bluuebunny/crossref_metadata_2025 huggingface dataset:
Methansulfinylchlorid-Lewissäure-Addukte CH3S(Cl)OMF5 (M = As, Sb) und Kristallstruktur von CH3S(Cl)OSbCl5 [1] / Methanesulfinylchloride Lewis Acid Adducts CH3S(Cl)OMF5 (M = As, Sb) and Crystal Structure of CH3S(Cl)OSbCl5 [1]
Authors: Minkwitz Rolf , Lohmann Ulrike , Preut Hans
Published: February 2015

CH3S(0)C1 reacts in HF as solvent with MF5 (M = As, Sb) to give products CH3S(Cl)OMF5 (M = As, Sb). The new compounds are stable below 253 K and were charac­ terized by Raman and NMR spectroscopy.

In addition, the crystal structure of CH3S(Cl)OSbCl5 has been determinated. The complex crystallizes in the monoclinic space group P21/n with a = 644.3(5), b = 1905.9(14), c = 900.0(7) pm, β = 99.27(6)° with four formula units per unit cell.
1,4-Dibromonaphthalene-2,3-diylbis(1′-bromo-2′-naphthoate)·CHCl3, a Potential Precursor to Lactone-Bridged Teraryls
Authors: Peters Karl , Peters Eva-Maria , Bringmann Gerhard , Harmsen Sven
Published: February 2015

The title compound was prepared from 1,4-dibromo- 2,3-dihydroxynaphthalene by two-fold esterification with 1-bromo-2-naphthoic acid. It crystallizes from chloroform in the triclinic system, space group P1̄; a = 1226.6(3), b = 1246.9(3), c = 1218.8(3) pm, α = 107.50°, β = 90.94°, γ = 113.56°. The asymmetric unit is described with a statistically disordered CHCl3.
Zwischenmolekulare Wechselwirkungen bei RSbCl2 und die Bildung cyclischer Organoantimon(III)-chalkogenide, (RSbE)n [R = (Me3Si)2CH, E = S, Se, Te] / Intermolecular Interactions of RSbCl2 and Formation of Cyclic Organoantimony(III) Chalcogenides, (RSbE)n [R = (Me3Si)2CH, E = S, Se, Te]
Authors: Mohammed Mohammed A. , Ebert Klaus H. , Breunig Hans Joachim
Published: February 2015

Alkylantimony Dichloride, Cyclostibane Chalcogenides The crystal structure of the compound (Me3Si)2CHSbCl2 (1) has been determined as obtained from the melt. It contains dimers with in­ termolecular Sb···Cl distances of 351.8 (1) pm. Reactions of 1 with the corresponding sodium chalcogenides yield the products (RSbS)n (2), (RSbSe)n (3) and (RSbTe)n (4) [R = (Me3Si)2CH], The mass spectra of 2-4 give peaks for the dimers, trimers and tetramers, while the NM R spectra of solutions of 2-4 in CDCl3 show that the trimers are the most abundant species in ring-ring-equilibria.
Strukturen ladungsgestörter oder räumlich überfüllter Moleküle, 80 [1 - 3] Strukturänderungen von p-Benzochinon durch Donator- und Akzeptor-Substituenten
Authors: Bock Hans , Nick Sabine , Seitz Wolfgang , Näther Christian , Bats Jan W.
Published: February 2015

The structures of seven di- or tetrasubstituted p-benzoquinone derivatives O=C(XC=CH )2C=O and O=C(XC=CX)2C=O with substituents X = -OCH3, -N(CH2)5, - N(CH2CH2)2O, -Cl, -CN and -⊕N(HC=CH)2C-N(CH3)2 are presented and discussed in comparison with published ones substituted by X = -Si(CH3)3, -C6H5, -N(CH3)2, -⊕N(HC=CH)2CN(CH3)2, -O⊖ , and - NO2. Based on the introduction, in which halfwave-reduction potentials, geometry-optimized quantum-chemical calculations on substituent perturbation and known structural data of p-benzoquinone derivatives are used to characterize their molecular ground states. The structural changes indicate how substituent perturbations might be rationalized. Of the categories defined - imperturbed, donor, donor/acceptor and acceptor perturbed - the donorsubstituted p-benzoquinones do exhibit the largest differences, often called cyanine distorsion. In very satisfactory agreement with extensive semiempirical calculations, all effects determined experimentally are discussed in terms of varying charge distribution. With respect to the biochemical importance of p-benzoquinone derivatives, this first structural summary points out important facets.
Nickelkomplexe mit Thioether-Chelatliganden: Elektrochemische Eigenschaften und Kristallstrukturen von [Ni(MeSCH2CH2SMe)2 (NCS)2], [Ni(EtSCH2CH2SEt)2(NCS)2] und [Ni(MeSCH2CH2SMe)2Br2]
Authors: Köckerling Martin , Henkel Gerald
Published: February 2015

Current interest in nickel complexes with sulfur donor ligands as models for the active sites of nickel-containing hydrogenases has prompted us to investigate the structural and electrochemical behaviour of nickel complexes with bifunctional thioether ligands. Crystals of [Ni(MeSCH2CH2SMe)2(NCS)2] (1) and [Ni(EtSCH2CH2SEt)2(NCS)2], (2) are triclinic, space group Pī, Z = 1, 1: a = 7.293(3) Å, b = 7.567(3) Å, c = 8.784(3) Å, α = 72.81(3)°, β = 78.41(3)°, γ = 85.14(3)°; 2: a = 8.611(1) Å, b = 8.101(1) Å, c = 9.163(1) ßrbÅ, α = 66.54(1)°, β = 76.19(1)°, γ = 67.88(1 )ßrb°. [Ni(MeSCH2CH2SMe)2Br2] (3) crystallizes in the monoclinic space group P21/n, a = 6.757(2) A, b = 7.881(2) Å, c = 14.674(4) Å, β = 94.05(2)°, Z = 2. In crystals of 1, 2 and 3 mononuclear neutral complex molecules are observed which have pseudo-octahedral trans-NiS4L2 coordination sites. The cyclovoltammograms of 1 and 3 in MeCN (Ag/AgCl/KCl, 3 mol/l) show only irreversible oxidation waves at +837 mV for 1 and +846 mV for 3, respectively, which are characteristic features of NCS⊖ and Br⊖ ions. In addition, a reduction wave at +393 mV is observed in 3. No redox response is found in the potential region between -700 and +100 mV which is used by the NiFe hydrogenase enzymes.
Zur Kristallchemie von CuDyMo2O8 und CuYbMo2O8
Authors: Müller-Buschbaum Hk. , Gallinat St.
Published: February 2015

