bluuebunny/crossref_metadata_2025 huggingface dataset:
Geochemical Constraints on the Early Thermal History of the Earth
Authors: Drake Michael J.
Published: February 2015

Theories of the formation of the Earth strongly suggest that the Earth should have been substantially molten during and immediately after accretion. Estimates of the composition of the upper mantle indicate that many elements are present in chondritic ratios. Experimental measurements of element partition coefficients show that segregation of perovskite, majorite garnet, or olivine would fractionate the ratios of these elements away from chondritic values. The implication of these geochemical observations is that the Earth did not undergo extensive fractionation during and immediately following accretion. One possibility is that the Earth did not become substantially molten. Alternatively, if the Earth was indeed substantially molten, then it is possible that minerals were entrained in magma and were unable to segregate. In the former case, the accretional process must have delivered gravitational potential energy more slowly than current theory predicts, and an origin of the Moon in a giant impact would be unlikely. In the latter case, the high Mg/Si ratio in the upper mantle of the Earth relative to most classes of chondrites would be intrinsic to the silicate portion of the Earth. Unless significant amounts of Si exist in the core, the high Mg/Si ratio is a bulk planetary property, implying that the accretional process did not mix material between 1 AU and 2-4 AU.
Electronic Spectra of Single-Crystal Maleonitriledithiolate Complexes of Iridium (I): [Ir(CO)2mnt] TBA (mnt ≡ [S2C2(CN)2]2-; TBA ≡ [(C4H9)4N] + )
Authors: Riedl U. , Gliemann G.
Published: February 2015

The polarized optical absorption and emission (spectra, decay times) of single-crystal [lr(CO)2mnt] TBA at temperatures 2 K≦T≤295 K and homogeneous magnetic fields O≦H≦6T are reported. The highly resolved spectra show 0-0 transitions with vibrational satellites and phonon side bands. Applied magnetic fields yield no effect on the emission. The lowest excited electronic states can be assigned to the spin-orbit components A′1 B′1 and B′1 of the charge transfer triplet 3A2 (symmetry C2v)
Methyl Nitrate, its Molecular Values, Magnetic Susceptibility Anisotropies, Molecular Electric Quadrupole Moment, Second Moments of the Electronic Charge Distribution, and Electric Field Gradient at the Nitrogen Nucleus
Authors: Spieckermann J. , Sutter D. H.
Published: February 2015

The high field molecular Zeeman effect of low-J rotational transitions has been observed in methyl nitrate. The spectrum is complicated by the presence of the small 14N nuclear quadrupole coupling. Methyl top internal rotating splitting is negligible in the transitions studied here. From line shape analyses the individual satellite frequencies in the Zeeman-hfs-multiplets could be determined with experimental uncertainties typically smaller than ±2 kHz. The molecular Zeeman parameters and the 14N nitrogen coupling constants were fitted simultaneously to the observed splittings. The molecular g-values are gaa = -0.1168(5), gbb= -0.0449(3), and gcc= -0.0235(4). The molecular magnetic susceptibility anisotropies in units of 10-6 erg gauss-2 mol-1 are 2ξaa -ξbb -ξcc = +1.24(54) and 2ξbb - ξcc - ξaa = +13.14(53). The 14N nuclear quadrupole coupling constants are χaa - + 0.308(17) MHz, χbb - χcc -0.262(31) MHz. The molecular electric quadrupole moments calculated from the observed rotational constants and Zeeman parameters in units of 10-26 esu cm2 are Qaa = +3.4(6), Qbb= -4.6(6), and Qcc= +1.2(10). Knowledge of the molecular structure and the molecular g-values also gives the diagonal elements in the paramagnetic susceptibility tensor and the ansiotropies in the second moments of the electronic charge distribution. The results in units of 10-6 era gauss-2 mole-1 are ξp
aa = + 118.14(10), ξp
bb = +279.73(14), and ξp
cc = + 357.40(26), and ⟨a2⟩ - ⟨b2⟩ = + 37.14(14) Å2, ⟨b2⟩ - ⟨c2⟩ = +20.46(22) Å2, and ⟨c2⟩ -⟨a2⟩ = -57.60(21) Å2
11Boron Quadrupole Hyperfine Structure in the Rotational Spectrum of Hydroxydifluoroborane
Authors: Vormann Kirsten , Dreizler Helmut
Published: February 2015

The 11B quadrupole hyperfine structure in the rotational spectra of three isotopic species of hydroxydifluoroborane, BF2OH, BF2OD, and BF2
18OH has been investigated and the quadrupole coupling constants of these species have been determined. Using the variation of the 11B quadrupole coupling constants with isotopic substitution, it has been possible to evaluate the complete quadrupole coupling tensor, including the off-diagonal element %ab, for each isotopic species.
Zur Chemie der l,3,5-Triaza-2-phosphinan-4,6-dione. Teil VI. Darstellung von 1,3,5-Triaza-2 λ3-, 1,3,5-Triaza-2 λ4- und 1,3,5-Triaza-2 λ5-phosphinan-4,6-dionen / Chemistry of the 1,3,5-Triaza-2-phosphinane-4,6-diones. Part VI. Synthesis of 1,3,5-Triaza-2λ3-, 1,3,5-Triaza-2λ4- and 1,3,5-Triaza-2λ5-phosphinane-4,6-diones
Authors: Farkens Michael , Meyer Thomas G. , Neda Ion , Sonnenburg Ralf , Müller Christian , Fischer Axel K. , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reactions of 1,3,5-trimethylbiuret with dicyclohexylaminodichlorophosphine and with pyrrolidinodichlorophosphine furnished the triazaphosphinane-diones 1 and 2. Oxidation reactions of the 2-diorganoam ino-1,3,5-triorgano-1,3,5-triaza-2 λ3-phosphinane-4,6-diones 1, 2, and 4-9, as well as 2-fluoro-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphinane-4,6-dione 10 with hydrogen peroxide, elemental sulphur, phenyl azide, 1-adamantyl azide,p-nitrobenzoyl azide, tetrachloro-orthobenzoquinone, tetrabromo-orthobenzoquinone, 3,5-di-t-butyl-orthobenzoquinone, and hexafluoroacetone led to the respective oxidation products, 12-32, involving either λ4P or λ5P. In the reaction o f the P(III)C1 derivative 11 with 3-m ethyl-l,5-diphenyl-l,5- bis(trimethylsilyl)biuret the bifunctional compound 33 was produced. The new com pounds 1,2 and 12-33 were characterized via their 1H, 13C and 31P and, where appropriate, 19F NMR spectra. In the case o f the four compounds, 3 (previously described in the literature [2]), 13, 31, and 33, single crystal X-ray diffraction studies were conducted. Unusually for this type of heterocycle 3 displays a 1,4-diplanar ring conformation because o f the bulky aromatic substituents. 13 shows an envelope conformation. The hydrogen peroxide solvent molecule has crystallographic inversion symmetry, but may be disordered. In 31 the coordination geometry at phosphorus is trigonal bipyramidal. The five-membered ring shows a twist conform ation associated with the bulky trifluoromethyl groups. The exocyclic P-N bonds in 33 are unusually long.
Metallkomplexe mit biologisch wichtigen Liganden, LXIX [1].
Authors: Lampeka Rostislav , Bergs Ralph , Krämer Roland , Polborn Kurt , Beck Wolfgang
Published: February 2015

