Published by De Gruyter

Volume 51 Issue 5

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Open Access June 2, 2014

Darstellung, ¹¹B-NMR-Spektren, Schwingungsspektren und Normalkoordinatenanalyse von conjuncto-Bis-hexahydro-closo-hexaborat, [B₆H₆-B₆H₆]^2-, sowie Kristallstruktur von [P(C₆H₅)₄]₂-conjuncto-[B₆H₆-B₆H₆] / Preparation, ¹¹B NMR Spectra, Vibrational Spectra and Normal Coordinate Analysis of conjuncto-Bis-hexahydro-closo-hexaborate, [B₆H₆-B₆H₆]^2-, and the Crystal Structure of [ P(C₆H₅)₄]₂-conjuncto-[B₆H₆-B₆H₆]

D. Bublitz, A. Franken, W. Preetz, H. Thomsen

Page range: 609-618

More Download PDF

Abstract

By reaction of [B 6 H 6 ] 2- with dibenzoylperoxide in dichloromethane conjuncto-[B 6 H 6 - B 6 H 6 ] 2- is formed. The product could be separated from excess [B 6 H 6 ] 2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [P(C 6 H 5 ) 4 ] 2 -conjuncto- [B 6 H 6 -B 6 H 6 ] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1̄ with a = 10.8315(10), b = 11,2422( 12), c = 20.340(2) Å, α = 91.278° (9), β = 90.178° (9), γ = 105.662°(9). The 11 B NMR spectrum reveals three signals with the intensity ratio 1:1:4, for two equivalent moieties of the conjuncto molecule ion with local C 4v symmetry. The IR and Raman spectra of the deprotonated Cs salts of the 10 B, 11 B and their respective D isotopomers of conjuncto-[B 6 H 5 -B 6 H 5 ] 4- exhibit characteristic shifts. Using averaged crystallographic data and assuming idealized D 4h symmetry, normal coordinate analyses have been performed based on a modified valence force field. With a set of eleven force constants (e.g. f d (BB) conjuncto = 2.9, f d (BB) cage = 1.6 mdyn/Å) very good agreement between observed and calculated frequencies has been achieved. From strong vibrational coupling with the B 6 clusters two vibrations result for the conjuncto B-B bond at 1142/1198 and 292/304cm -1 for 11 B/ 10 B species, respectively. They can be assigned as anti-phase and in-phase motions of the conjuncto B atoms related to the equatorial B 4 planes.

Open Access June 2, 2014

Reaktion von Iodomethylzinnverbindungen mit (S)-1-t-Butyloxycarbonyl-2-t-butyl-3-methyl-4-imidazolidinon (Boc-BMI) / Reaction of Iodomethyltin Compounds with (S)-1-t-Butyloxycarbonyl-2-t-butyl-3-methyl-4-imidazolidinone (Boc-BMI)

Karin Dölling, André Krug, Helmut Hartung, Horst Weichmann

Page range: 619-628

More Download PDF

Abstract

Diastereoselective alkylation of (S)-2-t-butyl-1-t-butyloxycarbonyl-3-methyl-4-imidazolidinone (Boc-BMI) 1 with R 3 SnCH 2 I yields triorganostannylmethylated Boc-BMI compounds, 2 and 3 (2: R = Me; 3: R = Ph). By halogenation 2 and 3 are transformed into the halostannylsubstituted compounds R 3-n X n SnCH 2 -Boc-BMI 4 - 8 (R = Me, Ph; n = 1, 2; X = Cl, Br). Analogously, the trifluoroacetyloxostannylated compounds 9 and 10 (9: R = Me; 10: R = Ph) are formed by reaction of 2 and 3 with trifluoracetic acid. 4 (R = Me; n = 1; X = Cl) has been structurally characterized in detail by NMR spectroscopy and X-ray analysis. Its tin atom is pentacoordinated by intramolecular coordination of the CO group of the imidazolidinone ring. The alkylation of 1 with Me 2 Sn(CH 2 I) 2 yields the bis-Boc-BMI tin compound 11 and the iodomethyl dimethylstannylmethylated Boc-BMI 12. 11 reacts with one or two equivalents of bromine to give the bromostannylated derivatives 13 and 14, respectively.

