyclopentadienyl-Chalcogeno-Ether, II. Palladium(II)- und Platin(II)-Komplexe von [C5(SMe)5]Mn(CO)3, [C5Cl2(SMe)3]Mn(CO)3 und [C5Cl2(SMe)2(PPh2)]Mn(CO)3./ Coordination Chemistry of π-Bonded Cyclopentadienyl Chalcogeno Ethers, II. Palladium(II) and Platinum(II) Complexes of [C5(SMe)5]Mn(CO)3, [C5Cl2(SMe)3]Mn(CO)3 and [C5Cl2(SMe)2(PPh2)]Mn(CO)3
Authors: Sünkel Karlheinz , Blum Adrian
Published: February 2015

Treatment of the cymantrene thioether [C5(SMe)5]Mn(CO)3 (IIb) with Na2PdCl4 or K2PtCl4 yields the bimetallic chelate complexes [C5(SMe)5]Mn(CO)3*MCl2 (M = Pd (2) or Pt (3)). Similarly, the S,P-chelate complexes [C5Cl2(SR)2(PPh2)]Mn(CO)3*PdCl2 (R = Me (4a), Ph (4b)) can be obtained from the corresponding mononuclear cymantrene derivatives and Na2PdCl4 or (PhCN)2PdCl2. Analysis of the 1H NMR spectra only allows for the Pt complex the identification of one meso form, which seems to be favoured by 2:1, together with the D,L forms. The crystal structures of [C5Cl2(SMe)3]Mn(CO)3*PdCl2(1, C11H9Cl4MnO3PdS3, triclinic, P1̄, a = 7.617(3) Å , b = 10.528(4) Å ,c = 12.473(5) Å , α = 72.95(3)°, β = 84.94(3)°, γ = 88.75(3)°, V = 952.6(6) Å3, Z = 2), 2 (C13H15Cl2MnO3PdS5, orthorhombic, Pn21/c, a = 12.739(5) Å , b = 9.992(3) Å , c = 16.884(5) Å , V = 2149(1) Å, Z = 4), and 4 (C23H18Cl6MnO3PPdS2, monoclinic, P21/c, a = 13.199(4) Å , b = 29.198(11) Å , c = 15.921(7) , β - 101.41(3)°, V = 6015(4) Å3, Z = 8) are reported and compared with each other and other bimetallic metallocene phosphine and thioether derivatives.
Synthese dreizähniger Phosphanliganden RP[(CH2)n]2 (Y = OR′ oder CO2R′, n = 1 oder 2) sowie einiger zweizähniger chiraler Phosphane R2PCH(CH3)CO2Me / Synthesis of Tridentate Phosphine Ligands RP[(CH2)nY]2 (Y = OR′ or CO2R′, n = 1 or 2) and Some Bidentate Chiral Phosphines R2PCH(CH3)CO2Me
Authors: Wolfsberger Werner , Bank Jürgen , Werner Helmut
Published: February 2015

The bis(γ-alkoxypropyl)phosphines RP(CH2CH2OR′)2 1-4 were prepared by the reaction of RPLi2 (generated by lithiation of RPH2 with n-BuLi) with ClCH2CH2OR′. Deprotonation of the alkyl group R of RPH2 by n-BuLi and other side reactions leading preferably to diphosphines of the formula R [R′O(CH2)2]PP[(CH2)2OR′]R are responsible for the low yields of 1-4. The bis(propionate) analogues PhP(CH2CH2CO2R′)2 5 and 6 were readily accessible by hydrophosphination of methyl and ethyl acrylate with phenylphosphine, whereas the corresponding compounds RP(CH2CO2R′)2 7 -14 were best prepared by desilylation of RP(SiMe3)2 with C1CH2CO2R′. A similar reaction between R2PSiMe3 and the commercially available R - (+) - ClCH(CH3)CO2Me resulted in the formation of the chiral phosphinoesters R2PCH(CH3)CO 2Me 15-17. In the case of 15 and 16 partial racemation took place during the preparation, whereas 17 could be isolated in an enantiomerically pure form.
Two Modifications of Hg5Re2O10
Authors: Schriewer-Pöttgen Marietta S. , Jeitschko Wolfgang
Published: February 2015

The previously reported mercury perrhenate Hg5Re2O10, prepared hydrothermally, has now been obtained by reaction of HgO with the mercury(II) metaperrhenate Hg(ReO4)2 in sealed silica tubes. A second modification of this compound can be obtained by reaction of elemental mercury with Hg(ReO 4)2 also in sealed silica tubes. Its crystal structure has been determined from single-crystal X-ray data: P21/c, a - 861.5(1), b = 1200.9(2), c = 1203.9(2) pm, β = 97.15(1)°, Z = 4, R = 0.024 for 1733 structure factors and 105 variables. Both modifications may be represented by the formula Hg2+-2Hg2O - 2ReO4-, indicating that mercury occurs in oxidation states I and II. In both modifications the mercury and some oxygen atoms form two-dimensionally infinte, puckered, cationic nets of the composition (Hg2+-2Hg2O)n , which are separated by the ReO4- tetrahedra. In the modification reported earlier the mercury oxygen nets consist of condensed 16-membered rings, while the nets of the present modification contain 10- and 22-membered rings.
Synthese eines Pyrochlors mit TiII: (Ta0.67TiII
0.33)2Sm2O7/ Synthesis of a Pyrochlore Containing TiII: (Ta0.67TiII
0.33)2Sm2O7
Authors: Peters E. , Müller-Buschbaum Hk.
Published: February 2015