(η5-C5Me5)

(M - Co, Rh, Ir) and (η5-p-cymene)(CI)

have been obtained by reactions of (η5-C5Me5)Co(CO)I2, [(η5-C5Me5)MCl2]2 (M = Rh, Ir) and [(η6-p-cymene)RuCl2]2 with 2-hydroxyiminocarboxylates. These complexes are also accessible by template synthesis from hydroxylamine or O-methylhydroxylamine, α-oxocarboxylate and (η5-C5Me5)Co(CO)I2 or [(η5-C5Me5)MCl2]2 (M = Rh, Ir). The structure of the SRu enantiomer of (η5-C5Me5)(I)

has been determined by X-ray diffraction.
Darstellung und Struktur von 2.3-Bis[2,4,6-tris(trifluoromethyl)phenyl]-1,2,3-selenadiphosphiran / Preparation and Structure of 2.3-Bis[2,4,6-tris(trifluoromethyl)phenyl]-1,2,3-selenadiphosphirane
Authors: Voelker Heike , Pieper Ursula , Roesky Herbert W. , Sheldrick George M.
Published: February 2015

Reaction of the diphosphene RfP=PRf (Rf = 2,4,6-tris(trifluoromethyl)phenyl-) with red selenium affords the selenadiphosphirane 1. The X-ray crystal structure of 1 was investigated.
Die Kristallstruktur von AsF5 · / The Crystal Structure of AsF5 ·
Authors: Lork Enno , Behrens Ulrich , Viets Detlef , Mews Rüdiger
Published: February 2015

The crystal structure of AsF5 ·

is reported. It crystallizes in the orthorhombic space group Pnma with a = 749.1(3) pm, b = 770.6(3) pm and c = 1630.0(5) pm, V = 960.9(6) · 106 pm3, Z = 4.
Homoleptische Carbenkomplexe, V [1]. Chelatartige Percarbenkomplexe des Palladiums und Platins / Homoleptic Carbene Complexes, V [1]. Chelating Percarbene Complexes of Palladium and Platinum
Authors: Fehlhammer Wolf Peter
Published: February 2015

Ten palladium and platinum complexes each containing two chelating bis(diaminocarbene) ligands have been synthesized in a one pot-reaction from PdI2, PtI2 or K2PtCl4, a tenfold excess (forty equivalents) of isocyanide and 1,2- or 1,3-diamines. An X-ray investigation of

(8) revealed a stereochemistry with the two spiro-linked seven-membered metallacycles strongly bending out of the PtC4 coordination plane in opposite directions. In addition, three palladium bis-chelates with mixed amine/carbene bidentate ligands were obtained from reactions of PdI2 with only four equivalents of isocyanide and the diamine.
Darstellung und Kristallstruktur der Cäsium-Selenidogermanate(IV) Cs4Ge4Se10 · 2CH3OH und Cs4Ge2Se8 / Preparation and Crystal Structure of the Cesium Selenidogerm anates(IV) Cs4Ge4Se10 · 2CH3OH and Cs4Ge2Se8
Authors: Sheldrick W. S. , Schaaf B.
Published: February 2015

Methanolothermal reaction of Cs2CO3 with Ge and Se at 190 °C yields Cs4Ge4Se10 · 2 CH3OH and Cs4Ge2Se8, the structures of which have been determined by X-ray structural analysis. The anion [Ge4Se10]4 in Cs4Ge4Se10)·2 CH3OH displays an adamantane-like structure in which four GeSe4 tetrahedra are linked via joint vertices. In con­trast Cs4Ge2Se8 contains the novel dinuclear anion [Ge2Se8]4-, the first example of a selenidogermanate(IV) exhibiting Se2 bridging units. Two GeSe4 tetrahedra are linked in this anion through Se-Se bonds to yield a six-membered ring, which displays a chair conformation and crystallographic C2h symmetry.
Polynuclear Gold(I) Complexes of Dendritic Amines: Formation of Terminal Tris[(triphenylphosphine)aurio(I)]ammonium Groups -N(AuPPh3)3
1+
Authors: Lange Peter , Beruda Holger , Hiller Wolfgang , Schmidbaur Hubert
Published: February 2015

The reactions of dendritic amines RN(CH2CH2CH2NH2)2 (R = Me, c-Hex, PhCH2) and N(CH2CH2NH2)3 with tris[(triphenylphosphine)aurio(I)]oxonium tetrafluoroborate [O(AuPPh3)3]+BF4
- in THF yield species with terminal imido cluster groups -N(AuPPh3)3
1+. The compounds have been obtained as stable crystalline solids in high yields and characterized by NMR spectroscopy as well as mass spectrometry and elemental analysis. The triply charged nonanuclear complex [N(CH2CH2N(AuPPh3)3)3]3+ exhibits major changes in the 1H spectroscopic data and in the chemical properties as compared with com pounds with dications [RN(CH2CH2CH2N(AuPPh3)3)2]2+ (R = Me, c-Hex, PhCH2). Excessive auration to give hypercoordinated species has not been observed
Cd0,73Cu0,27V2O6: Eine Verbindung mit Branneritstruktur / Cd0 ,73Cu0,27V2O6: A Compound with Brannerite Structure
Authors: Münchau S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Cd0.73Cu0.27V2O6 were prepared by solid state reactions. X-ray investigations lead to monoclinic symmetry, space group C3
2h-C2/m , a = 9.339, b = 3.5604, c = 6.893 Å, β = 111.85°, Z = 2. It belongs to the Brannerite structure, showing a statistical distribution of Cd2+ and Cu2+ on one point position. The crystal structure of Brannerites is discussed with respect to the distorted O2- octahedra around V5+ and the influence of the Jahn-Teller active Cu2+ ion to the shortened M2+O6 octahedra.
Kristallstruktur von (Ph3PNH2)4[Sb6O10Cl14] · 2CH3CN / Crystal Structure of (Ph3PNH2)4[Sb6O10Cl14]-2CH3CN
Authors: Fenske Dieter , Garbe Ralf , Dehnicke Kurt
Published: February 2015

The title compound has been obtained by the reaction of the phosphoraneiminato complex Cl2Sb(NPPh3) with chlorine, followed by partial hydrolysis in acetonitrile. The colourless crystals were characterized by a crystal structure determination. Space group P1̅, Z = 2, structure refine­ment with 8320 observed unique reflections, R = 0.063 with I > 2σ(I). Lattice dimensions at -70 °C: a = 1245.0(6); b = 1277.7(8), c = 1623.8(9) pm, a = 77.97(2)°, β = 86.52(2)°, γ = 67.07(2)°. The compound consists of Ph3PNH2
+ ions, [Sb6O10Cl14]4-ions, in which the central unit is a Sb4O6 skeleton with a double heterocubane-like arrangement with two missing corners, and of in­ cluded acetonitrile molecules without bonding interactions.
Cu6Br6(NPMe3)4, ein gemischt-valenter Kupfercluster / Cu6Br6(NPMe3)4, a Mixed-Valent Cluster of Copper
Authors: Köcker Rolf Meyer zu , Dehnicke Kurt , Fenske Dieter
Published: February 2015

Cu6Br6(NPMe3)4 has been prepared as a by-product from the reaction of CuBr with Me3SiNPMe3 in a CH2Cl2 suspension. The dark red-violet crystals, which contain three molecules CH2Cl2 per unit cell, have been characterized by a crystal structure determination.