Open Access June 2, 2014

Zur Reaktivität des Silaethens Me₂Si=C(SiMe₃)₂: Regioselektivität, Stereoselektivität und relative Geschwindigkeiten von En-Reaktionen [1] / On the Reactivity of Silaethene Me₂Si=C(SiMe₃)₂: Regioselectivity, Stereoselectivity and Relative Rates of Ene Reactions [1]

Nils Wiberg, Susanne Wagner

Page range: 629-636

More Download PDF

Abstract

Ene reactions of Me 2 Si=C(SiMe 3 ) 2 (1) with propene or with methyl derivatives of propene and 1,3-butadiene, respectively, of the formula R 1 CH=CR 2 -CH 2 R 3 take place regioselectively, as well as stereoselectively and are retarded by increasing bulk of R 1 , R 3 (for example H < CH 3 < CH=CH 2 < CH=CHMe), as well as accelerated by an increasing tendency of R 2 to donate electrons (for example H < CH 3 ≈ CH=CH 2 < CH 2 SiMe 2 [CH(SiMe 3 ) 2 ]). It is concluded from these studies, that ene reactions of 1 occur concerted and are HOMO ene -LUMO enophile controlled.

Open Access June 2, 2014

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]

Thomas Kräuter, Bert Werner, Bernhard Neumüller

Page range: 637-645

More Download PDF

Abstract

(PhCH 2 ) 2 GaBr (1) can be obtained by the redistribution reaction of GaBr 3 with Ga(CH 2 Ph) 3 in a molar ratio 1:2. Treatment of 1 or (PhCH 2 ) 2 GaCl with one equivalent of LiN(H)t-Bu gives the diorganogallium amide [(PhCH 2 ) 2 GaN(H)t-Bu] 2 (2). The toluene-insoluble PhCH 2 InCl 2 can be structurally investigated after dissolving in THF and crystallization as [PhCH 2 InCl 2 (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.

Open Access June 2, 2014

Preparation, Crystal Structure, and Properties of the Lanthanoid Carbides Ln₄C₇ with Ln = Ho, Er, Tm, and Lu

Ralf Czekalla, Wolfgang Jeitschko, Rolf-Dieter Hoffmann, Helmut Rabeneck

Page range: 646-654

More Download PDF

Abstract

The isotypic carbides Ln 4 C 7 (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 LU 4 C 7 were determined from X-ray powder data, and the last carbon positions were found and refined from neutron powder diffraction data: P2 1 /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 C 3 -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 LU 4 C 7 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 C 2 -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 C 3 -units. It may be described as a stacking variant of a previously reported structure of H O4 C 7 , now designated as the a-modification. The Lu 4 C 7 -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. Lu 4 C 7 is Pauli paramagnetic; β -H O4 C 7 and Er 4 C 7 show Curie-Weiss behavior with magnetic ordering temperatures of less than 20 K.

Open Access June 2, 2014

Die elektronische Struktur ternärer Übergangsmetallpnictide. I. AlB₂-Varianten / The Electronic Structure of Ternary Transition Metal Pnictides. I. AlB₂-Variants

Dirk Johrendt, Albrecht Mewis

Page range: 655-664

More Download PDF

Abstract

The electronic structure and bonding of some ternary AlB 2 -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 AIB 2 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.

Open Access June 2, 2014

Structure and Spin-Spin Interactions in a Linear Trinuclear Ni(II) Complex

Ayhan Elmali, Yalcin Elerman, Ingrid Svoboda, Hartmut Fuess, Klaus Griesar, Wolfgang Haase

Page range: 665-670

More Download PDF

Abstract

[Ni 3 (C 2 H 3 O 2 ) 2 (C 3 H 8 NO) 2 L 2 ] [(L=N,N′-1,3-propyl-disalicylaldimine), (C 2 H 3 O 2 )=acetate, (C 3 H 8 NO)=hydroxymethyl-dimethylamine] has been synthesized and its crystal structure determined, [C 44 H 54 N 6 O 10 Ni 3 ], 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 (J 1 = -2.2 cm -1 ) and between the terminal Ni atoms (J 2 = -1.7 cm -1 ).

Open Access June 2, 2014

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

Silke Busche, Karsten Bluhm

Page range: 671-676

More Download PDF

Abstract

Single crystals of the new compounds LnZn(B 5 O 10 ) (Ln = (A) Ce 3+ , (B) Nd 3+ , (C) T b 3+ ) were obtained by using a B 2 O 3 flux technique. X-ray investigations led to space group C 2h 5 -P2 1 /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(B 5 O 10 ) and is characterized by two-dimensional infinite 2 ∞ (B 5 O 10 ) 5- ions. Ln is tenfold coordinated by oxygen, and Zn 2+ occupies distorted ZnO 6 polyhedra.