High temperature reactions using a CO2-LASER led to a TiII containing phase of the composition (Ta0.67TiII
0.33Sm2O7, space group O7
h - Fd3̄m (No. 227), a = 10.385(2) Å . The oxidation state TiII which is stabilized by incorporation into the cubic pyrochlore structure was proved by the statistical occupation of the 16c point position by a Ta:Ti ratio of 2:1.
Reindarstellung und Kristallstruktur von Lithiumnitriddibromid, Li5NBr2 / Preparation and Crystal Structure of Lithium Nitride Dibromide, Li5NBr2
Authors: Marx Rupert , Mayer Hans Michael
Published: February 2015

Single phase Li5NBr2 was prepared by the reaction of Li3N and dry, OH-free LiBr under inert gas at 430 °C. In the quasi-binary system Li3-2xN1-xBrx, Li5NBr2 is the second most nitride rich compound after Li10N3Br. Following unit cell indexing using laboratory X-ray powder data the previously unknown structure of Li5NBr2 was solved from neutron powder diffraction data recorded at the flat-cone and powder diffractometer E2 at the rebuilt reactor BERII in Berlin. The title compound crystallizes in the orthorhombic space group Immm (No. 71), a = 603.79(4), b = 1181.3(1), c = 390.14(3) pm with two formula units per unit cell. The L i-N -sublattice comprises linear chains of vertex sharing Li6N-octahedra which are aligned along the short c-axis and are separated by chains of bromine atoms. The N-Br arrangement may be regarded as an ordered AX2 variant of a cubic close packing involving two kinds of atoms. Lithium atoms occupy the tetrahedral holes formed by one nitrogen and three bromine atoms, as well as the N - N edges of the N2Br2 tetrahedra.
Synthese und Struktur des Au12Pd-Clusters [(Ph3PAu)8(AuCl)4Pd] / Synthesis and Structure of the Au12Pd Cluster [(Ph3PAu)8(AuCl)4Pd]
Authors: Laupp Martin , Strähle Joachim
Published: February 2015

Photolysis of a mixture of (Ph3P)2Pd(N3)2, Ph3PAuN3 and PhsPAuCI yields [(Ph3PAu)8(AuCl)4Pd] after chromatographic separation. The cluster crystallizes in the triclinic space group P1̄ with a = 1675.45(8), b = 1870.57(6), c = 2673,15(9) pm, α = 82.30(3)°, β = 75.90(3)°, γ = 73.02(3)°, Z = 2. The twelve gold atoms form an icosahedron with the Pd atom in its center, and distances Pd-Au between 271.0(3) and 278.2(4) pm. The Au-Au distances range from 277.1(2) to 298.3(2) pm.
Die Synthese und Struktur von Clusteraziden: A4[Nb6Cl12(N3)6](H2O)2 mit A=Rb. Cs / Synthesis and Structure of the Cluster Azides: A4Nb6Cl12(N3)6](H2O)2 with A=Rb, Cs
Authors: Reckeweg Olaf , Meyer H.-Jürgen
Published: February 2015

The new compounds A4[Nb6Cl12(N3)6](H2O)2 (A = Rb, Cs) were synthesized from In4[Nb6Cl12Cl6] by substituting six terminal Cl ligands and the In+ ions in methanolic solution. An X-ray structure refinement was performed on single-crystal data of Rb4[Nb6Cl12(N3)6](H2O)2 (1) (space group P1̄, Z = 1, a = 912.5(1) pm, b = 937.2(1) pm, c = 1062.0(1) pm, α = 96.88(2)°, β = 101.89(1)°, γ = 101.44(2)°) and Cs4[Nb6Cl12(N3)6](H2O)2 (2) (space group PI, Z = 1, a = 920.9(5) pm, b = 947.9(7) pm, c = 1091.8(7) pm, α = 96.89(6)°, β = 103.35(5)°, γ = 101.60(5)°. Each of the centrosymmetric [Nb6Cl12(N3)6]4- ions of the isotypic compounds contains six terminal azide groups at the corners of the octahedral niobium cluster (d̄Nb-N = 226(1) pm (1), 225(1) pm (2), bond angles Nb-N-N 120-127°). The [Nb6Cl12(N3)6]4- ions are linked via Rb-N and Rb-Cl interactions of the Rb+ ions to form a three-dimensional structure. Crystals of the compounds react explosively on heating or mechanical pressure.
Notizen: Darstellung und Kristallstruktur von Cs3ClO / Preparation and Crystal Structure of Cs3ClO
Authors: Feldmann Claus , Jansen Martin
Published: February 2015