Cu6Br6(NPMe3)4 · 3 CH2Cl2: Space group P1̅, Z = 2, lattice dimensions at -95 °C: a = 1165.2(4), b = 1168.9(4), c = 1842.9(6) pm, a = 75.61(3)°, β = 84.15(3)°, γ = 61.08(2)°, 6918 observed unique reflections, R = 0.066. In the cluster molecule Cu6Br6(NPMe3)4 the copper atoms form a nearly ideal octahedron with Cu-Cu bond lengths of 268.8 pm in average. Each of the Cu atoms is con­nected with a terminal bromine atom. Four planes of the octahedron are capped by μ3-nitrogen atoms of the (NPMe3)- groups.
Molekül- und Kristallstruktur der Verbindung 8-(n-Butylaminophenyl- methyliden)-1,2,3,4,5,6,7-heptathiocan / Molecular and Crystal Structure of 8-(n-Butylaminophenyl- methylidene)-1,2,3,4,5,6,7-heptathiocane
Authors: Heinemann Frank W. , Hartung Helmut , Maier Nadja , Matschiner Hermann
Published: February 2015

By the reaction of acetophenone with sulfur and primary amines yellow-coloured crystals of the title compound are formed. It crystallizes in the monoclinic space group P21/n with lattice constants a = 1309.9(2) pm, b = 926.5(2) pm, c = 1582.2(2) pm and β = 114.00(1)°. The structure of the eight-membered heptathiocane ring is characterized by a crown confor­mation.

The range of the S-S distances [204.4(1)-207.3(1) pm], the S-S-S bond angles [107.2(1)- 109.0(1)°] and the S-S-S-S torsion angles [93.2(1)-97.7(1)°] is comparable to those observed in α-, β- and γ-sulfur.
BaCeN2, ein Bariumnitridocerat(IV) mit einer Struktur vom anti-TiP-Typ / BaCeN2, a Bariumnitridocerate(IV ) with a Structure of the anti-TiP Type
Authors: Seeger Oliver , Strähle Joachim
Published: February 2015

Reaction of Ba3N2 with CeN in the stoichiometric ratio 1:3 at 850 °C under an atmosphere of N2 followed by quenching yields air and moisture sensitive BaCeN2. The product crystallizes isotypically to β-RbScO2 with the anti-TiP type structure in the hexagonal space group P63/mmc with a = 365.06(2), c = 1266.03(3) pm, Z = 2. The structure was determined using X-ray and neutron powder diffraction data. In the structure the Ba2+ cations occupy trigonal prismatic holes with distances Ba-N = 288(1) pm while the Ce atoms are in octahedral positions with distances C e -N = 242.4(8) pm
Die Kristallstruktur von TIZnPO4 und TIZnAsO4 / The Crystal Structure of TIZnPO4 and TIZnAsO4
Authors: Andratschke Martina , Range Klaus-Jürgen , Weigl Claudia , Schießl Ulrike , Rau Franz
Published: February 2015

Single crystals of the title com pounds were obtained by high pressure synthesis in a modified Belt type apparatus. The compounds crystallize in the monoclinic system (space group P21) with a = 8.732(2), b = 5.468(1), c = 8.841(2) Å, β = 90.61(2)° for TlZnPO4 and a = 8.921(3), b = 5.631(1), c = 8.958(3) Å, β = 91.03(2)° for TlZnAsO4, Z = 4. The structures were refined from diffractom eter data to R = 0.072, Rw = 0.050 for 3700 (TlZnPO4) and to R = 0.093, Rw = 0.067 for 3943 (TlZnAsO4) independent absorption corrected reflections. The compounds are isotypic and belong to the “stuffed derivatives" of the Icmm structure type with a (ZnXO4)- network of alternating corner linked ZnO4 and XO4 tetrahedra (X = P, As) forming channels of six-membered rings in the direction of the a axis. These cavities contain two crystallographically independent Tl cations in an irregular coordination by eight nearest oxygen atoms
Darstellung und Strukturen von 2,2,4,4-Tetrafluor-1,3-diphosphetanen und -1,3-diphosphetan-disulfiden / Synthesis and Structures of 2,2,4,4-Tetrafluoro-1,3-diphosphetanes and of -1,3-diphosphetane Disulfides
Authors: Fild Manfred , Jones Peter G. , Ruhnau Karsten , Thöne Carsten
Published: February 2015

A simple route to 1,3-diphosphetanes [RPCF2]2 [R = Ph, Me, But] is described. The phosphaalkene intermediates RP=CF2, as well as the corresponding disulfides [R(S)PCF2]2 have been characterized. The crystal structures of [PhPCF2]2, and of the sulfides [Ph(S)PCF2]2 and [But(S)PCF2]2 are reported.
Synthese, Kristallstruktur und Eigenschaften von Tetraaminophosphoniumiodid [P(NH2)4]I / Synthesis, Crystal Structure, and Properties of Tetraaminophosphonium Iodide [P(NH2)4]I
Authors: Horstmann Stefan , Schnick Wolfgang
Published: February 2015

The title compound has been prepared starting from phosphorothionic triamide SP(NH2)3 by methylation of the sulfur atom and subsequent ammonolysis reaction in dry acetonitrile and dichloromethane, respectively, both at room temperature. Suitable single crystals are obtained from an acetonitrile solution in a temperature gradient between 70 °C and room temperature. The crystal structure of [P(NH2)4]I has been determined by single crystal X-ray methods (P4/nbm; a = 842.6(2), c = 486.7(2) pm, Z = 2). In the solid [P(NH2)4]+ - and I−-ions are found with significant N - H···I-hydrogen bonding interactions between anions and cations (H -I: 276.4 pm). The P - N - bond length in the cation (160.7(2) pm) represents the shortest P - NH2 bond distance reported to date indicating a significant electrostatic strengthening. The condensation behaviour of [P(NH2)4]I in solution and in the solid has been investigated.
A Novel Entry into Cyclopropanated Sugar Amino Acids
Authors: Fakhar-uz-Zaman  , Fatima Ayjaz , Malik Abdul , Voelter Wolfgang
Published: February 2015