Open Access June 2, 2014

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

Karsten Bluhm, André Wiesch

Page range: 677-680

More Download PDF

Abstract

Single crystals of NiHo 2 (B 2 O 5 ) 2 were prepared by a B 2 O 3 flux-technique in high temperature reactions at 1450 °C and investigated by X-ray diffraction. They crystallize in the space group C 2h 5 -P2 1 /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 CuTb 2 (B 2 O 5 ) 2 as well as to the gadolinite structure (FeY 2 (BeSiO 5 ) 2 ) and contains a two dimensional infinite anion with the formula 2 ∞ (B 2 O 5 ) 4- . The borate layers consist of four- and eight-membered rings of edge-sharing BO 4 tetrahedra. The layers are connected via copper-centered elongated oxygen-octahedra and slightly distorted tetragonal HoO 8 antiprisms.

Open Access June 2, 2014

Sulfur and Selenium Complexes of the Hydrido-tri(3,5-dimethyl-1-pyrazolyl) borate Nitrosylmolybdenum Fragment, [TpMo(NO)]. An X-Ray Crystal Structure Determination of TpMo(NO)(Se₅)

Max Herberhold, Guo-Xin Jin, Arnold L. Rheingold

Page range: 681-685

More Download PDF

Abstract

The reactions of hydrido-tri(3,5-dimethyl-1-pyrazolyl)borate nitrosylmolybdenum diiodide, Tp*Mo(NO)I 2 (2), with the oligochalcogenides (NH 4 ) 2 S 10 and (NEt 4 ) 2 Se 6 in THF solution lead to mononuclear cyclo-pentachalcogenido complexes, Tp*Mo(NO)(E 5 ) (E = S (3a), Se (3b)). In the presence of either H 2 S or H 2 Se (generated by slow “in situ” hydrolysis of AI 2 E 3 in moist THF solution) 2 is converted into binuclear chalcogenido-bridged products, Tp * 2 Mo 2 (NO) 2 (μ-E) 2 (E = S (4a), Se (4b)) which are more conveniently obtained from 3a,b by dechalcogenation with tri(″butyl)phosphane (1:4,5). The new chalcogen complexes 3a,b and 4a,b were characterized by IR, NMR and mass spectroscopy and compared with the related chalcogen compounds derived from pentamethylcyclopentadienyl nitrosylmolybdenum diiodide, Cp*Mo(NO)l 2 . The molecular structure of Tp*Mo(NO)(Se 5 ) (3b) has been determined; the complex contains a sixmembered MoSe 5 ; metallacycle in the chair conformation and a linearly coordinated nitrosyl ligand (angle Mo-N-O 178.9(17)°).

Open Access June 2, 2014

Synthese und Struktur von Ag₄[(PhN₃)₂C₆H₄]₂ (en)₂, einem vierkernigen Silber(I)komplex mit 1,2-Bis(phenyltriazenido)benzol als Ligand / Synthesis and Structure of Ag₄[(PhN₃)₂C₆H₄]₂ (en)₂, a Tetranuclear Silver(I) Complex with 1,2-Bis(phenyltriazenido)benzene as Ligand

Manfredo Hörner, Antônio Gilberto Pedroso, Johannes Beck, Joachim Strähle

Page range: 686-690

More Download PDF

Abstract

Ag 4 [(PhN 3 ) 2 C 6 H 4 ] 2 (en) 2 is obtained by the reaction of [Ag(NH 3 ) 2 ] + with 1,2-bis- (phenyltriazeno)benzene and ethylenediamine. It crystallizes in the monoclinic space group P2 1 /c with a = 1064.9(2), b = 2041.8(3), c = 1008.5(3) pm, β = 101.37(2)°, Z = 2. In the centrosymmetrical tetranuclear complex, the four Ag + ions form a zigzag chain with Ag-Ag distances of 293.34 and 280.42 pm. Ethylenediamine molecules chelate the two terminal Ag atoms of this chain. Each of the 1,2-bis(phenyltriazeno)benzene ligands in the deprotonated bis(triazenido) form [(PhN 3 ) 2 C 6 H 4 ] 2- is bridging three Ag+ ions. The Ag + ions are coordinated by three N atoms in a trigonal planar arrangement with Ag-N distances between 214.0 and 241.2 pm.