The preparation and crystal structure of Cs3ClO (a = 9,442(6), b = 4,452(2), c = 16,344(10) Å ) is reported. In contrast to other compounds M3XO (M = alkali metal; X = halide, auride) Cs3ClO does not crystalize as an anti perovskite or a related structure, but in the anti-NH4CdCl3 type of structure.
Notizen: Zur Struktur des Diazadimethylstannetidinderivats [(CH3)2Sn(NC(CH3)3)2GaCH3]2/ The Structure of the Diazadimethylstannetidine Derivative [(CH3)2Sn(NC(CH3)3)2GaCH3]2
Authors: Hausen Hans-Dieter , Kuhnle Rainer , Weidlein Johann
Published: February 2015

The title compound Me2Sn(NtBu)2GaMe (Me = CH3, tBu = C(CH3)3) is formed in only low yield by the reaction of diazadistannetidine [Me2SnNtBu]2 with galliumtrimethyl. It is dimeric in the solid state and crystallizes in the monoclinic space group P21/n with the cell parameters a = 923.4(1), b = 1832.8(2), c = 972.9(1) pm, β = 111.24(1)°, and Z = 2. The centrosymmetric dimer (point symmetry Q ) consists of three consecutive edge-sharing four-membered rings; the central Ga2N2 unit is formed by two Ga ← N donor-acceptor bonds of 203.7 pm. The two SnN2Ga rings and the central ring form angles of ± 113.7°. The compound is very similar to, but not isotypic with the homologous In/Si compound [Me2Si(NtBu)2InMe]2 [5],
Notizen: New Colchicine and Homoaporphine- N-Oxide Alkaloids from Colchicum Ritchii: The First Homoaporphine TV-Oxide Found in Nature
Authors: Abu Zarga Musa H. , Al-Qawasmeh Raed A. , Sabri Salim S. , Al-Tel Taleb H. , Voelter Wolfgang
Published: February 2015

From Colchicum ritchii R.Br (Liliaceae) of Jordanian origin, the new colchicine-type alkaloid (-)-O -methylspeciosine (1), the known alkaloid (-)-speciosine (2) and two new homoaporphine- N-oxides are isolated and characterized: (+)-kreysigine-N-oxide (5) and (+)-szovitsamine-N-oxide (6). Additinally, two photoisomers of the cholchicine alkaloids are identified after their isolation and their 1H and 13C NMR data reinvistigated: β-lumicornigerine (3) and β-lumidemecolcine (4).
Untersuchungen an Polyhalogeniden, XX [1] Darstellung und Kristallstruktur von Tetra(methyltriphenylphosphonium)docosaiodid (MePh3P)4I22 / Studies of Polyhalides, XX [1] Preparation and Crystal Structure of Tetra(methyltriphenylphosphonium)docosaiodide (MePh3P)4I22
Authors: Tebbe Karl-Friedrich , Farida Taraneh
Published: February 2015

The new compound (MePh3P)4I22 has been prepared by the reaction of Ph3MePI with iodine in a mixture of methanol and dichloromethane. It crystallizes in the triclinic space group P1̅ with a = 1018.4(3), b = 1333.0(4), c = 2042.9(6) pm, a = 88.56(2), β = 78.05(2), γ = 76.03(2)° and Z = 1. The crystal structure has been refined to RF = 0.0487 for 5525 reflections. It may be described as a layer-like packing of cations [CH3(C6H3)3P]+ and anions I22
4- divided in one I12
2- and two I5
- groups. The central I12
2- anion with point symmetry Q consisting of two L-shaped pentaiodide groups and a bridging iodine molecule is completed by two further end-on bonded pentaiodide ions with a rather short distance of 366.7(2) pm to the weakly bonded and nearly isolated docosaiodide ion.
Synthese und Kristallstruktur der ersten zinkhaltigen Pyroborate Ni1,5Zn0,5(B2O5) und Co1,5Zn0,5(B2O5) / Synthesis and Crystal Structure of the First Zinc Containing Pyroborates Ni1,5Zn0,5(B2O5) and Co1,5Zn0,5(B2O5)
Authors: Busche Silke , Bluhm Karsten
Published: February 2015

The first zinc containing pyroborates Ni1,5Zn0,5(B2O5) (A ) and Co1,5Zn0,5(B2O5) (B) were prepared by using a B2O3 flux technique. Single crystals were investigated by X-ray diffraction and showed triclinic symmetry, space group Ci
1-P1̅. The structures are isotypic to Co2(B2O5) with the lattice parameters (A ) a = 331.28(6), b = 613.87(11), c = 922.2(2), α = 104.067(11) °, β = 90.672(13) °, γ = 92.413(12) ° and (B) a = 315.89(2), b = 612.84(6), c = 927.72(6), α = 104.103(7) °, β = 91.020(6) °, γ = 92.540(7) °, Z = 2. All metal point positions show an octahedral oxygen coordination and a partly statistical distribution of Zn2+ and Ni2+ or Co2+, respectively. Isolated nearly planar B2O5 units connect ribbons consisting of edge sharing metal octahedra.
Zur Synthese und Kristallstruktur von Zinkboratoxiden mit isolierten, trigonal planaren BO3-Baugruppen: Zn5Mn(BO3)2O4 und ZnFe(BO3)O / Synthesis and Crystal Structure of Zinc Borate Oxides Containing Isolated Trigonal Planar BO3 Units: Zn5Mn(BO3)2O4 and ZnFe(BO3)O
Authors: Busche Silke , Bluhm Karsten
Published: February 2015