Reaction of sugar triflates (1) and (2) with tert-butyl cyanoacetate in presence of sodium hydride affords the cyclopropanated sugars (3) and (4), followed by selective hydrolysis of the ester group to free acids (5) and (6), respectively. Couplings of (5) and (6) with protected glycine and L-alanine lead to cyclopropanated sugar amino acids (7-10). The coupling of 6 with benzyl 3,4-(“exo”-aminomethyl)methano-3,4-dideoxy-β-L-arabinopyranoside (11) fur­ nished benzyl 3,4-[(C-cyano-amido)methano-(benzyl 3,4-(“exo”-methylene)methano-3,4-di-deoxy-β-L-arabinopyranosido)]-3,4-dideoxy-β-L-arbinopyranoside (12), suggesting an “exo” orientation of the ester group in 3 and 4.
Zur Kenntnis von K4CuV5O15Cl / On K4CuV5O15Cl
Authors: Martin F.-D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of K4CuV5O15Cl were prepared by crystallization from the melt. The yellow brown crystals show tetragonal symmetry, space group C1
4-P4, a = 8.8690, c = 5.4196 Å, Z = 1. K4CuV5O15Cl is strongly related to KBaCuV2O7Cl and K2V3O8. V(1) shows V2O7 double tetrahedra connected by square VO5 and CuO4Cl pyramids. The crystal structure is discussed with respect to the related compounds.
The Preparation of Some Mono-and Bis(thiolate)-2-butyne Complexes of Tungsten(II) of the Types [WI(SR)(CO)(dppm )(η2-MeC2Me)] {dppm = Ph2P(CH2)PPh2; R = Et, But, Ph or CH2Ph} and [W (SR)2(CO)(dppm)(η2-MeC2Me)]
Authors: Baker Paul K. , Flower Kevin R.
Published: February 2015

Equimolar quantities of [WI(CO)(NCMe)(dppm)(η2-MeC2Me)][BF4] {dppm = Ph2P(CH2)PPh2) and NaSR (R = Et. But ,Ph or CH2Ph) react in CH2Cl2 at room temperature to give the neutral thiolate complexes [WI(SR)(CO)(dppm)(η2-MeC2Me)] (1 → 4) in good yield. The complex [WI(CO)(NCMe)(dppm)(η2-MeC2Me)][BF4] also reacts with two equiv­alents of NaSR (R = Et. But, Ph or CH2Ph) in CH2Cl2 at room temperature to afford the bis(thiolate) complexes [W(SR)2(CO)(dppm)(η2-MeC2Me)] (5 → 8), in good yield. Com­plexes 1→8 have been characterized by elemental analysis (C, H and N), IR and 1H NMR spectroscopy. 13C NMR spectra of selected complexes indicate that the 2-butyne ligand is donating four electrons to the metal in both [WI(SR)(CO)(dppm)(η2-MeC2Me)] and [W(SR)2(CO)(dppm)(η2-MeC2Me)] type complexes.
Zur Chemie von Flechten aus der Türkei. Struktur von Nemetzon, dem Apothecienpigment von Haematomma nemetzii / On the Chemistry of Lichens from Turkey. Structure of Nemetzon, the Pigment of the Apothecia from Haematomme nemetzii
Authors: Huneck Siegfried , Himmelreich Uwe , Schmidt Jürgen , John Volker , Zeybek Ulvi
Published: February 2015

The lichens Haematomma nemetzii, a Ramalina species, and Tornabena scutellifera from Turkey have been analysed chemically. Nemetzon is a new anthraquinone from the apothecia of Haematomma nemetzii.
(Se,O)-Koordinierte Komplexe niedervalenter Hauptgruppenmetalle: Die Kristallstruktur von Bis(N,N-Diethyl-N′-benzoylselenoureato)blei(II) / (S e,O)-Coordinated Complexes of Subvalent Main Group Metals: The Crystal Structure of Bis(N ,N -diethyl-N′-benzoylselenoureato)lead(II)
Authors: Schuster M. , Bensch W.
Published: February 2015

Bis(N,N-diethyl-N′-benzoylselenoureato)lead(II) has been prepared and characterized by single-crystal structure analysis. Pb(C12H15N2OSe)2 crystallizes in the non-centrosymmetric orthorhombic space group Iba2. The cell parameters are a = 13.206(3), b = 20.542(4), c = 10.089(2) A and Z = 4. R = 0.025. The direction of the polar axis was determined unambig­ uously. Pb(II) is bidentally coordinated to two N,N-diethyl-N′-benzoylselenourea molecules. The coordination polyhedron is a distorted pseudo-trigonal bi-pyramid with one equatorial position occupied by an electron lone-pair. The Pb-Se and Pb-O bond lengths are 2.876(1) and 2.444(4) Å, respectively. In the crystal lattice, each Pb atom also shows interactions with two Se atoms of a neighboring molecule. The Pb-Se distance of that interaction is 3.643 Å.
[Mn(SPh)Cl3]2-, [Mn(SPh)3Cl]2-, [Mn2(SPh)6]2- und [Mn4(SPh)6Br4]2–: Synthese, Struktur und ausgewählte Eigenschaften einiger neuer Chalkogenolatkomplexe des zweiwertigen Mangans / [Mn(SPh)Cl3]2-, [Mn(SPh)3Cl]2-, [Mn2(SPh)6]2- und [Mn4(SPh)6Br4]2-: Synthesis, Structure and Selected Properties of Some New Chalkogenolate Complexes of Divalent Manganese
Authors: Stephan Hans-Oscar , Griesar Klaus , Haase Wolfgang , Henkel Gerald
Published: February 2015

