bluuebunny/crossref_metadata_2025 huggingface dataset:
An EPR and MS Investigation of Hexa-Substituted Pyrrolidine-l-oxyl Aminoxyl Stable Radicals. Unexpectedly Large y-Hydrogen Splittings
Authors: Zhang Yong-Kang , Janzen Edward G.
Published: February 2015

The y-hydrogen hyperfine splitting constant (γ-H hfsc) for stable aminoxyl (nitroxide) spin labels such as 2,2,5,5-tetramethylpyrrolidine-1-oxyl and their derivatives is usually very small (<1.0 G) and not distinguished with EPR spectrometry. Surprisingly, large γ-H hfsc’s (≥2 .0 G) have been detected with EPR for the first time from ten 2-alkyl-2-phenyl-3,3,5,5- tetramethylpyrrolidine-1-oxyl stable aminoxyl radicals. It is discovered that γ-H hfsc’s are very sensitive to the size and the substitution pattern of 2-alkyl groups. When the 2-alkyl group is CH3 or CD3, γ-H hfsc’s are not resolved in the EPR spectra. But if the 2-alkyl group is C2H5, one γ-H hfsc is very large, equal to 4.72 G in C6H6. If the substituent is longer than C2H5, such as n-C3H7, n-C4H9, n-C5H11, n-C6H13 and CH2=CHCH2
- substituents, the γ-H hfsc is slightly smaller, equal to 4.59 G. For secondary substituents such as sec-C4H9 and cyclo-C6H11 , the γ-H hfsc decreases to 2.00 G. Intermediate γ-H hfsc’s correspond to C6H5CH2 (3.18 G) or a tertiary alkyl group such as t-C4H9 (3.47 G). Variation of γ-H hfsc’s is based on the change of the pyrrolidine ring conformation which is a result of the 2-alkyl group influence. The structures of these aminoxyl radicals are characterized also with mass spectrometry. Possible MS fragmentation mechanisms are discussed.
Revised Structure of Haemoventosin
Authors: Rycroft David S. , Connolly Joseph D. , Huneck Siegfried , Himmelreich Uwe
Published: February 2015

The structure of the lichen pigment haemoventosin has been revised to 3,4,6,9-tetrahydro- 5,10-dihydroxy-7-m ethoxy-3S-m ethyl-l,6,9-trioxo-l H-naphtho-[2,3-c]pyran (3), mainly on the basis of long-range δC/δH correlations observed in 2D HMBC NMR experiments and long-range δH/δD isotope effects observed in partial deuteriation experiments with 10-O-acetylhaemoventosin; ortho- and para-quinonoid structures were distinguished by means of the transacetylation inferred in the sodium dithionite reduction of 10-O-acetylhaemoventosin.
Preparation and Characterization of (C6H5CH2CH2NH3)4BiI7 · H2O, (C6H5CH2CH2NH3)3BiBr6 and (C6H5CH2CH2NH3)3BiCl6
Authors: Papavassiliou G. C. , Koutselas I. B. , Terzis A. , Raptopoulou C. P.
Published: February 2015

The title compounds were prepared and characterized analytically, structurally, and spectroscopically. They contain isolated BiX6 (X = I. Br, Cl) anions. Their optical absorption spectra show excitonic bands in the UV-visible spectral region. These bands occur at higher energies than the corresponding bands of R3M2X9 (R = MemNH4-m; m = 1,2, 3, 4).
X-Ray Structure and Magnetic Properties of the Tetracupferronato-bis(μ-methoxy)-diiron(III) Complex
Authors: Elerman Yalcin , Kabak Mehmet , Svoboda Ingrid , Fuess Hartmut , Griesar Klaus , Haase Wolfgang
Published: February 2015

The tetracupferronato-bis(μ-methoxy)-diiron(III) complex has been synthesized in acetonitrile and its crystal structure determined. C26H26N8O10Fe2, monoclinic, space group C2/c, a =18.425(3), b = 12.999(2), c = 15.046(3) Å, β = 124.66(2)°,V = 2964(1) Å3, Z = 4, wR(2) = 0.097 from 1491 reflections (F2). Two iron(III) atoms are at special positions in six-fold coordination, bridged by O with a Fe-O-Fe angle of 102.4(1)° and a distance between two iron(III) centers of 3.075(1) Å. Temperature-dependent magnetic susceptibility measurements reveal a antiferromagnetic exchange interaction (J = -14 cm-1) between the iron(III) centers.
Struktur von Bis(3-phenyl-4-benzoyl-isoxazol-5-onato)kupfer(II)/Structure of Bis(3-phenyl-4-benzoyl-isoxazol-5-onato)copper(II)
Authors: Kraudelt Heide , Hinsche Gerald , Schilde Uwe , Uhlemann Erhard
Published: February 2015

The crystal structure of bis(3-phenyl-4-benzoyl-isoxazol-5-onato)copper(II) was determined for com parison with the copper complexes of 1-ghenyl-3-methyl-4-benzoyl-pyrazol-5-one and some β-diketones. Crystal data: a = 13,320(6) Å; b = 8,421(7) Å; c = 11,516(4) Å; β = 92,34(4)°; space group P21/c ; Z = 2; R = 0,041; 2088 unique reflexions.
Synthese und Kristallstruklur von Triblei-Diphosphato-Borat-Phosphat, eine Verbindung mit einem 1
∞[(PO4)2BPO4]6–-Anion / Synthesis and Crystal Structure of Trilead-Diphosphato-Borate-Phosphate, a Compound with a 1
∞[(PO4)2BPO4]6–-Anion
Authors: Park C. H. , Bluhm K.
Published: February 2015