Single crystals of (I) CuDyMo2O8 and (II) CuYbMo2O8 have been prepared by crystalli­sation from melts. Both com pounds crystallize with orthorhombic symmetry, space group D15
2h-Pbca with (I): a = 10.195(1), b = 9.721(2), c = 14.563(3); (II): a = 10.094(6), b = 9.628(9), c = 14.467(8) Å, Z = 8. The crystal structure is characterized by a triangular CuO3-polygon, a square antiprismatic coordination around the Rare Earth ions and the typical Mo O4 tetra­ hedra.
Preparation and Crystal Structure of the Isotypic Carbides Ln3.67TC6 (Ln = rare earth elements; T = Mn, Fe, Ru) and Eu3,16NiC6
Authors: Witte Anne M. , Jeitschko Wolfgang
Published: February 2015

The 14 carbides Ln3.67MnC6 (Ln = La-Nd) and Ln3.67TC6 (Ln = La-Nd, Sm; T = Fe, Ru) were prepared from the elemental components by arc-melting and subsequent annealing. Eu3.16NiC6 was obtained from a lithium flux. The crystal structures of these nearly isotypic, hexagonal compounds (P63/m, Z = 2) were determined from single-crystal X-ray data; La3.67- FeC6: a = 878.7(2), c = 535.1(1) pm, R = 0.052 for 548 structure factors and 25 variable parameters; Eu3.16NiC6: a -860.0(1), c = 548.2(2) pm, R = 0.015 for 606 structure factors and 25 variables. The structures differ from the previously reported Gd3Mn2C6 structure by the occupancy of one manganese position by rare earth atoms. Since the lanthanum atoms are larger than the manganese atoms, only two thirds of these manganese positions can be occupied by the lanthanum atoms in La3.67FeC6. Eu3.16NiC6 has similar atomic positions. The C-C bond distances in the C2 pairs are 130(2) and 126.5(5) pm in the La and Eu compounds, respectively. Magnetic susceptibility measurements with a SQUID magnetometer indicate La3.67FeC6 to be Pauli paramagnetic. A test for superconductivity was negative down to 3 K.
Bis(triphenylphosphoniumyIidyl)phosphane
Authors: Jochem G. , Schmidpeter A. , Nöth H.
Published: February 2015

Bis(ylidyl)phosphanes can be prepared from ylides and dichlorophosphanes or from bis-(ylidyl)phosphenium chlorides and organolithium compounds. By substituting in bis(ylidyl)-phosphenium chlorides the chloride ion for more basic anions, a large variety of bis(ylidyl)-phosphanes is accessible. They can be protonated at the ylidic carbon atoms, but alkylated and oxidized at the central phosphorus atom. As shown by 31P NM R in solution and by X-ray investigation of the crystal, the lone pair at the tervalent phosphorus is generally oriented synperiplanar to both phosphonio groups.
Liquid Crystalline Compounds in the Thiophene Series, Part 12+ Synthesis and Characterization of Side Chain Polysiloxanes with Low Transition Temperatures
Authors: Koßmehl Gerhard , Labahn Bettina
Published: February 2015

Polysiloxanes as side chain polymers containing the 2.2′-bithiophene unit, hexyl and octyl terminal groups and spacer units with 3, 5. 6 and 10 methylene groups were prepared and characterized. These polymers have monotropic liquid crystalline phases with transition tem ­ peratures below 0 °C (e. g. for polymer 6p: isotropic → liquid crystalline transition: -20 °C; liquid crystalline → solid transition: -43 °C). Polymers with a trimethylene spacer group must contain an octyl terminal group for forming liquid crystalline phase; a hexyl group does not form such a phase.
Synthese und [4+2]-Cycloadditionen von 4a, 8a-Methanophthalazin, das erste Propellan mit einem elektronenreichen und einem elektronenarmen 4π-Diensystem/Synthesis and [4+2] Cycloaddition Reactions of 4a, 8a-Methanophthalazine, the First Propellane with an Electronrich and an Electrondeficient 4π-Diene System
Authors: Laue Jörg , Seitz Gunther , Waßmuth Hans
Published: February 2015

Cyclopropabenzene 3 reacts with 3,6-bis(trifluoro)-1,2,4,5-tetrazine 4 to afford in high yield the 4a,8a-methanophthalazine 6, the first propellane, containing an electron rich cyclohexadiene system on the one hand and an electron deficient diazadiene system on the other hand. According to the principle of Diels-Alder reactions with inverse electron demand, electron rich dienophiles like ketene acetals, enamines or dimethyl hydrazones react predominantly with the diazadiene system to yield the azo-bridged cycoadducts of type 19 and/or the tricyclic tetrahydropyridazines like 20. In the same fashion several more or less angle strained cycloalkenes cycloadd to the diazadiene of the propellane 6 to give the novel polycyclic azo compounds 34, 36, 38,40, 42 and 44 with exo-configuration of the annulated cycloalkanes. Attack apparently occurs from less hindered face anti to the methano bridge of 6 with high stereo-and site-selectivity. As anticipated the electron deficient dienophiles 1,2,4-triazoline-3,5-dione 45 and the benzoquinone 46 add with different site selectiviy to 6 furnishing the polycyclic pyridazines 47 and 48 resp. again by exclusive anti attack. Treatment of 6 with both an electron rich and an electron deficient dienophile like 49 and 45 resp. affords the heptacyclic anti-anti-bis adduct 51 with analogously high site-and stereoselectivity.
Darstellung, 11B-, 13C-, 1H-NMR- und Schwingungsspektren von μ-Dimethylen-bis-hexahydro-closo-hexaborat, [B6H6(CH2)2B6H6]2-, sowie Kristallstrukturen von [As(C6H5)4]2[B6H6(CH2)2B6H6]·[(CH3)2CO] und [P(C6H5)4]2[B6H6(CH2)2B6H6]·[C2H5OH]/Preparation, 11B , 13C, 1H NMR and Vibrational Spectra of μ-Dimethylene-bis-hexahydro-closo-hexaborate, [B6H6(CH2)2B6H6]2- , and the Crystal Structures of [As(C6H5)4]2[B6H6(CH2)2B6H6]·[(CH3)2CO] and [P(C6H5)4]2[B6H6(CH2)2B6H6]·[C2H5OH]
Authors: Lübbe W. , Preetz W.
Published: February 2015

By reaction of [B6H6]2- with dibromoethane in acetonitrile μ-dimethylene-bis-hexahydro-closo-hexaborate(2-), [B6H6(CH2)2B6H6]2-, is formed. The compound was separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of [As(C6H5)4]2[B6H6(CH2)2B6H6]·[(CH3)2CO] (I) and [P(C6H5)4]2[B6H6(CH2)2B6H6]·[C2H5OH] (II) have been determined by single crystal X-ray analysis: I is triclinic, space group P1̄ with a = 10.264(2), b = 13.804(2) and c = 20.242(2) Å, α = 97.857(10)°, β = 92.734( 11)° and γ = 103.024( 13)°; II is monoclinic, space group P21/n with a = 12.742(2), b = 7.532(2) and c = 26.887(3) Å, β = 95.765( 10)°. The 11B NMR spectrum of this compound reveals the feature of monosubstituted octahedral B6 cages. The 13C NMR spectrum exhibits a triplet at 16.20 ppm with 1J(C,H) = 120.4 Hz. In the 1H NMR spectrum a singulet at 0.72 ppm of the CH2-groups and two singulets at 1.72 and -4.95 ppm of the BH fragments are observed. The IR and Raman spectra exhibit strong CH stretching bands between 2908 and 2789 cm-1, BH stretching bands between 2463 and 2396 cm-1, and the BC stretching vibration at 1144 in the IR and at 1150 cm-1 in the Raman spectrum.
Synthese und Dimerisierungsverhalten des 1,1-Bis(trimethylsilyl)-2-(2,5-diisopropylphenyl)silens/ Synthesis and Dimerization Behavior of 1,1 -Bis(trimethylsilyl)-2-(2,5-diisopropylphenyl)silene
Authors: Hoffmann Douglas , Reinke Helmut , Oehme Hartmut
Published: February 2015