[Me4N]2[Mn(SPh)Cl3] (1) was obtained by reaction of MnCl2·4H2O with one equivalent of NaSPh from methanolic solutions in the presence of [Me4N]Cl. Under similar conditions the compound [Et4N]2[Mn(SPh)3Cl] (2) waso isolated using [Et4N]+ cations. Crystal data: 1: a = 9.425(3), b = 11.903(3)t c -19.073(4) Å, space group P 21cn, Z = 4; 2: a = 14.420(7), b = 13.834(8), c = 17.918(10) Å, β = 90.69(4)°, space group P21/c, Z = 4. The structures were refined to R = 0.0839 (1) and 0.0328 (2), respectively. Besides the dianion [Mn(SPh)3Cl]2- (6), crystals of 2 contain traces of [Mn(SPh)2Cl2]2- (7) distributed over 3.8% of the anion positions. The existence of [Mn(SPh)Cl3]2- (5), 6 and 7 under similar conditions is interpreted in terms of ligand exchange solution equilibria. Within these mononuclear anions, the central metal/sulfur/halide cores show distorted tetrahedral stereochemistries. The reaction of MnCl2 with NaSPh (molar ratio 1:3) in hot mixtures of acetonitrile and DMF leads to [Mn2(SPh)6]2- (8), which can be isolated as crystalline [Ph4P]2[Mn2(SPh)6] (3) with a = 13.383(2), b = 13.565(2), c = 20.438(4) Å, β = 106.41(1)°, space group P21/c, Z = 2. The final refinement converged to R = 0.0380. 8 consists of two edge-sharing MnS4 tetrahedra showing structural similarities with other tetrahedral complexes of the type [M2(SR)6]2-. According to magnetochemical studies, the manganese atoms are antiferromagnetically coupled with J=-18.6(2) cm-1. Reaction of 3:2:1 molar ratio mixtures of NaSPh/MnBr2/[Et4N]Br in hot acetonitrile leads to [Et4N]2[Mn4(SPh)6Br4] (4) which crystallizes with a = 14.109(3), b = 27.556(5), c = 16.194(4) Å, β = 95.35(2)°, space group P 21/n, Z=4. The structure was refined to R = 0.0583. This compound is also available by reaction of [Et4N]2[Mn(SPh)4] with MnBr2 in a molar ratio of 3:5. The anion [Mn4(SPh)6Br4]2- (9) contains a central {Mn4S6Br4} core which exhibits an adamantane-like structure: A Mn4 tetrahedron is inscribed into a S6 octahedron with the S atoms bridging the edges of the Mn4 tetrahedron. Terminally bonded Br atoms complete the tetrahedral coordination spheres of the manganese atoms and thus form an outer Br4 tetrahedron. As a result, the symmetry of the central core comes close to Td. The observed distortion is attributed to intramolecular repulsions of the organic residues. Selected properties of compounds 1-4 are reported.
Chemie polyfunktioneller Moleküle, 114 [1]. Synthese und Struktur eines ionischen und nichtionischen, cyclischen Carbaphosphazens und eines Cobalt(III)phosphazen-Komplexes / Chemistry of Polyfunctional Molecules, 114 [1]. Synthesis and Structure of an Ionic and Non Ionic Cyclic Carbaphosphazene and of a Cobalt(III)phosphazene Complex
Authors: Ellermann Jochen , Sutter Jörg , Knoch Falk A. , Moll Matthias , Bauer Walter
Published: February 2015

Reaction of

(1) in CH2Cl2 with benzimidazole yields

. The salt [4]+BPh4
- has been prepared in THF by metathesis of [4]+Cl- with NaBPh4. Deprotonation of the cationic ring in [4]+BPh4
- was accomplished using 1,8-diazabicyclo[5.4.01,7]undec-7-ene and resulted in the six-membered carbacyclophosphazene

(6). Treating 1 with 8 -hydroxyquinoline in CH2Cl2 yields the octahedral cis-complex

= 8-oxyquinolinate group). The com pounds [4]+BPh4
-, 6 and 7 are characterized by their IR, Raman, 31P{1H} NMR, 13C{1H} NMR, 1H NMR and mass spectra. Crystals suitable for X-ray structure analyses have been obtained for [4]+BPh4
- and 7×0.5 CH2Cl2. The colourless plates of [4]+BPh4
- crystallize in the triclinic space group P1̄, with the lattice constants a = 1172.7(3), b = 1326.2(3), c = 1806.1(6) pm; α = 100.79(2), β = 103.71(3), γ = 108.18(2)°. The black blocks of 7×0.5 CH2Cl2 crystallize in the monoclinic space group P 21/c with the lattice constants a = 1159.0(10), b = 2008.9(10), c = 2034.6(12) pm; β = 105.86(5)°.
Silyl- und phosphinosubstituierte Methane: Präparative und strukturelle Untersuchungen zur Steuerung des Reaktionsverhaltens ambidenter Phosphinomethanide / Silyl and Phosphino Substituted M ethanes: Synthetic and Structural Investigations of the Reactivity of Ambidentate Phosphinom ethanides
Authors: Karsch Hans H. , Richter Roland , Deubelly Brigitte , Schier Annette , Paul Martin , Heckel Maximilian , Angermeier Klaus , Hiller Wolfgang
Published: February 2015

LiCH(PMe2)2 reacts with SiCl4 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphino methanes; Cl2Si[CH(PMe2)2]2 (3) or PhR2Si[CH(PMe2)2] (4) (R = Me) and (5) (R = Ph), respectively. 4 and 5 are deprotonated by nBuLi to give trimeric {Li[C(PMe2)2(SiMe2Ph)]}3 (6) and in the precence of TMEDA. monomeric {Li[C(PMe2)2(SiMe2Ph)]·TMEDA (7) or {Li[C(PMe2)2(SiPh3)]} · TMEDA (8), respectively. {Li[C(PMe2)(SiMe3)2]}2·TMEDA reacts with R2SiCl2 (R = Me. Cl) via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus generating an ylidic moiety. The obtained compounds (Me3Si)2(PMe2)C-SiR2-PMe2=C(SiMe3)2 (9) (R = Me) and (10) (R = Cl) are structurally characterized by X-ray crystallography as well as compounds 3, 5, 6 and 7. The observed variations in bond lengths and angles are explained to be mainly due to steric congestion. The ambidentate nature of phosphinomethanides thus clearly can be influenced by the nature of their carbanion substituents.
π-π Interactions between Pyrylium and Phenyl Rings in the Crystal
Authors: Balaban Teodor Silviu , Furmanova Nina G.
Published: February 2015

The crystal structures of two isomeric phenyl-substituted pyrylium perchlorates, 2,6-di-methyl-4-phenylpyrylium (1) and 2,4-dim ethyl-6-phenylpyrylium (2), have been determined. Both cations are planar in the crystal so that the electron deficient pyrylium rings can interact strongly with the phenyl rings of adjacent molecules forming stacks along the shortest crystallographic axis. The phenyl rings may act as donors in a charge transfer interaction which is more pronounced in 1 than in 2. Charge transfer appears as a non-mandatory consequence of the π-π stacking. The structures demonstrate the electrostatic nature of these interactions conforming to the model of Hunter and Sanders [ 1 ].
Weitere Verbindungen des Ba17Ln16Zn8Pt4O57- Typs mit Ln = Dy, Ho, Er, Y / More Compounds of the Ba17Ln16Zn8Pt4O57 Type with Ln = Dy, Ho, Er, Y
Authors: Sfreddo O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ba17Dy16Zn8Pt4O57 (I), Ba17Ho16Zn8Pt4O57 (II), Ba17Er16Zn8Pt4O57 (III) and Ba17YZn8Pt4O57 (IV) have been prepared by high temperature reactions using platinum crucibles. X-ray investigations led to tetragonal symmetry, space group C5
4h - I4/m, (I) - (IV): a = 22.905(1), 22.840(1), 22.795(1), 22.848(1) Å and c = 5.728(1), 5.722(1), 5.700(1), 5.709(1) Å,Z = 2. The crystal structure is characterized by small square, medium-sized quadrangular and large rectangular tunnels, which are filled by oxygen, barium and zinc. The polyhedra network is discussed with respect to the network of compounds of the Ba13Dy8Zn4Pt4O37 type.
Solvation Structure of Solvated Cu(I) Ions in Non-Aqueous Solvents as Studied by EXAFS and ab initio Molecular Orbital Methods
Authors: Inada Y. , Tsutsui Y. , Wasada H. , Funahashi S.
Published: February 2015