Single crystals of Pb3[(PO4)2BPO4] were obtained by melting B2O3, P2O3 and PbO at 960 °C. The structure is related to the Ba3[(PO4)2BPO4] type. X-ray investigations on single crystals led to the space group Pbca - D15
2h (Nr. 61) with a = 694.6(1), b = 1419.9(3), c = 2111.6(2) pm, Z = 8 . Boron and phosphorus are tetrahedrally coordinated by oxygen. The polyhedra form one-dimensional infinite helices that contain two additional PO4 groups connected to the BO4-unit. Lead is eightfold coordinated by oxygen. The relation to the crystal structure of Ba3[(PO4)2BPO4] is discussed.
Darstellung und Kristallstruktur von Bis(cyclohexylammonium)heptasulfid · Cyclohexylamin, [C6H11NH3]2S7·C6H11NH2/Preparation and Crystal Structure of Bis(cyclohexylammonium)heptasulfide · Cyclohexylamine, [C6H11NH3]2S7·C6H11NH2
Authors: Müller C. , Böttcher P.
Published: February 2015

The reaction of cyclohexylamine, sulfur, and hydrogen sulfide in a 2:1-mixture of ethanol and water gives a red cyclohexylammonium polysulfide solution. Orange crystals of the title compound can be obtained by slow cooling. The compound crystallizes in the centrosymmetric triclinic space group P1̄. The lattice constants are a = 8.478(7) Å , b = 11.97(1) Å , c = 14.141(8) Å, α = 102.60(6)°, β = 90.53(5)°, γ = 90.43(7)°. The S7
2--chain has an uncommon cis-trans-cis conformation with a sequence of the signs of torsion angles of (+--+) and (-++-).
Darstellung und Struktur von tripod-Cobalt-Aminocarboxylato-Komplexen / Syntheses and Structure of tripod Cobalt Aminocarboxylate Complexes
Authors: Sernau Volker , Hüttner Gottfried , Fritz Martin , Janssen Bernd , Büchner Michael , Emmerich Christiane , Walter Olaf , Zsolnai Laszlo , Günauer Diethelm , Seitz Thomas
Published: February 2015

Reaction of triphos (CH3C(CH2P(Ph)2)3) with Co(II)
aq(BF4)2 followed by reaction with aminoacids leads to the cationic complexes 1-6 ([triphosCoNH2CH(R)COO]+ (R = H; Gly (1), R = methyl: L-Ala (S-2), D-Ala (R-2), R = isopropyl: L-Val (3), R = N -propyl: L - Pro (4), R = phenyl: D-phenylglycine (5), R = benzyl: L - Phe (6 )), which can be isolated in good yields by crystallization as their B(Ph)4
- salts. The analogous reaction of the modified tripod ligand PhCH2C(CH2P(Ph)2)3 with L-alanine leads to the complex [PhCH2C(CH2P(Ph)2)3Co(L-Ala)]+, 7. The cations 1-7 have been characterized by spectroscopic methods and their structures determined by X -ray analyses which unequivocally demonstrate pentacoordinated Co(II) centers.
Indolyl- und Pyrrolylsilane – Synthese und Kristallstruktur / Indolyl- and Pyrrolylsilanes – Syntheses and Crystal Structures
Authors: Frenzel Andrea , Herbst-Irmer Regine , Klingebiel Uwe , Noltemeyer Mathias , Schäfer Martina
Published: February 2015

Lithium indolide and lithium pyrrolide react with fluoro- and chlorosilanes with formation of mono- and bis(indol-1-yl)- and -(pyrrol-1-yl)silanes, tris- and tetrakis(pyrrol-1-yl)silanes as well as of silanes substituted with different heteroaromatic systems. The crystal structures of the lithium indolide and the tetrakis(pyrrol-1-yl)silane have been determined and are discussed.
Untersuchungen an Polyhalogeniden, XXI [1] Die Ethyltriphenylphosphonium-Polyiodide EtPh3PIn mit n = 3,5 und 7 / Studies of Polyhalides, XXI [1] Ethyltriphenylphosphonium Polyiodides EtPh3PIn with n = 3,5 and 7
Authors: Tebbe Karl-Friedrich , Farida Taraneh
Published: February 2015

The compounds EtPh3PI3, EtPh3PI5 and EtPh3PI7 have been prepared by the stoichiometric reaction of EtPh3PI with iodine in a mixture of dichloromethane and ethanol. EtPh3PI3 cry­stallizes in the monoclinic space group P21/n with a = 1176.7(3) pm, b = 1202.5(3) pm, c = 1565.9(4) pm, β=93.22(2)° and Z = 4. The crystal structure has been refined to RF = 0.043 for 3394 reflections. EtPh3PI5 crystallizes in the monoclinic space group I2/a with a = 1913.9(4) pm, b = 1239.0(2)pm, c = 2435.1(4) pm, β = 115.84(1)° and Z = 8. The crystal structure has been refined to RF =0.052 for 3043 reflections. EtPh3PI7 crystallizes in the orthorhombic space group Pbca with a = 1702.7(4)pm. b = 1952.5(4) pm, c = 1809.8(4) pm und Z = 8. The crystal structure has been refined to RF = 0.053 for 3208 reflections. The structures may be described as layerlike packings of cations Ph3EtP+ and of anions I-
3, I-
5 and I-
7, respectively. The isolated triiodide ion I-
3 is slightly asymmetrical and slightly bent as expected. The pentaiodide ion I-
5 forms iodine ribbons like a rope ladder. The heptaiodide ion I-
7 is composed of pentaiodide groups and iodine molecules connected to puckered anionic layers.
Nitrogen-15 and Boron-11 NMR Spectroscopy of the System Acetonitrile / H-ZSM-5
Authors: Feyen F. C. , Burkert P. K.
Published: February 2015