Single crystals of the new compounds Zn5Mn(BO3)2O4 (A ) and ZnFe(BO3)O (B) were prepared by using a B2O3 flux technique. Zn5Mn(BO3)2O4 is isostructural with Ni5Ti(BO3)2O4 and ZnFe(BO3)O is isotypic with the mineral warwickite. X-ray investigations on single crystals led to (A ) space group D9
2h -Pbam, a = 926.41(10), b = 1236.67(8), c = 304.55(3) pm, Z = 2, and (B) space group D16
2h-Pnma, a = 924.62(4), b = 314.1(10), c = 935.3(2) pm, Z = 4. The structure of Zn5Mn(BO3)2O4 (A ) contains four octahedrally coordinated metal sites, one of these statistically occupied by Zn2+ and Mn4+. In the structure of ZnFe(BO3)O the ions Zn2+ and Fe3+ occupy statistically both distorted octahedral sites. Both structures contain isolated BO3 units and oxygen that is not coordinated to boron.
[Ni2(SC4H9)6]2-, ein neuartiger zweikerniger Nickel-Thiolato-Komplex mit kantenverknüpften NiS4-Tetraedern und [Ni(SC6H4SiMe3)4]2-, ein strukturchemisch verwandtes einkerniges Komplexion / [Ni2(SC4H9)6]2-, a Novel Binuclear Nickel-Thiolat Complex with NiS4 Tetrahedra Sharing Edges and [Ni(SC6H4SiMe3)4]2-, a Structurally Related Mononuclear Complex Ion
Authors: Müller Arnd , Henkel Gerald
Published: February 2015

Reaction of nickel(II) chloride with sodium or potassium tert-butane thiolate in acetonitrile affords the isotypical compounds [Ni2(StC4H9)6]Na2 ·4MeCN (1) and [Ni2(StC4H9)6]K2 · 4MeCN (2), respectively. Crystal data: 1: a = 9.859(3), b = 11.877(3), c = 19.675(5) Å , β = 96.11(2)°, space group P21/n, Z = 2:2: a = 9.854(2), b = 11.915(3), c = 20.558(5) Å , β = 99.62(2)°, space group P21/n, Z = 2. The structures were refined to R = 0.0599 (1) and 0.0562 (2), respectively. Both compounds contain the complex ion [Ni2(SrC4H9)6]2- (3), which is not only the first example of a tetrahedral nickel complex with alkane thiolate ligands, but also the first polynuclear nickel complex containing tetrahedral NiS4-units sharing a common edge. Reaction of nickel(II) chloride and sodium (2-trimethylsilyl)thiophenolate in acetonitrile leads to [Ni(SC6H4SiMe3)4]2- (5) with tetrahedral stereochemistry. The mononuclear complex ion is isolated aso [Ph4P]2[Ni(SC6H4SiMe3)4] · 5MeCN (4) with a = 13.771(2), b = 14.163(2), c = 25.873(4) Å , a = 77.44(1), β = 75.13(1), γ = 72.46(1)°, space group P1̅ and Z = 2. The final refinement converged to R = 0.0445.
Crystal Structure and Properties of Ti2In5
Authors: Pöttgen Rainer
Published: February 2015

Ti2In5 was prepared from the elemental components in a tantalum tube at 970 K and investigated by X-ray diffraction of powders as well as of single crystals. The crystal structure was refined from four-circle diffractometer data: P4/mbm, a = 1000.35(5) pm, c = 299.77(2) pm, V = 0.29998(5) nm3, Z = 2, wR2 = 0.0367 for 369 F2 values and 15 variables. Ti2In5 crystallizes with the Mn2Hg5 type structure. The indium atoms form consecutive planar layers which may be considered as a tesselation of triangles, squares, and pentagons. The titanium atoms occupy the pentagonal prismatic voids between these layers. Ti2In5 is Pauli paramagnetic and a good metallic conductor with a specific resistivity of 50 μΩcm at room temperature. The compound was previously described with the composition “Ti3In4”.
Chiral Synthesis of (R)-(-)(5Z)-4-Hydroxy-5-tetradecenoic Acid-4-lactone
Authors: Salas-Reyes V.
Published: February 2015

R -(-)(5Z)-4-hydroxy-5-tetradecenoic acid-4-lactone has been synthesized from D-glucose as the precursor. Regio and stereoselective transformations of hydroxyl groups as well as protection-deprotection protocols provide a novel route to this compound.
NOTIZEN: 2-Trifluoroacetyl-1-methyl-1, 2,3,4- tetrahydro-β-carboline, a Gaschromatographically Useful Derivative of the Mammalian Alkaloid Eleagnine
Authors: Peters Karl , Peters Eva-Maria , Bringmann Gerhard , God Ralf
Published: February 2015