The structure parameters around the Cu(I) ion in pyridine (PY), 4-methylpyridine (4MPY), 2-methylpyridine (2MPY), 2,6-dimethylpyridine (26DMPY), and acetonitrile (AN) were determined by the extended X-ray absorption fine structure (EXAFS) method. The solvation structures of the Cu(I) ion in PY, 4MPY, and AN are 4-coordinate tetrahedral with Cu-N bond lengths of 205, 205, and 200 pm, respectively. In the case of 2MPY and 26DMPY, the Cu(I) ion has a 3-coordinate triangular structure with a Cu-N bond length of 201 pm. Such a decrease in the coordination number was interpreted in terms of the bulkiness of the solvent molecules. In order to clarify the most stable solvation structure of the Cu(I) ion, we carried out ab initio molecular orbital calculations for the solvation system of [Cu(NCH)n]+ (n = 1 - 6 ) where the steric effect is negligible. The Gibbs free energy of solvation was the smallest in the case of n = 4 and the 4-coordinate tetrahedral solvation of the Cu(I) ion was theoretically evaluated as most stable. The enthalpy of solvation monotonously decreases with increasing n, while the entropy of solvation proportionally increases. Although a larger gain of enthalpy is observed for the octahedral structure rather than the tetrahedral one, the entropic loss for the former overcomes the enthalpic gain.
Neue dikationische Silicium-Komplexe mit N-Methylimidazol/New Dicationic Silicon Complexes with N-Methylimidazole
Authors: Hensen Karl , Kettner Markus , Pickel Peter , Bolte Michael
Published: February 2015

The reactions of the dibromosilanes Et2SiBr2, Ph2SiBr2, EtHSiBr2, PhHSiBr2 and MeHSiBr2 with N-methylimidazole (NMI) led to white powders stable at room temperature (with Et2SiBr2 an 1:2 adduct, with EtHSiBr2 and Ph2SiBr2 1:3 adducts, and with PhHSiBr2 and MeHSiBr2 1:4 adducts).

The compounds crystallize from solutions in chloroforme and acetonitrile. The X-ray single crystal investigations show in all five cases dicationic complexes.
Unerwartete Reaktionsprodukte bei der Umsetzung von Mesitylmagnesiumbromid mit Arsentribromid / Unexpected Products from the Reaction of Mesitylmagnesium Bromide and Arsenic Tribromide
Authors: Nöth Heinrich , Waldhör Ralf
Published: February 2015

Irrespective of the ratio of the reactands AsBr3 and mesMgBr (mes = mesityl), two products are formed in THF solution: dimesitylarsenic bromide and a magnesium bromoarsenate of composition MgAs5Br17 · n THF. The latter, on crystallization from acetonitrile, yields [Mg(NCMe)4(THF)2][As3Br11 ]. The anion of this salt can be described as derived from three face sharing AsBr6 octahedra. The lone pair of electrons at the As atoms is stereochemically not active.
α-Dicarbonylmonoxime als Nucleophile und Nachbargruppen / α-Dicarbonylmonoximes as Nucleophiles and Neighbour Groups
Authors: Möhrle Hans , Keller Georg
Published: February 2015

The α-dicarbonylmonooximes 1 and 11 do not react as simple “CH-acidic-compounds” in the Mannich condensation. In a concerted reaction with aminals in absolute dioxane they give rise to the products 4a - e and 12a - e with better practicability and much higher yields compared with the conventional method. The Mannich bases with a cyclic amine part show in the dehydrogenation, using mercury-EDTA, a neighbouring group participation of the oxime in type 4 and of the oxime or amide function in 12 yielding cyclized products. For the reaction a plausible mechanism is proposed.
Microwave-Assisted Oxidation of Alcohols Using Wet Alumina Supported Ammonium Chlorochromate in Solventless System
Authors: Heravi Majid M. , Aghayan Maryam M.
Published: February 2015

A simple and selective method for the oxidation of alcohols to carbonyl compounds is described that occurs on wet alumina supported ammonium chlorochromate under microwave irradiation in solventless system
Metallboranate und Boranatometallate, 25. 25Mg-Kernresonanzuntersuchungen an Magnesiumboranaten [1]
Authors: Nöth Heinrich , Wagner Gerhard E. W. J.
Published: February 2015

25Mg NMR spectroscopy has been used to study the solution behaviour of Mg(BH4)2 · 3 THF, RMg(BH4) · nL (L = various ethers) and ROMg(BH4) · nL. While the solution state of Mg(BH4)2·3 THF remains unchanged in THF or benzene, Schlenk type equilibria are observed for RMg(BH4) compounds. At low temperatures Mg(BH4)2 · nL and MgR2 · nL are the preferred constituents in solution. In contrast, the dimeric ROMg(BH4) compounds do not disproportionate into Mg(OR)2 · nL and Mg(BH4)2 · nL.
The Crystal Structure of N,N′-Bis-(1,3-dihydroxy-2-methylprop-2-yl)- pyrazine-2,3-dicarboxamide Semihydrate
Authors: Klepp Kurt O. , Cuthbertson Alan S. , Fischer Peter M. , Sandoshamb Jessie , Hartmann Michael , Hiebl Johann , Kollmann Hermann , Kremminger Peter , Rovenszky Franz
Published: February 2015

Crystals of the title compound were obtained by recrystallization of N,N′-bis-( 1,3-dihydroxy- 2-methylprop-2-yl)-pyrazine-2,3-dicarboxamide in aqueous methanol. C14H22N4O6 · 1/2H2O crystallizes in the triclinic system, s.g. P1̄ (No. 2) with a = 9.339(4) Å, b = 13.218(9) Å, c = 14.5137(9) Å, α = 70.95(4)°, β = 87.66(4)°, ɣ = 87.13(4)°, Z = 4. Its crystal structure has been determined from diffractometer data and refined to a conventional R of 0.050 (4008 observations, 464 variable parameters). The structure contains two crystallographically independent molecules which are alternatingly stacked above each other along the [001]-direction. Extensive intermolecular hydrogen bonding between these stacks leads to the formation of slabs parallel to (010). The hydrate water is only loosely attached to one of the molecules and has no apparent influence on the stacking.
Synthesis of Benzisochalcogenol and -azole Derivatives via ortho Metalation of Isophthalamides
Authors: Kersting Berthold , DeLion Michael
Published: February 2015