The interaction of adsorbed acetonitrile with microporous [Si,Al]-ZSM-5 and [Si,B]-ZSM-5 was investigated by solid state NMR.15N-CP MAS NMR of the system H-[Si,Al]-ZSM-5 / acetonitrile clearly shows the Bronsted and Lewis acid site interactions. Different coordination types of the complex ZSM-5/MeCN are considered. The accessibility of the acid sites of [Si,B]-ZSM-5, a material structurally analogous to zeolite ZSM-5, was studied by 11B-MAS NMR. The complexation of acetonitrile at the BO3 sites gives a narrow line at -4 ppm. In contrast to hydration phenomena of ZSM-5, the experiments show that acetonitrile is not capable of interacting with all of the BO3 sites of the borosilicate, presumably due to steric effects.
Heteronuclear Nucleobase Complexes as Tools for the Isolation of the Minor Rotamer of the Parent Compound: Synthesis and Crystal Structure Determination of Head-Head and Head-Tail Forms of trans-[(CH3NH2)2Pt(1-MeC-N3)2]2+ (1-MeC = 1-methylcytosine)
Authors: Holthenrich Dagmar , Sóvágó Imre , Fusch Gerd , Erxleben Andrea , Fusch Edda C. , Rombeck Ingo , Lippert Bernhard
Published: February 2015

The two rotamers (head-tail, 1, and head-head, 2) of the bis(1-methylcytosine)complex of trans-(CH3NH2)2Pt(II), have been crystallized as ClO4- (1, 2a) and PF6- (2b) salts and characterized by X-ray crystal structure analysis and 1H and 195Pt NMR spectroscopy. In aqueous solution, 1 is preferred over 2 by 70:30. Upon slow crystallization from H2O, 1 is obtained as the only product. Isolation of 2a and 2b has now been accomplished via formation of the heteronuclear derivative trans-[(CH3NH2)2Pt(1-MeC--N3,N4)2Hg]2+, in which the deprotonated 1-methylcytosinato ligands (1-MeC-) are oriented head-head, precipitation of Hg(II) by thiourea, and rapid crystallization of the parent compound. The solid state structures of 1 and 2b differ markedly in a number of aspects. Isolation of pure 1 and 2 permits a detailed study of the kinetics and thermodynamics of the interconversion of the two rotamers. From comparison with the behavior of 1 and 2 in H2O on the one hand and DMSO and DMF on the other a clear solvent effect on the rotamer distribution is seen which most likely relates to differences in H bonding between solvent and solute.
New Spiro-Tin Compounds: Reaction of N,N′-Dialkyl Sulfur Diimides with Cyclic Bis(amino)stannylenes - Unexpected Formation of a N-N Bond
Authors: Herberhold Max , Köhler Christian , Milius Wolfgang , Wrackmeyer Bernd
Published: February 2015

N,N′-Dialkyl sulfur diimides (1), R(NSN)R [R = Me (a), Et (b), nPr (c), nBu (d)] react with cyclic bis(amino)stannylenes such as 1,3-di-tert-butyl-4,4-dimethyl-1,3,4,2λ2-diazasilastannetedine (2) or 1,3-di-tert-butyl-4,4,5,5-tetramethyl-1,3,4,5,2λ2-diazadisilastannolidine (3) in a 2:1 ratio to give the new spiro-tin(IV) compounds 5a-d, 6b and 6c, built from the respective cyclic bis(amino)stannylene and a seven-membered ring in which the two sulfur diimide groups are coupled via a N-N bond and across the tin atom. A 1:1 adduct 4 is proposed as an intermediate which is the final product 4e in the case of R = tBu (1e). The products were characterized by multinuclear magnetic resonance (1H, 13C, 15N, 29Si, 119Sn NMR), and in the case of 5c the molecular structure was determined by single crystal X-ray structure analysis [monoclinic, space group C2/c ; a = 1504.1(3), b = 1393.3(3), c = 1688.6(3) pm; β = 115.71(3)°].
Umwandlung von η2-Thiocarbenkomplexen des Molybdäns und Wolframs in Metalla-thia-cyclopropan-Systeme / Conversion of η2-Thiocarbene Complexes of Molybdenum and Tungsten to Metalla-thio-cyclopropane Systems
Authors: Ogric C. , Schütt W. , Lehotkay T. , Herdtweck E. , Kreißl F. R.
Published: February 2015

Cationic η2-thiocarbene complexes of molybdenum and tungsten [Cp(CO)2

Me][ BF4] (M = Mo, W; R = Ph, Tol; L = CO, PMe3) react with the germylene Ge{N(tBu)CH2CH2N(tBu)}, the plumbylene Pb{N(SiMe3)2}2, or with sodium azide and sodium thiosulfate to give neutral metalla-thia-cyclopropane complexes Cp(CO)2-

. Instead of the expected cycloaddition or substitution reactions the formal addition of thiomethanolat at the carbene carbon atom is observed. On treating the corresponding trimethylphosphine substituted η2-thiocarbene complex of molybdenum [Cp(CO)(PMe3)

[BF4] with diethylamine or N,N,N′,N′-tetramethylguanidine a cationic molybda-thia-cyclopropane system is formed. The products have been characterized by 1H, 13C, 31P NMR, IR and mass spectra. The crystal structure of 5a has been determined; space group with a = 1340,4(2), b - 1097,7(1), c = 1101,8(5) pm and Z = 4.
Zur Synthese und Kristallstruktur von Kupferzinkpyroboratoxid Cu2Zn(B2O5)O / Synthesis and Crystal Structure of Copper Zinc Pyroborate Oxide Cu2Zn(B2O5)O
Authors: Busche Silke , Bluhm Karsten
Published: February 2015