The title compound was prepared by N -trifluoroacetylation of 1-methyl-1,2,3,4-tetrahydro- β-carboline (eleagnine, 3) using trifluoroacetic anhydride. It crystallizes from methanol in the orthorhombic system, space group Pbca; a = 1334.5(2), b = 1587.0(2) and c = 1237.5(1) pm. In the crystal the molecules are connected via hydrogen bonding to form zigzag chains parallel [001],
Synthesis and X-Ray Crystal Structure of a Polymeric Iodobismuthate Anion
Authors: Carmalt Claire J. , Farrugia Louis J. , Norman Nicholas C.
Published: February 2015

The reaction between [CH2=C(C6H4-4-NO2)CH2NMe3]I and eight equivalents of BiI3 in thf (tetrahydrofuran) afforded, after work-up, dark red crystals of the compound [CH2=C(C6H4-4-NO2)CH2NMe3]n[{Bi2I7}n], the structure of which was established by X -ray crystallography and shown to contain a polymeric iodobismuthate anion. An analogous reaction between [CH3(CH2)2COS(CH2)2N(CH3)3]I and eight equivalents of BiI3 afforded orange crystals of the compound [CH3(CH2)2COS(CH2)2N(CH3)3]4[Bi4I16] which was shown by X -ray crystallography to contain the tetranuclear [Bi4I16]4- anion.
Ubergangsmetallkomplexe mit Schwefelliganden, CXVI. Carbonylkomplexe mit [MoS4]-Zentren in mittleren und hohen Oxidationsstufen / Transition Metal Complexes with Sulfur Ligands, CXVI. Carbonyl Complexes with [MoS4] Centers in Medium and High Oxidation States
Authors: Sellmann Dieter , Kremitzl Hans-Jörg , Knoch Falk , Moll Matthias
Published: February 2015

In the quest of suitable precursors for the synthesis of Mo(IV) carbonyl complexes the compounds [Mo(CO)2(PCy3)(′buS4′)] (3) and [Mo(CO)2(PCy3)(′S4′)] (4) [′buS4′2- = 1,2-bis(2-mercapto-3,5-di-t-butyl-phenylthio)ethane(2-); ′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)] were synthesized via CO substitution from [Mo(CO)3(′buS4′)] (13) and [Mo(CO)3(′S4′)](14). 4 was characterized by X -ray structure analysis and exhibits, due to the sterically demanding PCy3, a strongly compressed [Mo(′S4′)] core.

Intramolecular redox reactions of 3, 4 and, in addition, [Mo(CO)2(PMe3)(′S4′)] (15) leading to thioether dealkylation via loss of C2H4 from the ′RS4′2- ligands and Mo(II)→ Mo(IV) oxidation yielded the Mo(IV) complexes [Mo(CO)(PCy3)(′buS2′)2] (6), [Mo(CO)-(PCy3)(′S2′)2] (7) and [Mo(CO)(PMe3)(′S2′)2] (8) [′buS2′)2]= 3,5-di-t-butyl-1,2-benzenedithiolate(2-), ′S2′2- = 1,2-benzenedithiolate(2-)]. Depending on the nature of the phosphines and the R substituents of the ′RS4′2- ligands, the syntheses required very specific reaction conditions ranging from thermolysis in vacuo to heating in boiling THF. For instance, [Mo(CO)2(PCy3)(′S4′)] (4) decomposes in CH2Cl2 solution even at ambient temperature yielding the binuclear Mo(II) complex [Mo(CO)(μ-′S4′)]2 (10), which was characterized by an X-ray structure determination. Thermolysis of 4 in vacuo at 80 °C , however, results in the formation of the Mo(IV) complex 7. By optimizing the reaction conditions preparative amounts of the prototype [Mo(CO)2(′buS2′)2] (1) have now also become accessible.

These findings can be rationalized in part on the basis of results obtained from cyclic voltammetry. The redox potentials of the Mo(IV) complexes are drastically shifted by about -0.5 V per substitution of CO by PR3, and the substitution of ′S2′2- by ′buS2′2- ligands causes a negative shift in the range from 0.03 V to 0.18 V.