The syntheses of benzofused isochalcogenazole derivatives via ortho-lithiation of isophthalamides is reported. N ,N′ -Dialkyl-isophthalamides, C6H4-1,3-(CONHR)2, bearing R = iPr or tBu substituents are readily ortho metalated by using 3.3 equiv. of n-BuLi/TMEDA. The organo lithium compounds react with S, Se, or Te to give 2-chalcogenol-isophthalamides, C6H3 -1,3- (CONHR)2-2-XH (X = S, Se, Te). Oxidation of the chalcogenols affords dichalcogenides under acidic and benzisochalcogenazoles under basic conditions, respectively. The formation of the five-membered heterocycles proceeds by disproportionation of the dichalcogenides. Oxidation of the benzisothiazoles by hydrogen peroxide gives access to substituted sulfin- and sulfonamides.
Polysulfonylamine, CXIX Wasserstoffbrücken in kristallinen Onium-dimesylamiden: Ein antidromes Achtringmuster als robustes supramolekulares Synthon - Drei prototypische Strukturen/Polysulfonylamines, CXIX Hydrogen Bonding in Crystalline Onium Dimesylamides: An Antidromic Eight-Membered Ring Pattern as a Robust Supramolecular Synthon - Three Prototypical Structures
Authors: Wijaya Kama , Moers Oliver , Blaschette Armand , Jones Peter G.
Published: February 2015

Syntheses and low-temperature X-ray structures are reported for three ionic solids of general formula BH+(MeSO2)2N-, where BH+ is 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidinium (1, monoclinic, space group P21/c), N,N′-diphenylformamidinium (2, monoclinic, P21/c), or 2-phenylaminopyridinium (3, triclinic, P1̄̄, two independent formula units). As a common feature, the onium cations in question exhibit a difunctional hydrogen-bond donor sequence H -N -C (sp2) - N - H geometrically complementary to an O - S - N fragment of the anion. Consequently, the three crystal packings consist of discrete cation-anion pairs (formula units) assembled by an N -H ··· N and an N - H O hydrogen bond. In both independent ion pairs of 3, the N -H ··· N bond originates from the pyridinium centre and the N - H - O bond from the amino group. The eight-membered ring [graph set N2 = R2
2(8), antidromic] that results in all these prototypical structures has potential as a new and robust supramolecular synthon. In each case, short C - H ··· O contacts with H ··· O ≤ 260 pm and C - H ··· O ≥ 140° are present; in 2, two Car - H ··· O hydrogen bonds are assisted by a C(formyl)- H ··· O contact and a π - π interaction to create a centrosymmetric formula unit dimer.
Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH2-, COOH- und P(O)(OR)2-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH2, COOH and P (O)(OR)2 Functionalized Side Chains
Authors: Liek Christian , Machnitzki Peter , Nickel Thomas , Schenk Stefan , Tepper Michael , Stelzer Othmar
Published: February 2015

Nucleophilic phosphanylation of ortho-fluorophenylacetic acid or ortho-fluorobenzylamine with PhPH2 using KOtBu as the base affords the hydrophilic tertiary phosphanes 3 and 4a with terminal CH2-COOH and CH2-NH2 substituents. The corresponding secondary phosphane ligands 2 or 5 may be obtained by Pd-catalyzed P-C coupling of ortho-iodophenylacetic acid with PhPH2 or selective nucleophilic phosphanylation of ortho-fluorophenylacetic acid. Novel phosphonatomethyl derivatives 7a, 7b of triphenylphosphane have been obtained in a two stage synthesis using ortho-iodobenzylchloride or meta-iodobenzylbromide as starting materials. Arbusov reaction with P(OEt)3 and Pd-catalyzed P-C coupling reactions with Ph2PH gave the esters 7a, 7b. Purification of 7a was achieved via its BH3 adduct 8a. Deprotection, hydrolysis and neutralisation with NaOH affords the water soluble sodium salts 9a,9b. α-Hydroxy and α-benzylamino derivatives 12 and 14 of ortho-diphenylphosphanobenzyl phosphonate (e.g. 7a) and the corresponding Me2P(O) analogs 13 and 16 are accessible in a straightforward manner by addition of (MeO)2P(O)H or Me2P(O)H to ortho-phosphanobenzaldehyde 11a or its benzaldimino derivative 15, respectively. An improved synthesis for 11a -11c has been developed. Reaction of 11a with the Wittig reagent Ph3P=C(H)COOEt and subsequent hydrolysis of the intermediate ester 17a affords ortho-diphenylphosphano cinnamic acid 17. The catalytical activity of 1,9a, 9b and related ligands in Suzuki-type coupling reactions has been investigated.
Aminocyclophosphazene Derivatives of Tungsten Carbonyl
Authors: Shrimal A. K.
Published: February 2015

Reactions of aminated cyclotri- and cyclotetra-phosphazenes, viz., N3P3L6 and N4P4L8 (L = -NC4H8O, -NC5H10, -HNC6H11 and -HNC8H17) with W(CO)6 have been studied. [(N3P3L6)W(CO)3] derivatives are obtained with N3P3L6 while N4P4L8 yield tetracarbonyl substituted derivatives, [(N4P4L8)W(CO)4]. Mixed ligand tungsten tricarbonyls of the type [C12H8N2)(N3P3L6 or N4P4L8)W(CO)3] have also been synthesized with [(o-phen)W(CO)4].
Schiff Bases of Methanesulfonylhydrazine. Synthesis, Spectroscopic Characterization, Conformational Analysis, and Biological Activity
Authors: Dodoff Nicolay I. , Özdemir Ümmühan , Karacan Nurcan , Georgieva Milka Ch. , Konstantinov Spiro M. , Stefanova Miglena E.
Published: February 2015

Three novel Schiff bases: salicylaldehyde methanesulfonylhydrazone (1), 2-hydroxyacetophenone methanesulfonylhydrazone (2) and 2-hydroxy-1-naphthaldehyde methanesulfonylhydrazone (3) have been synthesized. Compounds 1-3, as well as acetone methanesulfonylhydrazone (4) have been characterized by TLC, 1H NMR and IR spectra. The spectroscopic results for 1-3 have revealed the presence of an intramolecular hydrogen bond between the hydroxyl group and the imine N atom. The conformational isomerism of 1-4 with respect to the rotations around the SN and NN bonds have been studied by the method of molecular mechanics. Compounds 1-4 and methanesulfonylhydrazine exhibit antibacterial and cytotoxic effects.
Zirconium Reagents for Organometallic Synthesis. Crystal Structures of ZrCl4 ·2Et2O and (Et2N)ZrCl3·Et2O
Authors: Avtomonov Evgeni V. , Rufanov Konstantin A.
Published: February 2015