The compound Cu2Zn(B2O5)O was prepared by using a B2O3 flux technique, and single crystals were investigated by X-ray diffraction (monoclinic symmetry, space group C5
2h-P21/c ). The structure is isotypic to Cu2Co(B2O5)O with lattice parameters a = 327.38(2), b = 1479.4(3), c = 915.39(13), β = 95.794(11)°, Z = 4, but with the significant difference that zinc is pentacoordinated by oxygen. Copper exhibits a nearly square planar or a square pyramidal coordination, respectively. The structure contains isolated B2O5 units and oxygen which is not coordinated to boron.
Circular Dichroism Studies on Chiral 1,3,4,5-Tetrahydro-2H-1,5- benzodiazepin-2-ones
Authors: Khan Khalid Mohammed , Malik Farnaz , Hasan Mashooda , Perveen Shahnaz , Snatzke Günther , Voelter Wolfgang
Published: February 2015

From forty one chiral benzodiazepin-2-ones the UV and CD data are reported and the bands discussed with respect to corresponding electronic transitions respectively stereochemical features.
Synthese und Struktur saurer Ubergangsmetallsulfate - Ti(H5O2)(SO4)2(H2O)2 und Zr(H3O)2(SO4)3 / Synthesis and Structure of Acid Transition Metal Sulfates - Ti(H5O2)(SO4)2(H2O)2 und Zr(H3O)2(SO4)3
Authors: Trojanov S. , Stiewe A. , Kemnitz E.
Published: February 2015

From the ternary system Mn(SO4)n/2 / SO3 / H2O (Mn+ = Zr4+, Ti3+) two new acid metal sulfates, Ti(H5O2)(SO4)2(H2O)2 and Zr(H3O) 2(SO4)3, have been synthesized and structurally characterized. Ti(H5O2)(SO4)2(H2O)2 crystallizes in the orthorhombic space group Pnma with cell parameters a = 9.858(5), b = 18.32(2), c = 5.437(7)Å (Z = 4); Zr(H3O)2(SO4)3 crystallizes in the triclinic space group P1 with cell parameters a = 5.092(2), b = 8.533(3), c = 12.388(6)A, α = 92.95(3)°, β = 90.89(3)°, γ = 94.35(3)° (Z= 2). In the titanium compound there are slightly distorted TiO6 octahedra with Ti-O distances between 1.99 and 2.09 Å which are sharing corners with SO4 tetrahedra. Through hydrogen bonds layers are formed perpendicular to the b-axis. These layers are connected by H3O+ ions only. The structure of Zr(H3O)2(SO4)3 consists of three different SO4 tetrahedra and distorted ZrO7 polyhedra which are connected via common corners and edges to form columns parallel to the a-axis. The Zr-O distances vary from 2.13 to 2.18Å for equatorial positions, significantly longer than the axial Zr-O distances with 2.05Å.
Synthese und Kristallstruktur von (Cu,Fe)3,63Mo3O12. Ein Oxometallat mit eindimensional flächenverkniipften Oktaederketten / Synthesis and Crystal Structure of (Cu,Fe)3,63Mo3O12. An Oxometallate Showing One-Dimensional Chains of Face Sharing Octahedra
Authors: Sedello O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (Cu,Fe)3,63Mo3O12 have been prepared by crystallisation from melts. X-ray investigations lead to orthorhombic symmetry, space group D2
4-P212121, a = 5.0952(8), b = 10.637(2), c = 17.881(3) Å, Z = 4. (Cu,Fe)3,63Mo3O12 is isotypic to Cu3,85Mo3O12 or (Cu,Zn)3,75Mo3O12. Molybdenum shows tetrahedral coordination by oxygen. Cu+ and Fe2+ are probably distributed statistically over four different point positions. Interesting features of the crystal structure are one-dimensional chains of face shared (Cu,Fe)O6 octahedra.
Synthese, Kristallstruktur und Eigenschaften von Tetraaminophosphoniumchlorid [P(NH2)4]Cl / Synthesis, Crystal Structure, and Properties of Tetraaminophosphonium Chloride [P(NH2)4]Cl
Authors: Horstmann Stefan , Schnick Wolfgang
Published: February 2015

[P(NH2)4]Cl has been prepared by ammonolysis of phosphorus pentachloride in liquid ammonia. The product was purified by reacting the byproduct, ammonium chloride, with diethylamine and removing the diethylamine hydrochloride. Suitable single crystals were obtained from an acetonitrile solution in a temperature gradient between 60 °C and room temperature. The crystal structure of [P(NH2)4]Cl has been determined by single crystal X-ray methods (Pbcn, a = 470.8(2), b = 1622.3(3), c = 756.3(2) pm, Z = 4). In the solid, [P(NH2)4]+ and Cl- ions are found, resembling a TlI-analogous structure.

The N-H···Cl distances indicate N-H···Cl hydrogen bonding interactions. The distortion of the P-N sceleton of the cation and the very short P-NH2 distances (mean value: 161.2 pm) have been confirmed by ab initio calculations, which show a generalized anomeric effect of the electron pairs at nitrogen and pπdπ bonding.
Hochdrucksynthese und Strukturverfeinerung von Strontium-Danburit, SrB2Si2O8
Authors: Berger Thomas , Range Klaus-Jürgen
Published: February 2015