Open Access June 2, 2014

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]

W. Lübbe, W. Preetz

Page range: 691-697

More Download PDF

Abstract

By reaction of [B 6 H 6 ] 2- with ω,ω′-dibromo-o-xylene in acetonitrile the 1,2-xylylenepentahydro-closo-hexaborat, cis-[B 6 H 5 (CH 2 ) 2 C 6 H 4 ] - , is formed. The new ansa compound has been separated from excess [B 6 H 6 ] 2- and other reaction products by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of cis-[P(C 6 H 5 ) 4 ][B 6 H 5 (CH 2 ) 2 C 6 H 4 ] (I) and as-[(n-C 4 H 9 ) 4 N][B 6 H 5 (CH 2 ) 2 C 6 H 4 ] (II) have been determined by single crystal X-ray diffraction analysis: I is monoclinic, space group P 2 1 /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 11 B NMR spectrum confirms the structure with a hetero disubstituted octahedral B 6 cage with local C 2v symmetry. The 13 C and 1 H NMR spectra have been assigned in term of such a configuration. The IR and Raman spectra exhibit characteristic CH, BH, BC, B 6 and arene vibrations.

Open Access June 2, 2014

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

Angeline Stier, Klaus-Jürgen Range

Page range: 698-702

More Download PDF

Abstract

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.

Open Access June 2, 2014

Zur Darstellung neuer Polysiline und vernetzter Polysilane / Synthesis of Novel Polysilynes and Branched Polysilanes

Wolfram Uhlig

Page range: 703-710

More Download PDF

Abstract

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 29 Si NMR spectroscopy.

Open Access June 2, 2014

Na₂ZnO₂, ein neues Natriumzinkat / Na₂ZnO₂, a New Sodium Zincate

D. Trinschek, M. Jansen

Page range: 711-714

More Download PDF

Abstract

By reacting Na 2 O, which was produced in situ from NaN 3 and NaNO 2 , with reactive ZnO in the solid state, the synthesis of Na 2 ZnO 2 has been achieved. Na 2 ZnO 2 is metastable up to about 750°C. The novel sodium zincate crystallizes in the spaceogroup P2 1 /c (No. 14) with the lattice parameters a = 7.7352(2), b = 5.9782(2), c = 5.7248(2) Å, β = 94.934(3)°, Z = 4. According to a single crystal structure determination it is an representative of the anti type of the Ln 2 S 2 O (Ln = Er, Tm, Yb, Dy) structure.

Open Access June 2, 2014

Über die Reaktion von KPPh₂ mit Fe(CO)₅ und Fe(CO)₄CS; Molekülstruktur von [(CO)₄FePPh₂]^- / On the Reaction of KPPh*, with Fe(CO)₅ and Fe(CO)₄CS; Molecular Structure of [(CO)₄FePPh₂]^-

Wolfgang Petz, Frank Weller

Page range: 715-721

More Download PDF

Abstract

Fe(CO) 5 reacts with [PPh 2 ] - in THF at -78 °C to give the adduct [(CO) 4 FeCOPPh 2 ] - (3) which decomposes at elevated temperature to give [(CO) 4 FePPh 2 ] - (1), [Fe 2 (CO) 8 ] 2- (2) and (Ph 2 P) 2 probably via a radical mechanism. Attempts to transfer 3 with the electrophiles MeSO 3 CF 3 or Me 3 SnCl into the corresponding carbenes have failed and Fe(CO) 5 along with Ph 2 PMe and Me 3 SnPPh 2 , respectively, are formed. 1 adds one equivalent of CS 2 to generate [(CO) 4 FePPh 2 CS 2 ] - (4). The [K-18-Krone-6] salt of 1 crystallizes in the triclinic space group P 1̄ with the unit cell parameters a = 929.5(2), b = 1112 .1(2), c = 2017.9(4) pm, α = 100.29(3)°; β = 94.07(3) °; γ = 114.58(3) °. The existence of 3 is established by low temperature 31 P NMR spectroscopy.

Open Access June 2, 2014

Zur Synthese und Kristallstruktur von Bariumboroarsenat Ba(BAsO₅) mit einem Beitrag über Bariumorthoarsenat Ba₃(AsO₄)₂ / Synthesis and Crystal Structure of Barium Boroarsenate Ba(BAsO₅) with a Contribution on Barium Orthoarsenate Ba₃(AsO₄)₂