Tris(trimethylsilyl)silylmagnesium bromide, (Me3Si)3SiMgBr, reacts with 2.5-diisopropylbenzaldehyde to give 2,5-diisopropylphenyl-tris(trimethylsilyl)silylmethanol (1). With sodium hydride in THF compound 1 undergoes a rearrangement through 1,3-Si,O-trimethylsilyl migration affording bis(trimethylsilyl)silyl-(2,5-diisopropylphenyl)-trimethylsiloxy-methane (4). The deprotonation of 1 with organolithium reagents in ether leads to the elimination of lithium trimethylsilanolate according to a modified Peterson mechanism resulting in the formation of the transient silene (Me3Si)2Si=CH(2,5-iPr2C6H3) (2). Treatment of 1 with an excess of phenyllithium in diethylether at low temperature gives 1,1,1,3,3,3-hexamethyl-2- phenyl-2-(2,5-diisopropylbenzyl)-trisilane (3), formed in a nucleophilic addition of the excess PhLi to the silene intermediate and in the hydrolytic workup. Stochiometric quantities of MeLi in diethylether at -78 °C convert compound 1 into a head-to-head dimer of the silene 1,2,3,8a-tetrahydro-5,8-diisopropyl-1 -(2,5-diisopropylphenyl)-2,2,3,3-tetrakis-(trimethylsilyl)- 2,3-disilanaphthalene (5). Compound 5, presumably the kinetically preferred product of the cyclodimerization of 2, gradually transforms into the thermodynamically stable 3,4-bis(2,5- diisopropylphenyl)-1, 1,2,2-tetrakis(trimethyl-silyl)-1,2-disilacyclobutane (6). The E/Z-isomers of 6 have been characterized by X-ray crystal structural analyses.
Verknüpfung koordinativ ungesättigter Kupfer(II)-Monomere via Cyano-versus Tetrazolyl-Donor/ Linkage of Coordinatively Unsaturated Copper(II) Monomers via Cyano versus Tetrazolyl Donor
Authors: Saalfrank Rolf W. , Harbig Roland , Struck Oliver , Peters Eva-Maria , Schnering Hans Georg von
Published: February 2015

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a (HL2) or 2b (HL3) leads to the formation of the corresponding 2D-coordination polymers 4 (∞
2 [CuL2
2]) and 5 (∞
2 [CuL2
3]), respectively. Single-crystal X-ray diffraction of the supramolecular species 4 and 5 established unequivocally the structures of the regioisomeric coordination polymers. On the contrary, reactions of 2c (HL4) with methanolic copper(II) acetate solution and 2b (HL3) with methanolic zinc(II) acetate solution yield mononuclear chelate complexes 11 ([CuL4
2]) and 12 ([ZnL23(MeOH)2]). The structures of 11 and 12 have been established by X-ray structure analysis.
Vinamidinium-Salze als Nucleophile Vinamidinium Salts as Nucleophiles
Authors: Möhrle H. , Lieck-Waldheim U. von der
Published: February 2015

2,3-Dihydro-1,4-diazepinium salts could not be aminomethylated with conventional methods, but the hydrochlorides produced with methyleniminium salts the C-Mannich-compounds. The reactivity of the substrate was mainly controlled by electronic effects of the substituents. Aminomethylation of 1,5-diazapentadienium salts occurred only if the conformations caused no steric hindrance of the β-C-atom. Methyl substituted 2,3-dihydro-1,4-diazepinium salts reacted with 1,3,5 triazine to pyrimidine anellated derivatives.
The Crystal Structure of β-CsIO4, the Room-Temperature Modification of Cesium Periodate
Authors: Waal Danita de , Zabel Manfred , Range Klaus-Jürgen
Published: February 2015

The crystal structure of β-CsIO4, the room-temperature modification of cesium periodate, was determined as orthorhombic, space group Pnma, with a = 5.8644(5), b = 6.0326(4), c = 14.379(1) A and Z = 4.

The structure was refined to R1= 0.0309, wR2 = 0.0701 for 425 absorption-corrected reflections. β-CsIO4 is isostructural with β-CsReO4. The structure comprises isolated IO4 tetrahedra, linked together by Cs ions. The average I-O dis­tance was found to be 1.747 Å .
Synthese und Kristallstruktur des Barium -Kupfer-Tellurit-Tellurats BaCuTeO3TeO4 / Synthesis and Crystal Structure of the Barium Copper Tellurite-Tellurate BaCuTeO3TeO4
Authors: Sedello O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of BaCuTeO3TeO4 have been prepared by crystallisation from melts. X-ray investigations lead to orthorhombic symmetry, space group C16
2v-Ama2, a = 5.4869(8), b = 15.412(1), c = 7.2066(4) Å , Z = 4. This compound represents a new structure type, containing BaO10, CuO5, TeO6 and TeO4 polyhedra. The lone pair (E) of TeIV completes the TeIVO4 polyhedron to a trigonal TeO4E bipyramid. The Te to E distance is estimated by calculations of the Coulomb terms of lattice energy to 1.43 Å .
Eine silberhaltige Phase eines Oxoruthenats: Ag0,4 (Na2,3Ca4,3RuO8 / A Silver Containing Phase of an Oxoruthenate: Ag0,4Na2,3Ca4,3RuO8
Authors: Frenzen S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ag0.4Na2.3Ca4.3RuO8 have been prepared by heating Na2O2, CaO and ruthenium in closed silver tubes. Silver took part in the reaction. The crystal structure was investigated by X-ray techniques. AgO4Na2.3Ca4.3RuO8 crystallizes with orthorhombic symmetry, space group D19
2h-Cmmm ; a = 9.255(1), b = 6.683(1), c = 6.696(3) Å , Z = 2. It shows relations to the sodium chloride structure. A statistical distribution of Ag+ and Na+ can be separated in micro space by splitting one oxygen position to give a dumb-bell like O-Ag-O and an octahedral NaO6 coordination.
Kristallstrukturuntersuchung am Barium-Yanadyl-Vanadat: Ba2(VO)V2O8 / Crystal Structure Investigation of the Barium Vanadyl-Vanadate: Ba2(VO)V2O8
Authors: Feldmann J. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ba2(VO)V2O8 have been prepared by solid state reactions of Ba2V2O7, V2O3 and V2O5 in sealed silica tubes. This compound crystallizes with monoclinic symmetry, space group C2
2 -P21, a = 8.1174(9), b = 5.9699(9), c = 9.2903(9) Å , β = 113.94(1)°, Z = 2. V 5+ shows tetrahedral coordination. V 4+ inside 1
∞ [V (3)O4] chains is characterized by a square pyramidal coordination with a short apical V-O distance of 1.6 Å typically for vanadyl groups. Ba2(VO)V2O8 represents a new structure type and is not isotypic to Sr2(VO)V2O8.
Zweidimensionales Eis und H5O2
+-Ionen. Zur Bildung und Struktur tiefschmelzender molekularer und ionischer Hemi-bis Hexahydrate halogenierter Essigsäuren CClnF3-nCOOH (n = 1 bis 3) [1] / Two-Dimensional Ice and H5O2
+ Ions. On Formation and Structure of Low-Melting Molecular and Ionic Hemi-through Hexahydrates of Haloacetic Acids CClnF3-nCOOH (n = 1 to 3) [1]
Authors: Dahlems Thomas , Mootz Dietrich , Schilling Michaela
Published: February 2015