Single crystals of strontium danburite, SrB2Si2O8, were found after high-pressure treatment of SrSiO3/SiO2/Al2O3 mixtures at 40 kbar and 1400°C, obviously formed by an unwanted side reaction with the boron oxide-containing boron nitride capsules used. The crystals are orthorhombic, space group Pnma, with a = 8.1891 (5), b = 7.9311 (6), c = 8.9284(5) Å and Z = 4. The structure was refined to R = 0.031, Rw = 0.028 for 590 independent, absorption-corrected reflections. SrB2Si2O8 is isostructural with danburite (CaB2Si2O8). The structure comprises a tetrahedral framework of ordered B2O7 and Si2O7 groups which contains Sr in irregular coordination.
Metallkomplexe mit biologisch wichtigen Liganden, LXXXIV [1] Halbsandwich-Komplexe von Rhodium(III), Iridium(III), Cobalt(III), Ruthenium(II), Ruthenium(III) und Chrom(III) mit Aminosäureester-Liganden Metal Complexes with Biologically Important Ligands, LXXXIV [1] Half-Sandwich Complexes o f Rhodium(III), Iridium(III), Cobalt(III), Ruthenium(II), Ruthenium(III) and Chromium(III) with Amino Acid Ester Ligands
Authors: Bergs Ralph , Krämer Roland , Maurus Michael , Schreiner Bernhard , Urban Reinhold , Missling Christopher , Polbom Kurt , Sünkel Karlheinz , Beck Wolfgang
Published: February 2015

A series of cyclopentadienyl and pentamethylcyclopentadienyl complexes of cobalt, rhodium, iridium, ruthenium and chromium with a-amino-acid esters (L) as ligands was prepared and characterized: Cp*(Cl)2M(L) (1, 2: M = Rh, Ir), Cp(I)2Co(L) (4), [Cp(Ph3P)2Ru(L)]+BF- (6), [Cp(OC)(Ph3P)Ru]+BF- (7) and the paramagnetic compounds Cp*(Cl)2Ru(L) (8) and Cp(Br)2Cr(L) (9). AlaOMe and HisOMe form N ,O and N,N chelate complexes [Cp*(Cl)M(alaOMe)]+BF-
4 (3: M = Rh, Ir), [Cp(I)Co(hisOMe)]+BF4. Cp*Co(CO)I2 and GlyOMe gave the N,O-dipeptide ester complex Cp*(I)Co(glyglyOMe)]+BF-
4 (5). The crystal structures of Cp(I)2Co(glyOEt) and Cp*(Cl)2Ru(alaOMe) were determined by X-ray diffrac­tion. The complexes 1 and 2 undergo ester exchange reactions with CD3OD. [Cp*MCl2]2 (M = Rh, Ir) catalyze the exchange of the ethoxy group in Me2NCH2CO2Et by CD3OD.
Chemie polyfunktioneller Moleküle, 120 [1] Synthesen und Kristallstrukturanalysen von Tris(imido-tetraphenyl- diphosphinato-0,0')eisen(III) und des PP-verknüpften Phosphazens Ph2P-N=PPh2-PPh2=N-PPh2
Authors: Ellermann Jochen , Gabold Peter , Knoch Falk A. , Moll Matthias , Schmidt Astrid , Schütz Martin
Published: February 2015

While the reaction of anhydrous iron(III) chloride with the chelate ligand [(C6H5)2P(O)]2NH (6) is an efficient way to synthesize the new tricyclic compound imido-tetraphenyl-diphosphinato-O,O′iron(III), [Fe{O-P(Ph2)=N-P(Ph2)=O}3] (4), treatment of [(C6H5)2P]2NLi (1) with anhydrous iron(III) fluoride in THF represents a simple route to obtain the phosphorus-phosphorus connected species Ph2P-N=PPh2-PPh2=N-PPh2(7). Both compounds were charac­terized by X-ray crystallography, 1H ,31P {1H}, 13C {1H} NMR, IR, Raman and mass spectra.
Uber ein neues Oxoiridat(V) vom Sr4PtO6-Typ: NaSr3IrO6
Authors: Frenzen S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of NaSr3IrO6 have been prepared by heating mixtures of Na2O2, SrO and iridium in closed silver tubes and were investigated by X-ray techniques, NaSr3IrO6 crystal­lizes with trigonal (rhombohedral) symmetry in the space group D6
3d-R3̄ c , a = 9.636(2), c = 11.556(3) Å , Z = 6, and is isotypic to compounds of the Sr4PtO6 type. The substitution of Sr2+ by Na+ in NaSr3IrO6 led to an ordered metal distribution and an increase of the oxida­tion state from IrIV to Irv.
The Crystal Structure and Low Temperature 13C NMR Spectrum of the Seven-Coordinate Complex of Tungsten(II), [WI2(CO)3(NCPh)2]
Authors: Baker Paul K. , Muldoona David J. , Hursthouseb Michael B. , Colesb Simon J. , Laveryc Aidan J. , Shawcross Andrew
Published: February 2015

The crystal structure of [WI2(CO)3(NCPh)2] (1) has been determined by X-ray methods. The crystals are orthorhombic, space group Pnam, a = 7.815(3), b = 13.839(5), c = 18.475(3) Å, Z = 8, R = 0.0346 for 1497 observed data. The complex [WI2(CO)3(NCPh)2] has a seven-coordinate geometry, which may be described as a distorted capped octahedron, with the two iodo-ligands mutually trans, while each nitrile is trans to a carbonyl group. The capped octahedral geometry consists of a capping carbonyl (C(10)} on the face defined by I(1), C(20) and C(20)#. However, the geom etry may also be described as a capped trigonal prism, which has one triangular face occupied by three carbonyl groups and the second triangular face occupied by N(1) , N (1)# and I(1) atoms, respectively. The iodide I(2) occupies the capping position on the rectangular face defined by the atoms C(20), C(20)#, N (1), and N (1)# . The low temperature 13C NMR spectrum (203 K, CD2Cl2) of 1 shows a single carbonyl resonance at 219.27 ppm which indicates that the complex is undergoing a rapid fluxional process in solution at 203 K.
Synthese und röntgenographische Charakterisierung von zwei neuen Verbindungen des Ludwigit-Strukturtyps: Co5Sn(BO3)2O4 und Co5Mn(BO3 )2O4/Synthesis and X -Ray Characterization of Two New Compounds with Ludwigite-Structure: Co5Sn(BO3)2O4 and Co5Mn(BO3)2O4
Authors: Utzolino Anne , Bluhm Karsten
Published: February 2015