Cheong-Hwa Park, Karsten Bluhm

Page range: 722-726

More Download PDF

Abstract

Single crystals of Ba(BAsO 5 ) (I) and Ba 3 (AsO 4 ) 2 (II) were obtained by melting B 2 O 3 , arsenic pentoxide and BaO at 1100°C. Both compounds crystallize trigonally, space groups (I): C 3 2 - P3 1 (Nr. 144), (II): D 3d 5 - R3̄m (Nr. 166), with the lattice parameters (I): a = 726.7(1), c = 710.6(1) pm, Z = 3 and (II): a = 576.7(1), c = 2116.3(2) pm, Z = 3. Ba(BAsO 5 ) is isotypic to Pb(BAsO 5 ) (Stillwellite structure) and Ba 3 (AsO 4 ) 2 to Ba 3 (PO 4 ) 2 . The structure of Ba(BAsO 5 ) is characterized by helical chains of rings of two borate tetrahedra and one arsenate tetrahedron. Barium is tenfold coordinated by oxygen. A rod-like sequence of coordination polyhedra, AsO 4 - Ba(2)O 10 -Ba(1)O 12 -Ba(2)O 10 -AsO 4 is characteristic in the crystal structure of Ba 3 (AsO 4 ) 2 .

Open Access June 2, 2014

Synthese und Kristallstruktur von (TeCl₃)₂MoCl₆ und β-(TeCl₃)₂ReCl₆ / Synthesis and Crystal Structure of (TeCl₃)₂MoCl₆ and β-(TeCl₃)₂ReCl₆

J. Beck, P. Biedenkopf, K. Müller-Buschbaum

Page range: 727-732

More Download PDF

Abstract

Single crystals of (TeCl 3 ) 2 MoCl 6 and β-(TeCl 3 ) 2 ReCl 6 are obtained by the reactions of TeCl 4 with MoCl 4 at 195 °C and of TeCl 4 / Te with ReCl 5 at 150 °C, respectively. The com pounds form dark-red moisture sensitive crystals. The crystal structure determinations show, that both crystallize isotypically ( rhombohedral, space group R3̄, (TeCl 3 ) 2 MoCl 6 : a = 1116,9(1), c = 3539,5(5) pm. 1966 unique reflections for 69 parameters, final R = 0.058; β-(TeCl 3 ) 2 ReCl 6 : a = 1113,3(3), c = 3546(2) pm. 1653 unique reflections for 70 parameters, final R = 0.034). The structures consist of octahedral MCl 6 2- anions (with M=Mo,Re) and pyramidal TeCl 3+ cations. The ions are interconnected through long Te-Cl bridges (291,1- 295,6 pm) to give distorted TeCl 6 octahedra. MCl 6 and TeCl 6 units are connected via edges and corners, resulting in a complex layer structure with layers parallel to the ab-plane. In the previously reported a-form of (TeCl 3 ) 2 ReCl 6 , only connections via corners are observed.

Open Access June 2, 2014

A-Pr₂S₃, D-Ho₂S₃ und E-Yb₂S₃:Synthese und Einkristallstrukturuntersuchungen / A-Pr₂S₃, D-Ho₂S₃ and E-Yb₂S₃:Synthesis and Single Crystal Structure Investigations

Thomas Schleid, Falk Lissner

Page range: 733-738

More Download PDF

Abstract

The oxidation of reduced chlorides (MCl 2 ) or chloride-hydrides (MClH x ) of the lanthanides with sulfur (700-850 °C, 7 d, sealed tantalum capsules or evacuated silica vessels) usually results in the formation of the sesquisulfides M 2 S 3 as the main products. In the presence of appropriate fluxes (e.g., alkali halides), the products often are obtained as single crystals, and the flux decides which modification is favoured. Ternary halides of the trivalent lanthanides with the corresponding alkali metal can mostly be found as the second components. Crystal growth and structural investigations of thus produced single crystals of Pr 2 S 3 (from PrClH 0.67 + S + NaCl, 5:5:1, A type: orthorhombic, Pnma (No. 62), Z = 4, a = 748.22(5), b = 405.51(3), c = 1560.74(9) pm, R = 0.024, R w = 0.020), Ho 2 S 3 , (from U - Ho 2 S 3 , + KI, 1:1, D type: monoclinic, P2 1 /m (No. 12), Z = 6, a = 1746.15(9), b = 400.23(3), c = 1012.43(6) pm, β = 98.529(4)°, R = 0.041, R w = 0.035), and Yb 2 S 3 (from T-Yb 2 S 3 + KI, 1:1, E type: trigonal, R3̄c (No. 167), Z = 6, a = 674.97(2), c = 1820.11(9) pm, R = 0.019, R w = 0.018) are reported here. In accordance with the lanthanide contraction, the trivalent cations (M 3+ ) exhibit sulfur coordination numbers of 7 and 8 in A -Pr 2 S 3 , 6 and 7 in D -Ho 2 S 3 , and 6 in E -Yb 2 S 3 (corundum-type structure).