Hydrate formation of haloacetic acids CClnF3-nCOOH (n = 1, 2, 3) has been studied by DTA and temperature-dependent X-ray powder diffraction, and evidence obtained for five phases, all melting at temperatures below ambient. The hydrates have been confirmed and further characterized by their crystal structures at -150 °C. Three lower hydrates, CCl2FCOOH· 0.5H2O (space group P21/c and Z = 8 formula unites per unit cell), CClF2COOHH2O (P21/c, Z = 4), and CClF2COOH ·4H2O (P1̄, Z = 2), have molecular structures with the acid and water molecules hydrogen-bonded in two-dimensional arrays. The structures of the remaining hydrates, CCl2FCOOH·6H2O and CCl3COOH · 6H2O (similar, but not isotypic, both P1̄ and Z = 2), are ionic, as (H5O2
+)(CX3COO-) · 4H2O , and three-dimensional. The neutral water molecules are hydrogen-bonded in ice-like layers rare in crystal chemistry. Also, CCl2FCOOH is established only as the second acid of which a lower hydrate is molecular and a higher one ionic.
Hydrolyse von Trifluoracetylaceton-salicylhydrazon / Hydrolysis of Trifluoroacetylacetone Salicylhydrazone
Authors: Kraudelt Heide , Ludwig Eberhard , Schilde Uwe , Uhlemann Erhard
Published: February 2015

The reaction of trifluoroacetylacetone with salicylhydrazone gives acetone salicylhydra­ zone besides the expected trifluoroacetylacetone salicylhydrazone. The resulting mixture was analyzed by mass spectroscopy. The structure of acetone salicylhydrazone was determined by X-ray analysis. Crystal data: a = 12,8493(12) Å, b = 6,1084(8) Å, c = 12,757(3) Å; space group Pna21; Z = 4; R = 0,051 ; 750 unique reflexions.
CsNaTe - Darstellung und Charakterisierung von Cäsiumnatriumtellurid / CsNaTe - Preparation and Characterization of Cesium Sodium Telluride
Authors: Fischer Karsten , Feldbaum-Möller Elisabeth , Vogt Petra , Winter Volker , Sabrowsky Horst
Published: February 2015

The dark green compound CsNaTe has been prepared. The characterization by X-ray powder methods leads to a tetragonal lattice (P4/nmm) with a = 530.8 (4), c = 853.2 (1) pm and Z = 2. The structure ist related to the PbFCl structure type.
Optische Absorption der Auride M3AuO ( M = K, Rb, Cs) / Optical Absorption of the Aurides M3AuO (M = K, Rb, Cs)
Authors: Feldmann Claus , Jansen Martin
Published: February 2015

The optical absorption of the aurides M3AuO (M = K, Rb, Cs) and CsAu has been determ inated by UV/VIS spectroscopy. The band gaps have been found to be 2,35(2) eV (Cs3AuO) and 2,30(2) eV (CsAu). This corresponds to a more pronounced anionic character of gold in Cs3AuO as compared to CsAu. In the case of K3AuO and Rb3AuO no band gap was detectable.
Synthese und Eigenschaften von Benzylgallium(indium)-Verbindungen. Die Kristallstrukturen von [(PhCH2)2GaBr]2, [(PhCH2)2GaN(H)t-Bu]2 und [PhCH2InCl2(THF)2] / Synthesis and Properties of Benzylgallium(indium) Compounds. The Crystal Structures of [(PhCH2)2GaBr]2, [(PhCH2)2GaN(H)t-Bu]2 and [PhCH2InCl2(THF)2]
Authors: Kräuter Thomas , Werner Bert , Neumüller Bernhard
Published: February 2015

(PhCH2)2GaBr (1) can be obtained by the redistribution reaction of GaBr3 with Ga(CH2Ph)3 in a molar ratio 1:2. Treatment of 1 or (PhCH2)2GaCl with one equivalent of LiN(H)t-Bu gives the diorganogallium amide [(PhCH2)2GaN(H)t-Bu]2 (2). The toluene-insoluble PhCH2InCl2 can be structurally investigated after dissolving in THF and crystallization as [PhCH2InCl2(THF)2] (3). 1 - 3 were characterized with NMR, IR and MS techniques as well as by X-ray structure determinations. 1 forms two crystallographic independent dimers while 2 is a centrosymmetric dimer in the solid state. 3 is a monomer with a trigonal-bipyramidal coordination sphere at the indium center.
Preparation, Crystal Structure, and Properties of the Lanthanoid Carbides Ln4C7 with Ln = Ho, Er, Tm, and Lu
Authors: Czekalla Ralf , Jeitschko Wolfgang , Hoffmann Rolf-Dieter , Rabeneck Helmut
Published: February 2015

The isotypic carbides Ln4C7 (Ln = Ho, Er, Tm, Lu) were prepared by arc-melting of the elemental components, followed by annealing at 1300 °C. The positions of the metal and of some carbon atoms of the monoclinic crystal structure of LU4C7 were determined from X-ray powder data, and the last carbon positions were found and refined from neutron powder diffraction data: P21/c, a = 360.4(1), b = 1351.4(3), c = 629.0(2) pm, β = 104.97(2)°, Z = 2, R = 0.026 for 429 structure factors and 15 positional parameters. The structure contains isolated carbon atoms with octahedral lutetium coordination and linear C3-units, with C-C bond lengths of 132(1) and 135(1) pm. This carbide may therefore be considered as derived from methane and propadiene. The hydrolysis of LU4C7 with distilled water yields mainly methane and propine, while the hydrolyses of the corresponding holmium and erbium carbides resulted in relatively large amounts of saturated and unsaturated C2-hydrocarbons in addition to the expected products methane and propine. The structure comprises two-dimensionally infinite NaCl-type building elements, which are separated by the C3-units. It may be described as a stacking variant of a previously reported structure of HO4C7, now designated as the a-modification. The Lu4C7-type β -modification was obtained at higher temperatures. Its structure was refined by the Rietveld method from X-ray powder data to a residual R = 0.037 for 320 F values and 15 positional parameters. Lu4C7 is Pauli paramagnetic; β -HO4C7 and Er4C7 show Curie-Weiss behavior with magnetic ordering temperatures of less than 20 K.
Die elektronische Struktur ternärer Übergangsmetallpnictide. I. AlB2-Varianten / The Electronic Structure of Ternary Transition Metal Pnictides. I. AlB2-Variants
Authors: Johrendt Dirk , Mewis Albrecht
Published: February 2015