The compounds Co5Sn(BO3)2O4 (I) and Co5Mn(BO3)2O4 (II) were prepared by using a B2O3 flux technique. Single crystals were investigated by X-ray diffraction and showed orthorhombic symmetry, space group D2h
9-Pbam (No. 55), I a = 944.4; b = 1233.8; c = 310.5 pm; Z = 2 and II a = 925.07; b = 1241.67; c = 305.24 pm; Z = 2. Both compounds are isotypic to the mineral Ludwigite. All metal point positions show an octahedral oxygen coordination. Co2+ and M4+ (M = Sn or Mn) occupy one point position statistically. Both structures contain isolated, trigonal planar BO3 units and oxygen atoms that are not coordinated to boron.
Synthese und Kristallstruktur von Dibariumzink-bis(cyclotriborat) Ba2Zn(B3O6)2/Synthesis and Crystal Structure of Di-barium Zinc Bis-cyclotriborate Ba2Zn(B3O6)2
Authors: Busche Silke , Bluhm Karsten
Published: February 2015

Single crystals of the new compound Ba2Zn(B3O6)2 were obtained by using a B2O3 flux technique. They crystallize in an as yet unknown structure type. X-ray investigations led to space group Ci
1-P1̄

(Nr.2) with lattice parameters a = 715.5(2), b = 720.5(2), c = 1178.9(4), a = 78.96(2)°, β = 85.45(2)°, γ = 60.12(1)°, Z = 2. The structure is characterized by iso­lated (B3O6)3--rings and contains two ninefold coordinated Ba-sites. Zn2+ is tetrahedrally coordinated by oxygen. The relation to the crystal structures of high-temperature BaB2O4 and Ba2Ca(B3O6)2 is discussed.
InIII -Phthalocyanine: Darstellung, Eigenschaften und Kristallstruktur von b-Bis(triphenylphosphin)iminium-cis-di(cyanato(N))phthalocyaninato- (2-)indat(III)/ InIII Phthalocyanines: Synthesis, Properties and Crystal Structure of b-Bis(triphenylphosphine)iminium cis-Di(cyanato(N ))phthalocyaninato(2-)indate(III)
Authors: Aβmann Barbara , Franken Andreas , Homborg Heiner
Published: February 2015

[In(Cl)Pc2-] reacts with bis(triphenylphosphine)iminium cyanate ((PNP)OCN) in dichloromethane to yield green-blue b(PNP) cis[In(NCO)2Pc2-] · CH2Cl2, which crystallizes in the triclinic space group P1̄ (No. 2) with Z = 2. The two cyanato(N) ligands are in a mutually cis coordination (∠ (NNCO-In -NNCO) = 84.2(3)°). The In atom is displaced out of the plane of the four Niso atoms towards the two cyanato(N) ligands (d(In-Ct(Niso)4) = 0.988 Å). The average In-NNC0 and In-Niso bond distances are 2.16(1) and 2.216(8) Å, respectively. The NNCO-In -NNCO moiety deviates by ~ 4° from the staggered conformation relative to the In-(Niso)4 sceleton. Though the cyanato(N) ligands are essentially linear, there are different In-N -C angles (164.4(9) and 147.1(8)°) probably due to crystal packing effects. The Pc2- ligand is distorted in an asymmetrically convex manner. The PNP cation adopts the bent conformation (∠(P-N(K)-P) = 143.5(6)°). The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc3-/Pc2- (-0.87 V) < InI/InIII (-0.63 V) < Pc2- /Pc- (0.69 V).The UV-VIS-NIR spectra and the vibrational spectra are discussed.
Eine neue Verbindung im System Ba/Ln/Zn/Pt/O: Ba4Sm4Zn3PtO15/On a New Com pound in the System Ba/Ln/Zn/Pt/O : Ba4Sm4Zn3PtO15
Authors: Sfreddo O. , Rabbow Ch. , Müller-Buschbaum Hk.
Published: February 2015

Reactions of mixtures of BaCO3, ZnO, Sm2O3 (3:5:1) heated in platinum crucibles up to 1250 °C led to big black single crystals of Ba4Sm4Zn3PtO15. The new compound crystallizes with hexagonal symmetry, space group C6v
4mc, a = 11.657, c = 6,789 Å , Z = 2. It is isotypic with Ba6Nd2Al4O15 but shows an ordered Pt4+ and Zn2+ distribution over the aluminium positions. The octahedrally coordinated barium sites of the Ba6Nd2Al4O15 type are occupied by Sm3+. In comparison to compounds of the composition Ba6Ln2M4O15 (M = Al, Fe, Co), Ba4Sm4Zn3PtO15 is the first example containing different oxidation states at the M3+ positions.
Darstellung, 11B-, 13C-, 1H-NMR - und Schwingungsspektren von μ-Pentamethylen-bis-hexahydro-closo-hexaborat, [B6H6(CH2)5B6H6]2-, und μ-Hexamethylen-bis-hexahydro-closo-hexaborat, [B6H6(CH2)6B6H6]2/Preparation, 11B, 13C, 1H NMR and Vibrational Spectra of μ-Pentamethylene-bis-hexahydro-closo-hexaborate, [B6H6(CH2)5 B6H6 ]2-, and μ-Hexamethylene-bis-hexahydro-closo-hexaborate, [B6H6(CH2)6B6H6]2-
Authors: Lübbe W. , Preetz W.
Published: February 2015