Open Access June 2, 2014

Über die Kristallstruktur der Phenylsulfinsäure C₆H₅SO₂H [11] / On the Crystal Structure of Phenylsulfinic Acid C₆H₃SO₂H [1]

Rolf Minkwitz, Andreas Kornath, Ulrike Lohmann

Page range: 739-743

More Download PDF

Abstract

Phenylsulfinic acid C 6 Fr 5 SO 2 H 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 C 6 H 5 SO 2 H and C 6 H 5 SOCl are reported and discussed.

Open Access June 2, 2014

Darstellung und ¹¹B-NMR-Spektrum von Heptabromo-closo-heptaborat, [B₇Br₇]^2- sowie Kristallstruktur von [(C₅H₅N)₂CH₂][B₇Br₇] / Preparation and ¹¹B NMR Spectrum of Heptabromo-closo-heptaborate, [B₇Br₇]^2-, and the Crystal Structure of [(C₅H₅N)₂CH₂][B₇Br₇]

A. Franken, H. Thomsen, W. P reetz

Page range: 744-746

More Download PDF

Abstract

By reaction of conjuncto-[B 6 H 6 -B 6 H 6 ] 2- in alkaline solution with excess bromine the heptabromo-closo-heptaborate, [B 7 Br 7 ] 2 is formed. The crystal structure of [(CsH 3 N) 2 CH 2 ][B 7 Br 7 ] has been determined by single crystal X-ray diffraction analysis (monoclinic, space group P2 1 /a with a = 15.0843(14), b = 9.8882(14), c = 17.057(2) Å, β = 114.039°(7)). In accordance with the D 5h point symmetry, the anion shows two singlets at -23.3 and -0.1 ppm with the intensity ratio 2:5 in its 11 B NMR spectrum.

Open Access June 2, 2014

Notizen: Hochdrucksynthese und Einkristall-Strukturverfeinerung von Calciumaurat(III), CaAu₂O₄ / High Pressure Synthesis and Single-Crystal Structure Refinement of Calcium Aurate (III), CaAu₂O₄

Anja Louzikova, Klaus-Jürgen Range

Page range: 747-750

More Download PDF

Abstract

Single crystals of calcium aurate(III), CaAu 2 O 4 , were obtained by high-pressure treatment of a CaO/Au 2 O 3 /KO 2 mixture at 40 kbar, 1200 °C in a modified Belt-type apparatus. The crystals are tetragonal, space group I4 1 /a, with a = 5.9868(7), c = 10.043(1) Å, c/a = 1.678 and Z = 4. CaAu 2 O 4 is isostructural with LaPd 2 O 4 , SrAu 2 O 4 and BaAu 2 O 4 . Its structure comprises square-planar AuO 4 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 (<Ca-O> = 2.490 Å) in a slightly distorted dodecahedron.

Open Access June 2, 2014

Notizen: Die Kristallstruktur von Calciumchromat(VI), CaCrO₄ / The Crystal Structure of Calcium Chromate (VI), CaCrO₄

Gabriele Weber, Klaus-Jürgen Range

Page range: 751-753

More Download PDF

Abstract

The zircon-type structure of calcium chromate( VI), CaCrO 4 , has been confirmed and refined from single-crystal X-ray data. The compound crystallizes tetragonaly, space group I4 1 /amd, with a = 7.222(2), c = 6.285(1) Å, c/a = 0.8703 and Z = 4. The structure comprises isolated, slightly distorted CrO 4 tetrahedra ( C r-O = 1.646(3) Å ) which are connected with CaO 8 dodecahedra (<Ca-O> = 2.556 Å) by edge- and corner-sharing. The three-dimensional framework thus created contains rather large holes which are, however, empty in the case of CaCrO 4

Open Access June 2, 2014

5-Bromo-2-(chloroacetamido)benzophenone - a Synthetic Precursor to 6-Bromoviridicatina

Karl Peters, Eva-Maria Peters, Gerhard Bringmann, Thomas Mader

Page range: 754-756

More Download PDF

Abstract

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 P2 1 /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.