The electronic structure and bonding of some ternary AlB2-type compounds AMX (A=2a-, X=5b-element, M=transition metal) were studied by means of Extended-Hückel and TBLMTO- ASA calculations. Previous geometric stability criteria of the AIB2 structure have been extended, and reasons for some structural peculiarities and distortions are given. A simple orbital interaction scheme based on local symmetry is used as starting point to investigate the electronic properties of these compounds, whereas the band structures of the ZrBeSi-type SrPdAs and the Peierls-distorted variants CaPdAs and BaPdP are described in more detail. The results of calculations and resistivity measurements are discussed within the scope of Zintl’s concept under consideration of the transition metal d-orbitals. It turns out that these solids can be described as metallic Zintl compounds.
Structure and Spin-Spin Interactions in a Linear Trinuclear Ni(II) Complex
Authors: Elmali Ayhan , Elerman Yalcin , Svoboda Ingrid , Fuess Hartmut , Griesar Klaus , Haase Wolfgang
Published: February 2015

[Ni3(C2H3O2)2(C3H8NO)2L2] [(L=N,N′-1,3-propyl-disalicylaldimine), (C2H3O2)=acetate, (C3H8NO)=hydroxymethyl-dimethylamine] has been synthesized and its crystal structure determined, [C44H54N6O10Ni3], triclinic, space group P1̄, a = 9.560(1), b = 10.681(1), c = 12.200(1) Å, α = 112.17(1), β = 101.25(1), γ = 90.32(1)°, V = 1127.3 Å, Z = 1.The molecule is linearly trinuclear with octahedral coordination of each nickel ion. The Ni-Ni distance is 3.048( 1) Å. Each nickel(II) atom is in an octahedral coordination. Magnetic susceptibility measurements in the range 4.2 < T < 280 K have revealed antiferromagnetic coupling between adjacent Ni atoms (J1 = -2.2 cm-1) and between the terminal Ni atoms (J2 = -1.7 cm-1).
Synthese und Kristallstruktur von Lanthanoidzinkboraten LnZn(B5O10) mit Ln = Ce, Nd, Tb / Synthesis and Crystal Structure of Rare Earth Zinc Borates LnZn(B5O10) with Ln = Ce, Nd, Tb
Authors: Busche Silke , Bluhm Karsten
Published: February 2015

Single crystals of the new compounds LnZn(B5O10) (Ln = (A) Ce3+, (B) Nd3+, (C) T b3+) were obtained by using a B2O3 flux technique. X-ray investigations led to space group C2h
5-P21/n (Nr. 14) with lattice parameters: (A) a = 874.5(1), b = 761.4(1), c = 950.0(1), β = 92.80(1)°, (B) a = 868.6(2), b = 760.9(2), c = 946.0(2), β = 92.99(2)°, (C) a = 858.2(2), b = 760.5(2), c = 939.3(2), β = 93.56(2)°, Z = 4. The structure is isotypic with CoSm(B5O10) and is characterized by two-dimensional infinite 2
∞ (B5O 10)5- ions. Ln is tenfold coordinated by oxygen, and Zn2+ occupies distorted ZnO6 polyhedra.
Synthese und Kristallstruktur von NiHo2(B2O5)2, das erste Nickellanthanoidborat mit einem 2
∞(B2O5)4- -Anion / Synthesis and Crystal Structure of NiHo2(B2O5)2, the First Nickel Lanthanoid Borates with a (B2O5)4- Anion
Authors: Bluhm Karsten , Wiesch André
Published: February 2015

Single crystals of NiHo2(B2O5)2 were prepared by a B2O3 flux-technique in high temperature reactions at 1450 °C and investigated by X-ray diffraction. They crystallize in the space group C2h
5-P21/c (Nr. 14) with a = 451.0(4); b = 724.8(3); c = 938.8(6) pm; β = 91,39( 1)°; Z = 2. The compound is isotypic to CuTb2 (B2O5)2 as well as to the gadolinite structure (FeY2(BeSiO5)2) and contains a two dimensional infinite anion with the formula 2
∞ (B2O5)4-. The borate layers consist of four- and eight-membered rings of edge-sharing BO4 tetrahedra. The layers are connected via copper-centered elongated oxygen-octahedra and slightly distorted tetragonal HoO8 antiprisms.
Darstellung, 11B-, 13C-, 1H-NMR-Spektren und Schwingungsspektren von 1,2-Xylylen-pentahydro-closo-hexaborat,cis-[B6H5(CH2)2C6H4]- , sowie Kristallstrukturen von cis-[P(C6H5)4][B6H5(CH2)2C6H4] und cis-[(n-C4H9)4N][B6H5(CH2)2C6H4] / Preparation, 11B, 13C, 1H NMR Spectra and Vibrational Spectra of 1,2-Xylylene-pentahydro-closo-hexaborate, cis-[B6H5(CH2)2C6H4]-, and the Crystal Structures of cis-[P(C6H5)4][B6H5(CH2)2C6H4] and cis-[(n-C4H9)4N ][B6H5(CH2)2C6H4]
Authors: Lübbe W. , Preetz W.
Published: February 2015

By reaction of [B6H6]2- with ω,ω′-dibromo-o-xylene in acetonitrile the 1,2-xylylenepentahydro-closo-hexaborat, cis-[B6H5(CH2)2C6H4]- , is formed. The new ansa compound has been separated from excess [B6H6]2- and other reaction products by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of cis-[P(C6H5)4][B6H5(CH2)2C6H4] (I) and as-[(n-C4H9)4N][B6H5(CH2)2C6H4] (II) have been determined by single crystal X-ray diffraction analysis: I is monoclinic, space group P 21/n with a = 13.715(5), b = 11.118(1) and c = 19.702(2) Å, β = 103.47(2)°; II is orthorhombic with a = 10.204(7), b = 13.352(4) and c = 20.824(8) Å. The 11B NMR spectrum confirms the structure with a hetero disubstituted octahedral B6 cage with local C2v symmetry. The 13C and 1H NMR spectra have been assigned in term of such a configuration. The IR and Raman spectra exhibit characteristic CH, BH, BC, B6 and arene vibrations.
Dicyanometallate, VII [1] Darstellung und Kristallstruktur von Gadolinium-tris-dicyanoaurat (I), Gd[Au(CN)2]3·2,3H2O / Dicyano Metallates, VII [1] Preparation and Crystal Structure of Gadolinium-tris-dicyanoaurate (I), Gd[Au(CN)2]3·2,3H2O
Authors: Stier Angeline , Range Klaus-Jürgen
Published: February 2015