In the reaction of [B6H6]2- with diiodopentane or diiodohexane in dichloromethane μ-pentamethylene-bis-hexahydro-closo-hexaborate, [B6H6(CH2)5B6H6]2- (I), and μ-hexamethylene-bishexahydro-closo-hexaborate, [B6H6(CH2)6B6H6]2- (II), are formed, respectively. The products were separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose and have been identified and characterized by 11B, 13C, 1H NMR and vibrational spectroscopy.
2,5,8,11-Tetra-tert-butyl-peri-xanthenoxanthene and its Dication Spectroelectrochemistry and Model Calculations on a Dioxa-22-π-system
Authors: Frenking Gernot , Rieker Anton , Salbeck Josef , Speiser Bernd
Published: February 2015

Spectroelectrochemistry of 2,5,8,1 1-tetra-tert-butyl-peri-xanthenoxanthene 1 yields the UV/VIS spectra of the corresponding radical cation 1+ and dication 12+. The bathochromic shift for the dication 12+ relative to 1 and to the isoelectronic hydrocarbon anthanthrene (2) can be understood by quantum mechanical calculations (ab initio, AM1) of model structures.
Electroreduction of Organic Compounds, 27 Electrochemical Dehalogenation of Endosulfane
Authors: Gassmann J. , Voss J. , Adiwidjaja G.
Published: February 2015

Partial dechlorination takes place if Endosulfane® is electrolysed in methanol solution at lead cathodes. The products are detected and identified by GC/MS, IR and NMR spectroscopy. The structure of the product 2 is confirmed by an X-ray structural analysis.
Novel Enantiomerically Pure Ferrocenes
Authors: Zeijden Adolphus A . H. van der , Sieler J. , Hovestreydt E.
Published: February 2015

A chiral ferrocene (CpE
2Fe) was synthesized by reaction of CpELi with FeCl2(THF)1.5 The cyclopentadienyl ligand CpE contains a dimethylamino group that is separated from the Cp backbone by two stereogenic carbon centres. Reaction of CpE
2Fe with excess Mel affords the ammonium salt CpE
2Fe.2MeI. Its solid state structure was determined by X-ray diffraction methods.
Strukturverfeinerung von Kalium - periodat bei 297 und 150 K/Structure Refinement of Potassium Periodate at 297 and 150 K
Authors: Waal Danita de , Range Klaus-Jürgen
Published: February 2015

The scheelitetype structure of potassium perio­date, KIO4, has been confirmed and refined from single-crystal X-ray data at two temperatures. The compound crystallizes tetragonally, space group I41/a, with a = 5.726(1), c = 12.607(4) Å at 297(1) K, and a = 5.704(3), c = 12.478(8) Å at 150(1) K, respectively. Except for a significant decrease in the anisotropic displacement factors, the changes in the structural parameters at low temperature are rather small.
Geordnete Metallverteilung in KBaVO4 und KSrVO4 mit β-K2SO4-Struktur / Ordered Metal Distribution in KBaVO4and KSrVO4 Showing β -K2SO4 Structure
Authors: Schrandt O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of KBaVO4(I) and KSrVO4(II) have been prepared by crystallization from V2O5 flux. The yellowish crystals show orthorhombic symmetry, space group D16
2h-Pnma with (I): a = 7.774(2), b = 5.899(1), c = 10.375(2) Å , (II): a = 7.400(2), b = 5.812(1), c -9.961(1), Z = 4. Both compounds show an ordered distribution of K+ and Ba2+ and Sr2+ respectively. The different sizes of the KO10 and BaO9 (SrO9) polyhedra are discussed with respect to those of the β-K2SO4 structure, considering the calculations of the Coulomb terms of lattice energy.
Metallkomplexe mit funktionalisierten Schwefelliganden, X [1] Ruthenium(II)-und Platin(II)-1-alkin-1-thiolato-Komplexe. Kristallstrukturanalyse von trans-(Ph3P)2Pt[S-C≡C-C(CH3)3]2 / Metal Complexes of Functionalized Sulfur Containing Ligands, X [1] Synthesis of Ruthenium (II) and Platinum(II) 1-Alkyne-1-thiolato Complexes. X-Ray Structure Analysis of trans-( Ph3P)2Pt[C-C≡C-C(CH3)3]2
Authors: Weigand Wolfgang , Weishäupl Michael , Robl Christian
Published: February 2015

The 1-alkyne-1-thiolates R-C ≡C-SLi [1a: R = C(CH3)3, 1b: R = C6H11 ] react with L2PtCl2 (L = PPh3, 1/2 dppe) and CpRu(PPh3)2Cl, respectively to give the complexes trans-(Ph3P)2Pt[S-C ≡C-C(CH3)3]2 (2a), cis-dppePt[S-C≡C-C(CH3)3]2 (2b), and CpRu(PPh3)2-(S-C ≡ C-R) [3a: R = C(CH3)3, 3b: R = C6H11]. 2a has been characterized by 31P CP/MAS NM R spectroscopy and its crystal structure determined by X-ray diffraction.
The Crystal Structure of Diammonium trans-Tetraammindisulfitonithenate(II)Tetrahydrate,trans-(NH4)2[Ru(SO3)2(NH3)4]·4H2O,and the Tuning of the trans-Influence of the Sulfite Ligand
Authors: Breitinger Dietrich K. , Breiter Roman
Published: February 2015