About this journal

Objective
Zeitschrift fuer Naturforschung B (ZNB) publishes novel research in all areas of inorganic chemistry, organic chemistry, and analytical chemistry. In particular, the journal focuses on solid state chemistry, coordination chemistry, main group element chemistry, synthetic organic chemistry, natural product chemistry and, to a lesser extent, on analytical chemistry. For more than 65 years Zeitschrift fuer Naturforschung B has been open to contributions from all fields of experimental and theoretical chemistry. Zeitschrift fuer Naturforschung B publishes 12 issues per volume/year. Sometimes double issues occur.

Topics

Solid state chemistry
Coordination chemistry
Main group element chemistry
Organic chemistry
Natural product chemistry

Article formats
Original (full) papers, research notes and preliminary communications, reports on specific research topics of current interest (reviews)

> Information on submission process

Volume 51 Issue 5

Issue of Zeitschrift für Naturforschung B

Abstract

Reaktion von Iodomethylzinnverbindungen mit (S)-1-t-Butyloxycarbonyl-2-t-butyl-3-methyl-4-imidazolidinon (Boc-BMI) / Reaction of Iodomethyltin Compounds with (S)-1-t-Butyloxycarbonyl-2-t-butyl-3-methyl-4-imidazolidinone (Boc-BMI)

Abstract

Zur Reaktivität des Silaethens Me2Si=C(SiMe3)2: Regioselektivität, Stereoselektivität und relative Geschwindigkeiten von En-Reaktionen [1] / On the Reactivity of Silaethene Me2Si=C(SiMe3)2: Regioselectivity, Stereoselectivity and Relative Rates of Ene Reactions [1]

Abstract

Abstract

Preparation, Crystal Structure, and Properties of the Lanthanoid Carbides Ln4C7 with Ln = Ho, Er, Tm, and Lu

Abstract

Die elektronische Struktur ternärer Übergangsmetallpnictide. I. AlB2-Varianten / The Electronic Structure of Ternary Transition Metal Pnictides. I. AlB2-Variants

Abstract

Structure and Spin-Spin Interactions in a Linear Trinuclear Ni(II) Complex

Abstract

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

Abstract

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

Abstract

Sulfur and Selenium Complexes of the Hydrido-tri(3,5-dimethyl-1-pyrazolyl) borate Nitrosylmolybdenum Fragment, [Tp*Mo(NO)]. An X-Ray Crystal Structure Determination of Tp*Mo(NO)(Se5)

Abstract

Synthese und Struktur von Ag4[(PhN3)2C6H4]2 (en)2, einem vierkernigen Silber(I)komplex mit 1,2-Bis(phenyltriazenido)benzol als Ligand / Synthesis and Structure of Ag4[(PhN3)2C6H4]2 (en)2, a Tetranuclear Silver(I) Complex with 1,2-Bis(phenyltriazenido)benzene as Ligand

Abstract

Abstract

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

Abstract

Zur Darstellung neuer Polysiline und vernetzter Polysilane / Synthesis of Novel Polysilynes and Branched Polysilanes

Abstract

Na2ZnO2, ein neues Natriumzinkat / Na2ZnO2, a New Sodium Zincate

Abstract

Über die Reaktion von KPPh2 mit Fe(CO)5 und Fe(CO)4CS; Molekülstruktur von [(CO)4FePPh2]- / On the Reaction of KPPh*, with Fe(CO)5 and Fe(CO)4CS; Molecular Structure of [(CO)4FePPh2]-

Abstract

Zur Synthese und Kristallstruktur von Bariumboroarsenat Ba(BAsO5) mit einem Beitrag über Bariumorthoarsenat Ba3(AsO4)2 / Synthesis and Crystal Structure of Barium Boroarsenate Ba(BAsO5) with a Contribution on Barium Orthoarsenate Ba3(AsO4)2

Abstract

Synthese und Kristallstruktur von (TeCl3)2MoCl6 und β-(TeCl3)2ReCl6 / Synthesis and Crystal Structure of (TeCl3)2MoCl6 and β-(TeCl3)2ReCl6

Abstract

A-Pr2S3, D-Ho2S3 und E-Yb2S3:Synthese und Einkristallstrukturuntersuchungen / A-Pr2S3, D-Ho2S3 and E-Yb2S3:Synthesis and Single Crystal Structure Investigations

Abstract

Über die Kristallstruktur der Phenylsulfinsäure C6H5SO2H [11] / On the Crystal Structure of Phenylsulfinic Acid C6H3SO2H [1]

Abstract

Darstellung und 11B-NMR-Spektrum von Heptabromo-closo-heptaborat, [B7Br7]2- sowie Kristallstruktur von [(C5H5N)2CH2][B7Br7] / Preparation and 11B NMR Spectrum of Heptabromo-closo-heptaborate, [B7Br7]2-, and the Crystal Structure of [(C5H5N)2CH2][B7Br7]