The results of IR spectroscopical m onitoring the substitution of CO by PMe3 in [Mo(CO)(PMe3)(′RS2′)2] yielding [Mo(PMe3)2(′RS2′)2] suggested an associative substitution mechanism via the intermediate [Mo(CO)(PMe3)2(′RS2′)2]. The formation of [Mo(CO)-(PMe3)(′buS2′)2] (12) from [Mo(PMe3)2(′buS2′)2] (9) and CO under standard conditions further shows that the direct coordination of CO to Mo(IV ) centers is also possible if these centers are surrounded by thiolate donors. The results are discussed with respect to the reactivity of the Mo centers of the FeMo cofactors in nitrogenases.
Magnetic Studies on the 1-D Antiferromagnetic Chains of enH2Mn(Fe)F5
Authors: Frommen C. , Schröder L. , Bentrup U. , Massa W. , Pebler J.
Published: February 2015

Measurements of the 57Fe Mössbauer effect and of magnetic susceptibilities have been performed on the 57Fe doped or pure quasi-1-d antiferromagnetic chain compound enH2MnF5 as a function of temperature. Particular attention was paid to the regions very near the Néel point at TN = 14.5(5) K. The Mössbauer spectra fitted by the Blume-Tjon model show definite relaxation effects, which are attributed to short-range order with temperature-dependent relaxation times. The soliton model of non-linear excitations was applied. Experimental data confirm the predicted exponential temperature dependence of the thermal excitation of moving domain walls. From the activation energy EA/k = 184(5) K and the 1-d exchange energy J/k = -13.6(2) K a local anisotropy energy D/k of -2.4 (3) K was obtained which is smaller than D/k = -3.5 K derived from our single crystal measurements of magnetic susceptibilities. Within the 3-d magnetic ordering the interchain interaction amounts to J′/k ≈ 0.22(4) K (J′/J = 15.8 10-3). A zero-spin reduction ⊿S/S equal to 17% was obtained. 1-d correlations are observed for TN<T< |J|S (S + 1)/k ≈ 78 K, and a crystallographic phase transition at 216 K was indicated in the magnetic properties as well as by DSC and X-ray powder diffraction measurements.
Die Synthese und Kristallstruktur von cobalthaltigen Boratoxiden: Co1,5Ti0,5(BO3)O und Co1,5Zr0,5(BO3)O / Synthesis and Crystal Structure of Cobalt Containing Borate Oxides: Co1.5Ti0.5(BO3)O and Co1.5Zr0.5(BO3)O
Authors: Utzolino Anne , Bluhm Karsten
Published: February 2015

Single crystals of Co1.5Ti0.5(BO3)O (I) and Co1.5Zr0.5(BO3)O (II) were obtained by a B2O3 flux technique. Both compounds crystallize with orthorhombic symmetry, space group D16
2h-Pnma (Nr. 62), I a = 928.1; b = 311.1; c = 940.1 pm; Z = 4 and II a = 949.5; b = 323.42; c = 934.7 pm; Z = 4. The compounds are isotypic to the mineral warwickite. All metal ions are octahedrally coordinated by oxygen ions. The structure contains isolated, trigonal planar BO3 units and oxygen that is not coordinated to boron.
Das AXX′2-Spinsystem: Theoretische Betrachtungen und Beispiele / The AXX′2 Spin System: Theory and Examples
Authors: Dolhaine Hans , Fuhler Rainer , Hägele Gerhard , Kläui Wolfgang
Published: February 2015

Algebraic equations for transition frequencies and intensities are derived for the AXX′2 spin system. In favourable cases the resonance frequency νA and all coupling parameters JAX, JAX′ and JXX′ can be extracted from the A-part of the AXX′2 spectrum. Examples of deceptively simple spectra are discussed.
Ruthenocenophanes
Authors: Herberhold Max , Bärtl Thomas
Published: February 2015

The new dinuclear [1.1]metallocenophanes, bis(dimethylsila)-[1.1]ferrocenophane (2a) and bis(dimethylsila)-[1.1]ruthenocenophane (2b), were synthesized by the reaction of dilithium di(cyclopentadienyl)dimethylsilane with FeCL·2 thf and RuCl2·4 dmso in tetrahydrofuran solution, and compared with the known bis(methylene)-bridged analogues [1.1]ferrocenophane (8a) and [1.1]ruthenocenophane (8b), respectively. A series of mononuclear [n]ruthenocenophanes including 1,1,2,2 -tetramethyl-[2]ruthenocenophane (10b), 1,2 - bis(dimethylsila)-[2]ruthenocenophane (3b), 1,3-bis(dimethylsila)-2-oxa-[3]ruthenocenophane (4b) and 1,4-bis(dimethylsila)-[4]ruthenocenophane (5b) was also prepared and studied together with the corresponding [n]ferrocenophanes, 10a and 3a-5a. 1,1′-Dilithioruthenocene was found to be a versatile starting material for the synthesis of silicon-substituted ruthenocene derivates such as Ru(C5H4-R)2 (R = SiMe3 (6b), Si2Me5 (7b)) and [n]ruthenocenophanes (3b- 5b). A complete set of 1H, 13C and 29Si NMR data is presented, and the available structural data are discussed with respect to the tilt angle a of the cyclopentadienyl ring ligands which is larger in the more strained [2]ruthenocenophanes than in the corresponding [2]ferrocenophanes.
Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil IX. Umsetzungen einiger 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-dione mit Hexafluoraceton / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part IX. Reaction of some 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-diones with Hexafluoroacetone
Authors: Neda Ion , Farkens Michael , Fischer Axel K. , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reactions of 2-(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (1), 2-bis(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2A3-phosphorinan- 4,6-dione (2), 2-methoxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (3) and 2-trimethylsiloxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (5) with hexafluoracetone are described. In the case of 2 and 3 the reaction furnished the spirocyclic compounds 7 and 8. 2-Bis(2-chloroethyl)amino-1,3,5-triphenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (4) did not react. In the case of 1 and 5 rearrangement reactions took place; the (2-chloroethyl)amino substituent of 1 reacted with one of two equivalents of hexafluoroacetone with formation of the spirocyclic phosphorane 6. The reaction of 5 with tetrabromoorthobenzoquinone gave the phosphoryl compound 9. Compounds 6 - 8 were characterized via their 1H-, 13C-, 19F- and 31P-NMR and mass spectra, compound 9 via its 1H-, 13C- and 31P-NMR and mass spectra. An X-ray crystal structure determination of 8 was conducted; in the six-membered ring the phosphorus atom lies 73 pm out of the plane of the other atoms, and displays trigonal bipyramidal coordination.
Koordinationsverhalten des Pentafluorphenylxenonium Salzes [C6F5Xe]+[AsF6]- gegenüber Pyridinen unterschiedlicher Basizität / Co-ordinative Behaviour of the Pentafluorophenylxenonium Salt [C6F5Xe]+[AsF6]- to Pyridines of Different Basicity
Authors: Frohn Hermann Josef , Schroer Thorsten , Henkel Gerald
Published: February 2015