Reaction of 3 equivalents of ZrCl4 · 2Et2O (1) with 1 equivalent of (Et2N4Zr in diethyl ether readily affords crystalline (Et2N)ZrCl3 · 2Et2O (2) in almost quantitative yield. The product was characterised by elemental analysis and by 1H. 13 C NMR, and MS techniques. The reactivity of this reagent towards C-H acidic compounds has been studied using cyclopentadiene as a C-H acid. The crystal structures of both 1 and 2 have been determined by X-ray diffractometry. The coordination polyhedra reveal a nearly perfect octahedral geometry with a trans Et2O ligation for 1 and a cis one for 2.
X-Ray Structure Analysis of Substituted 5-(2,3-Dihydro-7-benzofuryl)- 1-methylpyrazolo[4,3-d]pyrimidin-7-one (Biagra)
Authors: Voelter Wolfgang , Maichle-Mössmer Cäcilia , Khanfar Monther A. , El-Abadelah Mustafa M. , Sabri Salim S.
Published: February 2015

X-ray crystal structure data for the title compound dihydrobenzofuryl-pyrazolo[4,3-d]pyrimidin- 7-one (2) reveal that the two bicyclic heteroaryl systems are virtually coplanar along their joint C (5)-C(11) axis with an interplanar angle of 1.13°. This planar conformation is held by an intramolecular hydrogen bond between the pyrimidinone N(6)-H and the O(17) lone pair of the dihydrobenzofuryl moiety. The spatial interatomic distance for O(17)-N(6), determined as 2.04 Å, favours this H-bridge.
Crystal Structure and Magnetic Properties of a Linear Trinuclear Ni(II) Complex
Authors: Kavlakoglu E. , Eimali A. , Elerman Y. , Werner R. , Svoboda I. , Fuess H.
Published: February 2015

Linear Trinuclear Nickel(II) Complex, Super-Exchange Interactions, Antiferromagnetic Coupling [Ni3(C2H32(CH3O)2L2] [L = 13-bis(5-chlorosalicylideneamino)propan-2-ol dianion, (C2H3O2)- = acetate, (CH3OH) = methanol] was synthesized and its crystal structure was determined. It crystallizes in the monoclinic spaceeroup P21 /n with a = 12.694(2), b = 13.281 (4), c = 15.420(3) Å, β = 111.25(2)°, V = 2422.9(9) Å3 ,Z = 2 . The molecule is a "linear" trinuclear complex with nearly octahedral coordination of each nickel ion. Adjacent nickel(II) ions are bridged by the phenolic oxygen atoms of the ligands and the oxygen atoms of the acetato ligands. The coordination sphere of the terminal nickel(II) ions is completed by the oxygen atom of the methanol. Adjacent nickel(II) centers are separated by 3.043(1) Å and weakly antiferromagnetically coupled (J1 = -3 .4 cm-1). The terminal nickel(II) centers are separated by 6.086(1) Å and very weakly antiferromagnetically coupled (J2 = -0 .3 cm-1) which follows from temperature-dependent magnetic susceptibility measurements in the temperature range 4.5 to 318 K. The magnetic moment rises from 2.99 μB at 4.5 K to 5.42 μB at 318 K. In the X(T) curve no characteristic maximum was observed.
Spectro-Electrochemistry of Diethyldithiocarbamate Complexes of Ni(II), Pd(II) and Pt(II)
Authors: Yaman Şeniz Özalp , Önal Ahmet M. , Isci Hiüseyin
Published: February 2015

The electrochemical behaviour of Na(Et2NCS2) and M(Et2NCS2)2 (M= Ni(II), Pd(II) and Pt(II); Et2NCS2
-= diethyldithiocarbamate) as studied by cyclic voltammetry in the acetonitrile-( n-Bu)4NBF4 solvent-electrolyte couple at room temperature vs. Ag/Ag+ reference electrode. Constant potential electrolyses of the complexes were carried out at their first oxidation peak potentials and monitored in situ by UV-VIS spectrophotometry. The electrolysis of Ni(Et2NCS2)2 in solution yielded the dimer of the ligand, (Et2NCS2)2, and Ni2+(sol) as final products. During this electrochemical process the formation of a Ni(III) complex species as an intermediate has been observed. The electrochemical oxidation of bis(diethyldithiocarbamato) complexes of Pd(II) and Pt(II) yielded [Pd(Et2NCS2)3]+ and [Pt(Et2NCS2)3]+, respectively.
Untersuchungen an Polyhalogeniden, XXXXII [1]. Das Pentaiodid-Ion I5
-; Eine Übersicht: Darstellung und Kristallstruktur der Verbindung [Rb(C16H24O6)](I5) · H2O
Authors: Pantenburg Ingo , Tebbe Karl-Friedrich
Published: February 2015

[Rb(benzo-18-crown-6)](I5) H2O could be prepared by the reaction of benzo-18-crown-6, rubidium iodide, and iodine in ethanol / dichloromethane. It crystallizes in the monoclinic space group P21/a with a = 1881.8(3), b = 1439.0(2), c = 2269.0(3) pm, ß = 111.24(1)° and Z = 8. The crystal structure was refined to RF = 0.038 for 5310 reflections. It contains two independent molecules. The two cations and the coordinating water molecules form a zigzag chain running along [100] paralleled by two structurally similar pentaiodide chains with one leg of the V-shaped pentaiodide ion forming the backbone of the chain. In both cases the other leg stands out in a novel fashion without forming a coplanar cis or trans configuration known from other pentaiodides. Anionic motifs of other crystalline pentaiodides are summarized and discussed.
Dependence of the Distortion of the Square Pyramids in N, N-Dimethylethylenediammonium Pentachloroantimonate(III) on the Geometry of Hydrogen Bonds
Authors: Bujak Maciej , Zaleski Jacek
Published: February 2015

N ,N-Dimethylethylenediammonium pentachloroantimonate(III) crystallizes in the monoclinic system, in space group P21/c (a = 12.460(2), b = 10.252(2), c = 10.330(2) Å, β = 97.75(3)°, V = 1307.5(4) Å3, Z = 4, dc = 1.997, dm = 1.99(2) g/cm3). The crystal structure of [(CH3)2NH(CH2)2NH3][SbCl5] consists of isolated [SbCl5]2- anions and [(CH3)2NH(CH2)2NH3]2+ cations. The [SbCl5]2- anion has a distorted square pyramidal geometry, presenting one short axial and four long equatorial Sb-Cl bonds. The square pyramids are characteristically stacked one close to the other, parallel to the c axis. The voids between the anionic sublattice are filled by [(CH3)2NH(CH2)2NH3]2+ cations. The five non-equivalent Sb-Cl bond distances within the [SbCl5]2- square pyramid are significantly different. The equatorial Sb-Cl bonds are in the range 2.427(2)-2.968(2) Å, whereas the axial one is 2.384(1) Å long. The study reveals that N-H...C1 hydrogen bonds are responsible for the deformation of equatorial Sb-Cl bonds from the mean value of 2.654(7) Å. Analysis of intermolecular interactions between the [SbCl5]2- pyramids in the structure, reflected in changes of Sb-Cl bond lengths from the values characteristic of non-interacting pyramids, leads to the conclusion that the van der Waals radius of Sb is significantly smaller than that estimated by Pauling.