The title compound has been prepared by adding a stoichiometric amount of gadolinium nitrate hexahydrate to an aqueous solution of potassium dicyanoaurate(I). Single crystals could be obtained by slow evaporation from the saturated solution. The compound crystallizes hexagonally, space group P-62m, with a = 6.6319(6), c = 9.108(2) Å, c/a = 1.3734 and Z = 1. The structure comprises layers of considerably bent dicyanoaurate groups. The gold atoms form a nearly regular 3.6 .3.6 - Kagomé net with a layer sequence AA.. and an Au - Au distance of 3.316(2) A, i. e. remarkably shorter than that found in KAu(CN)2 (Au - Au = 3.652(1) Å). Above and below the gold layers, the terminal nitrogen atoms of the dicyanoaurate groups build up a two- dimensional net work in the a,b plane, thereby creating trigonal- prismatic holes, which are occupied by the gadolinium ions. Up to three water molecules per unit cell complete the coordination sphere around the gadolinium ion to form a tricapped trigonal prism. The analogous compounds with Ln = Sm, Eu, Tb and Dy are obviously isostructural with the Gd compound, as can be inferred from preliminary X-ray studies.
Zur Darstellung neuer Polysiline und vernetzter Polysilane / Synthesis of Novel Polysilynes and Branched Polysilanes
Authors: Uhlig Wolfram
Published: February 2015

The reductive coupling of halogenated oligosilanes with potassium-graphite leads to novel polysilynes and branched polysilanes. The ratio of quarternary silicon atoms, monoorganosilyland diorganosilylgroups in the polymers can be modified by variation in the structure of the starting materials. In this way the properties of the preceramic polymers (molecular weights, solubility, content of carbon, degree of cross-linking) are influenced. The compounds are characterized by 29Si NMR spectroscopy.
Über die Kristallstruktur der Phenylsulfinsäure C6H5SO2H [11] / On the Crystal Structure of Phenylsulfinic Acid C6H3SO2H [1]
Authors: Minkwitz Rolf , Kornath Andreas , Lohmann Ulrike
Published: February 2015

Phenylsulfinic acid C6Fr5SO2H crystallizes in the orthorombic space group Pna21, a = 734.3(4), b = 579.9(5), c = 1476.5(9) pm, with four formula units per unit cell. The configuration of the sulfur atom is pyramidal. The molecules form infinite chains via strong hydrogen bonds. The Raman spectra of C6H5SO2H and C6H5SOCl are reported and discussed.
Notizen: Hochdrucksynthese und Einkristall-Strukturverfeinerung von Calciumaurat(III), CaAu2O4 / High Pressure Synthesis and Single-Crystal Structure Refinement of Calcium Aurate (III), CaAu2O4
Authors: Louzikova Anja , Range Klaus-Jürgen
Published: February 2015

Single crystals of calcium aurate(III), CaAu2O4, were obtained by high-pressure treatment of a CaO/Au2O3/KO2 mixture at 40 kbar, 1200 °C in a modified Belt-type apparatus. The crystals are tetragonal, space group I41/a, with a = 5.9868(7), c = 10.043(1) Å, c/a = 1.678 and Z = 4.

CaAu2O4 is isostructural with LaPd2O4, SrAu2O4 and BaAu2O4. Its structure comprises square-planar AuO4 groups (< Au-O > = 2.007 Å), which are stacked into columns along [100] and [010], These columns are connected by shared corners forming a three-dimensional framework. The Ca ions are situated in tunnels created by the gold-oxygen partial structure. They are surrounded by eight oxygen atoms ( = 2.490 Å) in a slightly distorted dodecahedron.
5-Bromo-2-(chloroacetamido)benzophenone - a Synthetic Precursor to 6-Bromoviridicatina
Authors: Peters Karl , Peters Eva-Maria , Bringmann Gerhard , Mader Thomas
Published: February 2015

The title compound 4 was obtained by amidation of 2-amino-5-bromobenzophenone and chloroacetic anhydride. It crystallizes from chloroform in the monoclinic system, space group P21/n; a = 2561(1), b = 586.1(1), c = 969.2(6) pm, and β = 97.18(5)°. An intramolecular hydrogen bond quasi forms an additional six-membered ring.
Polynuclear Gold Complexes of the Carbodiimide Unit [N=C=N]2-
Authors: Schneider W. , Angermaier K. , Schmidbaur H.
Published: February 2015

The reaction of N,N′-bis(trimethylsilyl)carbodiimide with equimolar quantities of tris[(triphenylphosphine)gold]oxonium tetrafluoroborate in dichloromethane at -40°C gives high yields of a trinuclear complex {[(Ph3P)Au]2NCN[Au(PPh3)]}+ BF4
-(1). According to variable temperature NMR data the cation is fluxional in solution with a rapid site exchange of the [(Ph3P)Au] units, but has an unsymmetrical (N,N,N′) low temperature ground state configuration. A single crystal X-ray diffraction study has shown that in the crystal lattice these cations are associated further into cyclic, hexanuclear dimers through two short head-to-tail Au-Au contacts (auriophilicity). Treatment of complex 1 with one equivalent of [(Ph3P)Au]+ BF4
- in tetrahydrofuran affords a tetranuclear complex {[(Ph3P)Au]2NCN[Au(PPh3)]2}2+ 2BF4
- (2). The ambient temperature NMR spectra of 2 suggest a fluxional, pseudo-symmetrical structure, but at low temperature a set of three 31P signals (1:2:3 intensity) indicates an aggregation into higher nuclearity species with non-equivalent [Au(PPh3)] units
Zur Kristallchemie eines Natrium-Cadmium-Oxoiridats: Na3Cd2IrO6 / On the Crystal Chemistry of a Sodium Cadmium Oxoiridate: Na3Cd2IrO6
Authors: Frenzen S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Na3Cd2IrO6 have been prepared by crystallization from melts in closed silver tubes. The crystal structure was investigated by X-ray techniques. Na3Cd2IrO6, crystallizes with monoclinic symmetry, space group C3
2h-C2/m; a = 5.663(2), b = 9.783(3), c = 5.689(2) Å, β = 109.95(2)°, Z = 2. It is isotypic to M+
5A7+O6 (M = Li, Na; A = Re, Os) and shows relations to the sodium chloride structure in spite of an ordered distribution of Na+, Cd2+ and Ir5+
Die Kristallstrukturen der Eisen- und Cobalt-Hexacyanokomplexe Rb2LiM(CN)6 und Rb2NaM(CN)6 / The Crystal Structures of the Iron- and Cobalt-Hexacyanocomplexes Rb2LiM(CN)6 and Rb2NaM(CN)6
Authors: Peschel Stefan , Paulus Werner , Babel Dietrich
Published: February 2015