The arylxenonium cation in the salt [C6F5Xe]+ [AsF6]- is isoelectronic to C6F5I, but coordinatively unsaturated with respect to N-bases like MeCN and pyridines. Co-ordination of strongly basic pyridines causes weakening of the Xe-C bond and C6F1 radical formation. The thermal decomposition of pyridine co-ordinated arylxenonium cations gives three groups of products: C-pentafluorophenylated pyridines, N-pentafluorophenylated pyridinium and N-protonated pyridinium salts. The co-ordination ability of the different pyridines shows a good correlation (C6F5 group) with the 19F NMR shift values of the p-F atom and the coupling constants 3J (19F-129Xe). An X-ray structure analysis was performed for the co-ordination product [C6F5Xe · 2,6-C5H3F2N ]+ [AsF6]- and for [C6F5-C5H5N]+ [(C6F5)2BF2]-, which was obtained by thermolysis of the corresponding adduct.
Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil X. Umsetzungen von 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ4- phosphorinan-4,6-dion mit Triazin-Derivaten sowie mit einigen Aldehyden / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part X. Reactions of 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ4 -phosphorinan-4,6-dione with Triazine Derivatives and with Some Aldehydes
Authors: Neda Ion , Farkens Michael , Thönnessen Holger , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reactions o f 2-hydro-1,3,5-trim ethyl-1,3,5-triaza-2-oxo-2λ4 -phosphorinan-4,6-dione 1 with the triazine derivatives, 1,3,5-trimethyl- and 1,3,5-tribenzyl-hexahydro-1,3,5-triazine, are described. The reaction of three equivalents of 1 with one equivalent of the triazine derivative gave 2 and 3. Both compounds were characterized via their 1H, 13C, and 31P NMR spectra, mass spectra and, in the case of 2, by an X-ray crystal structure analysis, which showed an almost planar six-membered ring; hydrogen bonds of the form N-H···O link the molecules in centrosymmetric pairs. The reactions of 1 with the aldehydes glyoxylic acid, 2-hydroxybenzaldehyde and 3,4,5-trimethoxybenzaldehyde gave addition products. The C (:O) group o f the aldehyde is inserted into the P -H bond o f 1. The resulting compounds 4 ,5 and 6 were characterized through their 1H, 13C, and 31P NMR spectra, and mass spectra.
Heterocyclische Spirocyclohexadienone aus substituierten Phenolen / Heterocyclic Spirocyclohexadienones from Substituted Phenols
Authors: Möhrle H. , Schake D.
Published: February 2015

Mannich bases were prepared from substituted phenols with aliphatic amines and formaldehyde. Amine exchange with N-methyl-2-naphthylamine followed by a Hofmann Martius rearrangement gave rise to o,o′-amino-hydroxy-diphenylmethane derivatives. Under cyclization conditions some of these compounds produced spirocyclohexadienones, which are the ipso analogs to the hypothetic intermediates postulated in the aminomethylation mechanism of phenols.
Ba2Na(CN2)(CN)3, ein neues Cyanamid-cyanid mit interpenetrierenden Teilstrukturen / Ba2Na(CN2)(CN)3, a Novel Cyanamide Cyanide with Interpenetrating Substructures
Authors: Berger Ute , Schnick Wolfgang
Published: February 2015