Abstract

Notizen: Hochdrucksynthese und Einkristall-Strukturverfeinerung von Calciumaurat(III), CaAu2O4 / High Pressure Synthesis and Single-Crystal Structure Refinement of Calcium Aurate (III), CaAu2O4

Abstract

Notizen: Die Kristallstruktur von Calciumchromat(VI), CaCrO4 / The Crystal Structure of Calcium Chromate (VI), CaCrO4

Abstract

5-Bromo-2-(chloroacetamido)benzophenone - a Synthetic Precursor to 6-Bromoviridicatina

Abstract

Zur Reaktivität des Silaethens Me₂Si=C(SiMe₃)₂: Regioselektivität, Stereoselektivität und relative Geschwindigkeiten von En-Reaktionen [1] / On the Reactivity of Silaethene Me₂Si=C(SiMe₃)₂: Regioselectivity, Stereoselectivity and Relative Rates of Ene Reactions [1]

Preparation, Crystal Structure, and Properties of the Lanthanoid Carbides Ln₄C₇ with Ln = Ho, Er, Tm, and Lu

Die elektronische Struktur ternärer Übergangsmetallpnictide. I. AlB₂-Varianten / The Electronic Structure of Ternary Transition Metal Pnictides. I. AlB₂-Variants

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

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

Sulfur and Selenium Complexes of the Hydrido-tri(3,5-dimethyl-1-pyrazolyl) borate Nitrosylmolybdenum Fragment, [TpMo(NO)]. An X-Ray Crystal Structure Determination of TpMo(NO)(Se₅)

Synthese und Struktur von Ag₄[(PhN₃)₂C₆H₄]₂ (en)₂, einem vierkernigen Silber(I)komplex mit 1,2-Bis(phenyltriazenido)benzol als Ligand / Synthesis and Structure of Ag₄[(PhN₃)₂C₆H₄]₂ (en)₂, a Tetranuclear Silver(I) Complex with 1,2-Bis(phenyltriazenido)benzene as Ligand

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

Na₂ZnO₂, ein neues Natriumzinkat / Na₂ZnO₂, a New Sodium Zincate

Über die Reaktion von KPPh₂ mit Fe(CO)₅ und Fe(CO)₄CS; Molekülstruktur von [(CO)₄FePPh₂]^- / On the Reaction of KPPh*, with Fe(CO)₅ and Fe(CO)₄CS; Molecular Structure of [(CO)₄FePPh₂]^-

Zur Synthese und Kristallstruktur von Bariumboroarsenat Ba(BAsO₅) mit einem Beitrag über Bariumorthoarsenat Ba₃(AsO₄)₂ / Synthesis and Crystal Structure of Barium Boroarsenate Ba(BAsO₅) with a Contribution on Barium Orthoarsenate Ba₃(AsO₄)₂

Synthese und Kristallstruktur von (TeCl₃)₂MoCl₆ und β-(TeCl₃)₂ReCl₆ / Synthesis and Crystal Structure of (TeCl₃)₂MoCl₆ and β-(TeCl₃)₂ReCl₆

A-Pr₂S₃, D-Ho₂S₃ und E-Yb₂S₃:Synthese und Einkristallstrukturuntersuchungen / A-Pr₂S₃, D-Ho₂S₃ and E-Yb₂S₃:Synthesis and Single Crystal Structure Investigations

Über die Kristallstruktur der Phenylsulfinsäure C₆H₅SO₂H [11] / On the Crystal Structure of Phenylsulfinic Acid C₆H₃SO₂H [1]

Darstellung und ¹¹B-NMR-Spektrum von Heptabromo-closo-heptaborat, [B₇Br₇]^2- sowie Kristallstruktur von [(C₅H₅N)₂CH₂][B₇Br₇] / Preparation and ¹¹B NMR Spectrum of Heptabromo-closo-heptaborate, [B₇Br₇]^2-, and the Crystal Structure of [(C₅H₅N)₂CH₂][B₇Br₇]

Notizen: Hochdrucksynthese und Einkristall-Strukturverfeinerung von Calciumaurat(III), CaAu₂O₄ / High Pressure Synthesis and Single-Crystal Structure Refinement of Calcium Aurate (III), CaAu₂O₄

Notizen: Die Kristallstruktur von Calciumchromat(VI), CaCrO₄ / The Crystal Structure of Calcium Chromate (VI), CaCrO₄