The crystal structures of four isotypic cyano complexes, belonging to the monoclinic type of cryolite (P21/n, Z = 2), were determined by single crystal X-ray methods and in one case also by neutron diffraction: Rb2LiFe(CN)6 (a = 717.3, b = 748.0, c = 1030.2 pm, β = 90.24°; Fe - C = 193.6, C - N = 114.5, Li - N = 227.0 pm), Rb,NaFe(CN)6 (a = 724.5, b = 772.5, c = 1055.2 pm, β = 90.39°; Fe - C = 193.9, C - N = 114.2, Na - N = 250.4 pm), Rb,LiCo(CN)6 (a = 715.5, b = 741.2, c = 1025.0 pm, β = 90.14°; Co - C = 189.6, C - N = 114.3, Li - N = 226.9 pm), Rb2NaCo(CN)6 (a = 722.5, b = 766.3, c = 1049.2 pm, β = 90.33°; Co - C = 189.9 (188.8), C - N = 113.4 (7/5.5), Na - N = 250.6 (249.6 pm). The irregular [RbN8l coordination polyhedra exhibit average distances close to Rb - N = 336 pm. Details are discussed and the results compared with those of related compounds
Synthesis, Infrared and X-Ray Studies of Diphenyltellurium(IV) Nitrosocarbamylcyanmethanides. X-Ray Evidence for Stability of a Tritelluroxane Fragment -Ph2Te-O-Ph2Te-O-Ph2Te-
Authors: Domasevitch Konstantin V. , Skopenko Victor V. , Rusanov Eduard B.
Published: February 2015

Diphenyltellurium(IV) derivatives of the types Ph2Te{ACO}2 (1), Ph4Te2O{ACO}2 (2) and Ph6Te3O2{ACO} (3) (ACO = nitrosocarbamylcyanmethanide -ONC(CN)C(O)NH2) have been prepared. The IR spectroscopic data reveal that the ambidentate ligands are coordinated to the tellurium(IV) atom in a monodentate manner via the nitroso oxygen atom. The crystal and molecular structure of 3 has been determined from X-ray diffraction data (triclinic, space group P1̅ with a = 12.382(2), 6=13.100(2), c = 14.944(3) Å, a = 87.74( 1), β = 85.04(2), 7 = 66.29( 1)°, V = 2211.0 A , Z = 2, R = 0.040). The structure is made up of unsymmetric molecules, in which the tellurium atoms are linked by oxo bridges to form chains Te-O-Te-O-Te (d(Te-O) ca. 1.94-2.09 A). The Te-0 (nitroso group) bond lengths are in the range 2.33 - 2.36 Å
Zur Reaktivität des Germaethens Me2Ge=C(SiMe3)2: Mechanistische Aspekte der Diels-Aider- und En-Reaktionen [1] / On the Reactivity of Germaethene Me2Ge=C (SiMe3)2: Mechanistic Aspects of Diels Alder and Ene Reactions [1]
Authors: Wiberg Nils , Wagner Susanne
Published: February 2015

Diels-Alder and ene reactions of germaethene Me2Ge=C(SiMe3)2 (2) with butadienes

respectively, take place regioselectively, as well as stereoselectively. They are accelerated by an increasing tendency of substituents in butadiene or propene to donate electrons (e.g. 2-methylbutadiene > butadiene; 2-methylpropene > propene), and retarded by an increasing bulkyness of substituents in 1,4- or 1,3-positions (e.g. 1-methylbutadiene > 2-methylbutadiene; 1-vinylpropene > propene). It is concluded from these studies that Diels-Alder and ene reactions of 2 occur - like those of Me2Si=C(SiMe3)2 (1) or of ethenes >C=C< - in a concerted way and are HOMOdiene-LUMOdienophile and HOMOene-LUMOenophile controlled. Thus 2 and 1 behave as carbon analogues. With regard to a specific diene or ene (e.g. anthracene; toluene), 2 is the better dienophile or enophile than 1 or ethenes. With a fixed diene/ene mixture (e.g. butadiene/propene), 2 acts as the better dienophile, while 1 is the better enophile. These results can be explained by the π/π*- energy difference and the double bond polarity decreasing in the direction 1 > 2. Only cis-piperylene gives a [2+2] cycloadduct with 2. besides two [4+2] cycloadducts, and an ene reaction product
Eine unerwartete Synthese des Triphenyphosphazenium-chlorids, [(C6H5)3PNH2]+CI– und eine Neubestimmung seiner Kristallstruktur / An Unaspected Synthesis of Triphenylphosphazenium Chloride, [(C6H5)3PNH2]+Cl– , and a Redeterm ination of its Crystal Structure
Authors: Vogt H. , Fischer A. , Jones P. G.
Published: February 2015

Triphenylphosphazenium chloride has been prepared by the reaction of triphenylphosphine with trimethylsilylazide in impure, wet dichloromethane. Yields are improved as stoichiometric quantities of water are added. Colourless crystals are obtained by recrystallization from the same solvent. The crystals are triclinic, space group P1̅, Z=2, a = 894,6(3), b - 979,8(3), c = 1142,9(4) pm, α = 107,27(3), β = 93,70(3), y = 92,97(3)°. In the solid state the compound exists as [(C6H5)3PNH2]+ cations, and Cl- anions. Dimeric units are formed by H-bonding. The crystal structure contains one molecule CH2Cl2 per one molecule (C6H5)3PNH2Cl. The cation has a slightly irregular tetrahedral geometry around the P-atom with a relatively short P-N bond
Preparation of an Aminoxyl Analog of the Anticancer Agent Miltefosine
Authors: Sosnovsky George , Lukszo Jan , Brasch Robert C.
Published: February 2015

The synthesis and a few properties of hexadecyl 2-[N,N-dimethyl-N-(2,2,6.6-tetramethyll- oxyl-piperidin-4-yl)ammonio] ethyl phosphate are described. This compound is a spin labeled analog of the antineoplastic drug hexadecylphosphocholine (Miltefosine)
Triterpene Glycosides from Polygala klotzschii
Authors: Krebs Hans Ch. , Sollinger Petra
Published: February 2015

Polygala klotzschii is a toxic plant growing in Brazil. From the methanolic extract of its leaves, two triterpene glycosides could be isolated. Their structures have been determined by spectroscopic means as well as through degradation reactions and by preparing the alditolacetates. The glycosides were identified as 28-0-[β-D-glucofuranosyl(1-2)-β-D-xylopyranosyl(1-4)-α-L-rhamnopyranosyl(1-4)-[α-D-xylopyranosyl(1-3)]-β-D-xylopyranosyl]-3-0-β-D-glucopyranosyl- medicagenate (1) and 28-0-[α-L-rhamnopyranosyl( 1 -4)-a-L-rhamnopyranosyl( 1 -4)-[/3-Dxylofuranosyl( 1-2)-β-D-xylopyranosyl( l-3)]-β-D-xylopyranosyl]-3-0-β-D-glucopyranosyl- 16α-hydroxymedicagenate (2) respectively
Synthese und Redoxverhalten schwefelsubstituierter Naphthochinone-1,4 / Synthesis and Redox Behaviour of Sulfur Substituted Naphthoquinones-1,4
Authors: Knieß Torsten , Mayer Roland
Published: February 2015