Ba2Na(CN2)(CN)3 was obtained by the reaction of Ba2N with melamine and NaCN at 700 °C. The compound was structurally characterized by single-crystal X-ray investigations (Fd3̄m, a = 1518.8(3) pm, Z = 16). In the crystal structure the Ba2+ ions form a cubic close packed arrangement, the Na+ and the CN2-
2 ions occupy the octahedral interstices. The CN-ions are located within the close packed Ba2+ layers. The unit cell of Ba2Na(CN2)(CN)3 contains two interpenetrating substructures of the zinc-blende structure type, building up a variant of NaTl. A reversible phase transition has been observed during cooling of the compound. Whereas the Ba2(CN2)(CN)3 sublattice remains nearly unaffected in this process, the Na+ ions of the low-temperature phase are statistically distributed on two crystallographic positions.
Synthese und Struktur von Zn(HSO4)2(H2SO4)2 und Cd(HSO4)2 / Synthesis and Structure of Zn(HSO4)2(H2SO4)2 und Cd(HSO4)2
Authors: Kemnitz E. , Werner C. , Stiewe A. , Worzala H. , Trojanov S.
Published: February 2015

From the binary systems M2SO4/H2SO4 (M = Zn, Cd), two new hydrogen sulfates, (Zn(HSO4)2(H2SO4)2 and Cd(HSO4)2, have been synthesized and structurally characterized. Both compounds crystallize in the monoclinic space group P21/c with cell parameters a = 5.047(2), b = 15.430(4), c = 7.958(3) Å and β = 104.16(4)° (Z= 2) for Zn(HSO4)2(H2SO4)2 and a = 5.339(1), b = 13.351(3), c = 8.508(2) Å and β = 92.22(3)° (Z = 4) for Cd(HSO4)2. In the zinc compound there are slightly distorted centrosymmetric ZnO6 octahedra with Zn-O distances of 2.05-2.13 A which are sharing corners with SO4 tetrahedra. HSO4 and H2SO4 tetrahedra are linked via hydrogen bonds to form layers perpendicular to the c-axis. In the crystal structure of Cd(HSO4)2 there exist two crystallographically different HSO4 tetrahedra. The CdO6 octahedra with Cd-O distances between 2.24 and 2.31 A are strongly angle-distorted. Besides hydrogen bonds of medium strength (do···o = 2.66 Å) there are also much more weaker ones (do···o = 3.04 Å). Considering these latter ones zigzag chains in z-direction can be recognized.

The relatively low stability of Cd(HSO4)2 in comparison with other metal-II-hydrogen sulfates is discussed with respect to its structural pecularities.
Methanolothermale Synthese und Kristallstruktur von Tetraselenidoarsenaten( V) und -antimonaten(V) des Rubidiums und Cäsiums / Methanolothermal Synthesis and Crystal Structure of Tetraselenidoarsenates(V) and -antimonates(V) of Rubidium and Cesium
Authors: Wachhold Michael , Sheldrick William S.
Published: February 2015

Tetraselenidoarsenates(V) and -antimonates(V), Rubidium, Cesium, Methanolothermal Synthesis, Crystal Structure Methanolothermal reaction of M2CO3 (M = Rb, Cs) with E2Se3 (E = As, Sb) and Se at temperatures in the range 180 -200°C leads to the formation of tetraselenidoarsenates(V) and -antimonates(V) M3ESe4 in moderate to quantitative yields. All four compounds crystallize in the (NH4)3AsS4 structure type (space group Pnma) and contain isolated slightly distorted tetrahedral ESe3-
4 anions with crystallographic CS symmetry. Both of the independent cations are coordinated in an irregular manner by seven Se atoms.
Preparation and Crystal Structure of the Mercury(I) Dimolybdate(VI) Hg2Mo2O7
Authors: Wessels Annemarie L. , Jeitschko Wolfgang
Published: February 2015

Crystal Structure, Magnetic Susceptibility, Mercury Molybdates(VI) Yellow, flat, needle-shaped, diamagnetic crystals of Hg2Mo2O7 were obtained by decomposition of Hg2MoO4 in evacuated, sealed silica tubes at 550 °C. Their crystal structure was determined from four-circle diffractometer data: P1̄, a = 709.7(2), b -714.4(2), c = 803.8(2) pm, α = 64.89(1)°, β = 66.09(1)°, γ = 66.45(1)°, Z = 2, R = 0.030 for 3165 structure factors and 66 variables. The molybdenum atoms are coordinated by four oxygen atoms at 171 to 195 pm in a very distorted tetrahedral arrangement. These tetrahedra are linked via a common oxygen atom, thus forming Mo2O7 groups. The tetrahedral oxygen coordination of each molybdenum atom is augmented by two additional oxygen atoms at 218 to 231 pm, which leads to a distorted octahedral coordination for the molybdenum atoms. These MoO6 octahedra are connected via common corners and edges and in this way they form two-dimensionally infinite sheets, which are separated by the Hg2 pairs (Hg-HG distance: 252.2 pm).
The Oxidation of Partially Acylated Myoinositols
Authors: Kurzer Frederick , Chapman Dennis
Published: February 2015

1,3,4,6-Tetrakis-and 1,3,4,5,6-pentakis-acylmyoinositols are obtained by the controlled catalyzed acylation of myoinositol. The extent of the substitution depends both on the reaction conditions and the structure of the acylating agent, including steric factors. Chromic acid oxidation converts the acylmyoinositols into the corresponding 2-ketones. Under electron impact, the compounds undergo stepwise deacylation.