Chloro substituted naphthoquinones-1,4 1 react with di-Na-4,5-dithio-1,3-dithiol-2-thiones 2 and other dithiolates to give new sulfur containing heterocyclic quinones 3 and 4 as possible preliminary states to synthesize tetrathiafulvalenes. The reaction of 1 with di-Li-2,2- bis(methylthio)-1,1-ethylendithiol 8 yields the appropriate bis-(methylthio)methylen substituted naphthoquinones 9. The redox behaviour of the new compounds was investigated by cyclic voltammetry
Die Synthese und Kristallstruktur von Ba2Mn(B3O6)2 und Ba2Co(B3O6)2 / Synthesis and Crystal Structure of Ba2Mn(B3O6)2 and Ba2Co(B3O6)2
Authors: Utzolino Anne , Bluhm Karsten
Published: February 2015

Single crystals of Ba2Mn(B3O6)2 (I) and Ba2Co(B3O6)2 (II) were prepared by using a B2O3 flux technique, Ba2Mn(B3O6)2 in an argon atmosphere. X-ray investigations on single crystals of both compounds yield the space group C3i
2R3̄ (No. 148) with 3 formula units in the cell of dimensions (I) a = 711.01(4), c = 1694.90(3) pm and (II) a = 707.2(2), c = 1673.8(1) pm. The crystal structure is built by nearly planar (B3O6)3- rings and contains one ninefold coordinated Barium site. Mn(I) and Co(II) are octahedrally coordinated by oxygen. The compounds are isotypic to B2Ca(B3O6)2.
Eine neue Modifikation von Na2Zn2O3 / A New Modification of Na2Zn2O3
Authors: Trinschek D. , Jansen M.
Published: February 2015

A new modification of Na2Zn2O3 has been synthesized via solid state reaction. According to the single crystal structure determination, the compound crystallizes in the space group P43212 (No. 96) with lattice parameters a = 6.1812(2), c = 9.4479(4) Å, Z = 4. The structure consists of ZnO4 tetrahedra connected via edges and corners forming a threedimensional network. The structure can be described as an distorted anti spinel.
Synthese und Struktureines Strontium-Vanadyl-Phosphats: Sr2(VO)(PO4)2 / Synthesis and Structure of a Strontium Vanadyl Phosphate: Sr2(VO)(PO4)2
Authors: Wadewitz C. , Müller-Buschbaum Hk.
Published: February 2015

Dark green single crystals of Sr2(VO)P2O8 have been prepared by solid state reactions in closed quartz tubes. X-ray investigations led to monoclinic symmetry, space group C2h
6-I2/a, a = 6.744(4), b = 15.866(4), c = 7.032(2) Å, β = 115.41(2), Z = 4. Sr2(VO)P2O8 is isotypic to Sr2(VO)V2O8 and shows V4+ in split positions. The split positions are in non-centric octahedral coordination forming a short vanadium to oxygen distance typical for the vanadyl group. The crystal chemistry of the monovanadyl orthophate Sr2(VO)P2O8 is discussed considering related divanadyl phosphates.
Phosphinoalkylnitrile: Synthese und Koordinationsverhalten an Palladiumzentren / Phosphinoalkylnitnles: Synthesis and Coordination Behaviour at Palladium Centres
Authors: Pitter Stephan , Dinjus Eckhard , Jung Beate , Görls Helmar
Published: February 2015

Phosphinoalkylnitriles R2P-(CH2)n-CN {R = isopropyl (ipr), phenyl (ph), cyclohexyl (chex), n = 3, 6, 10} have been prepared starting from the corresponding secondary phosphines in an easy three step synthesis. All new compounds were characterized by their 1H -, 13C and 31P NMR data. Some of these new P, N ligands were used to prepare complexes [{R2P- (CH2)n-CN}2PdCl2] which were also identified by their NMR data. In addition the crystal structures of three derivatives, [{ipr2P-(CH2)3-CN}2PdCl2] 7a, [{ph2P-(CH2)3-CN}2PdCl2) 7b and [{ph2P-(CH2)6-CN}2PdCl2] 8b were determined by X-ray analysis. The coordination mode of the phosphinoalkylnitriles in these complexes was found to be P-bonded resulting in a trans configuration. Palladium catalysts with 5a as ligand show high activies in the co-oligomerization of butadiene and carbon dioxide. The δ-lactone 11a is formed under very mild conditions.
Supram olekulare chloridverbrückte Metall(II)chlorid-Diazin-Komplexe: Kristallstrukturen von [Cd(pyrazin)Cl2], [Zn(pyrazin)Cl2] und [Zn(pyrimidin)C l2] / Supram olecular Chloride Bridged Metal(II) Dichloride Diazine Complexes: Crystal Structures of [Cd(pyrazine)Cl2], [Zn(pyrazine)Cl2], and [Zn(pyrimidine)Cl2]
Authors: Pickardt Joachim , Staub Benedikt
Published: February 2015

Single crystals of [Cd(pyrazine)Cl2],[Zn(pyrazine)Cl2] and [Zn(pyrimidine)Cl2] were obtained by a diffusion technique from aqueous solutions of the metal dichlorides and solutions of the respective diazine.

The structures consist of “supramolecular” networks of-M-Cl-M - and -M-diazine-M-chains.
Synthese und Kristallstruktur von Ba(HSO4)2(H2SO4)3 und Sr(HSO4)2(H2SO4) / Synthesis and Structure of Ba (HSO4)2(H2SO4)3 and Sr(HSO4)2(H2SO4)
Authors: Werner C. , Kemnitza E. , Worzalab H. , Trojanov S.
Published: February 2015

From the binary systems M2SO4/H2SO4 (M = Ba. Sr), two new hydrogen sulfates, (Ba(HSO4)2(H2SO4)3 and Sr(HSO4)2(H2SO4), have been synthesized and structurally characterized.

Ba(HSO4)2(H2SO4)3 crystallizes in the orthorhombic space group P21212, with unit cell parameters a = 4.680(1), b = 11.267(2), c = 29.188(6)A, Z = 4. BaO9 trigonal prismatic polyhedra with Ba-O distances of 2.68 - 3.02 Å from nine different SO4 tetrahedra are connected via common bases and build “isolated” columns consisting of O-S-O bridged double chains along the x-axis. HSO4 and H2SO4 tetrahedra are linked via hydrogen bonds to form columns. Sr(HSO4)2(HTSO4) crystallizes in the triclinic space group P1̄ with unit cell parameters a = 5.971(1), b = 8.468(2), c = 10.226(2)Å, α = 81.71(3), β = 83.30(3), γ = 70.69(3)°, Z = 2. Sr is coordinated by nine oxygen atoms from seven different SO4 tetrahedra with Sr-O distances of 2.47 - 2.84 Å. The SrO9 polyhedra build layers consisting of O-S-O bridged chains. Three crystallographically different SO4 tetrahedra are linked via hydrogen bonds to form a kind of flattened cylinder along the x-axis.