trans-(NH4)2[Ru(SO3)2(NH3)4]·4H2O(1) (monoclinic, P21/n; a = 629.8(3), b = 1000.6(2), c = 1345.7(5) pm, β = 112.25(4)°, Z = 2; R = 0.021; Rw = 0.017) is obtained as pale greenish-yellow crystals by reaction of trans-[Ru(SO3H)2(NH3)4] (2) with aqueous ammonia, and crystallization at +5 °C. The compound, when isolated, is stable at room temperature for only a few days even under inert gas, but persists under the mother liquor. In the centrosymmetric anion trans-[Ru(SO3)2(NH3)4]2- the bonds Ru-S = 230.5(1) pm are significantly longer than in the neutral complex 2 (227.6(1) pm), whereas the Ru-N bonds are the same in both com­plexes within experimental error (averages 214.1 and 214.0 pm). Hence, the mutual trans-influence of the sulfite ligands is weakened on protonation; the bonding of the co-ligands in cis-position is not affected. The internal structure of the sulfite ligand in 1 with long S-O bonds (average 151.2(5) pm) and small angles O-S-O (average 106.1(6)°) and the weakened Ru-S bond are a good match. The structure of 1 is held together by a complex network of hydrogen bonds, in which all potential hydrogen-bond donors (OH2, NH4
+, NH3) and acceptors (H2O ,SO3) are involved. The structural findings are reflected in the vibrational spectra.
Über die Darstellung, spektroskopische Charakterisierung und Kristallstruktur von Trifluormethylazosulfbn-N,N-dimethylamid (CH3)2NS(O)2NNCF3 / On the Preparation, Spectroscopic Characterization and Crystal Structure of Trifluoromethylazosulfon-N,N-dimethylamid (CH3)2NS(O)2NNCF3
Authors: Minkwitz Rolf , Jakob Jens , Kornath Andreas , Preut Hans
Published: February 2015

The reaction of Trifluoronitrosomethan with (CH3)2NS(O)2NH2 in THF and Na2CO3 as
Syntheses and Properties of Cerium Diphthalocyanines in High Oxidation States; Crystal Structure of [Ce(Pc)2](BF4) 0.33
Authors: Ostendorp G. , Rotter H. W. , Homborg H.
Published: February 2015

Ring oxidized green Cerium(IV)diphthalocyanines, [Ce(Pc)2]X (X = (poly)halide, NO3
-) are prepared by chemical oxidation of (nBu4N)[Ce(Pc2-)2] with the corresponding halogen in solution or of solid [Ce(Pc2-)2] with aqueous HNO3 Electrochemical oxidation of (nBu4N)[Ce(Pc2-)2] in solution in the presence of (nBu4N)BF4 yields [Ce(Pc)2](BF4)0.33, which crystallizes in the tetragonal space group P4/nnc (a, b = 19.643(3) Å, c = 6.525(3) A, Z = 2). The CeIV ion is eightfold coordinated by the isoindole N atoms (Niso) of the two staggered (ca. 41°), slightly distorted Pc ligands. The “[Ce(Pc)2]0.33+” subunits are arranged in infinite columns along [001] with the Ce atoms statistically disordered over two positions and Ce - Niso bond lengths of 2.45(1) and 2.69(1) A, respectively The UV-VIS spectrum is dominated by the transitions of the Pc2- ligand at ca. 15,000 (B band), 30,000 and 36,000 cm -1 (Q, N region). A low energy (“metallic”) band at ca. 2800 cm -1 typical for partially oxidized systems is present. The UV-VIS-NIR spectrum of [Ce(Pc)2]NO3 indicates a cofacial Pc2- - P c- complex. In addition to the π-π’ transitions of the Pc2- moiety at ca. 14,000, 30,000 and 36,000 cm-1, the Ch transition of the Pc- ring is observed at ca. 19,200 cm -1 and the typical NIR band at 6380 cm -1. Oxidation of a thin film of (PNP)[Ce(Pc2-)2] with dry Br2/ N2 gas yields purple [Ce(Pc-)2]Brx, whose UV-VIS-NIR spectrum shows the diagnostic features of dimeric Pc- radicals with intense bands at ca. 14,000 and 18,000 cm -1 assigned as B and Q1 bands, respectively. At ca. 9000 cm-1 the typical QD absorption is observed. The vibrational spectra are dominated by the transitions of the Pc- ligand at 1305/1445 cm -1 (IR) and 560/1120/1172/1591 cm-1 (resonance Raman). Excitation with 1064 nm strongly enhances the sym. C e-N stretch at 163 c m -1.
Tieftemperatur-Kristallstruktur der Einschlußverbindung {[N(CH3)4]+Cl]2
-} · CH3CN · H2O / Low-Temperature Crystal Structure of the Inclusion Compound {[N(CH3)4]+Cl]2
-} · CH3CN · H2O
Authors: Minkwitz Rolf , Bröchler Raimund , Preut Hans
Published: February 2015

The crystal structure of {[N(CH3)4
+Cl]2}·CH3CN · H2O is reported. Crystalls are orthorhombic, space group Pnma, with a = 1622.9(15), b = 671.3(6), c = 1511.2(11) pm, V = 1646(2) 106 pm3 and Z = 4.
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)
Authors: Dölling Karin , Krug André , Hartung Helmut , Weichmann Horst
Published: February 2015

Diastereoselective alkylation of (S)-2-t-butyl-1-t-butyloxycarbonyl-3-methyl-4-imidazolidinone (Boc-BMI) 1 with R3SnCH2I 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 R3-nXnSnCH2-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 Me2Sn(CH2I)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.
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)
Authors: Herberhold Max , Jin Guo-Xin , Rheingold Arnold L.
Published: February 2015

The reactions of hydrido-tri(3,5-dimethyl-1-pyrazolyl)borate nitrosylmolybdenum diiodide, Tp*Mo(NO)I2 (2), with the oligochalcogenides (NH4)2S10 and (NEt4)2Se6 in THF solution lead to mononuclear cyclo-pentachalcogenido complexes, Tp*Mo(NO)(E5) (E = S (3a), Se (3b)). In the presence of either H2S or H2Se (generated by slow “in situ” hydrolysis of AI2E3 in moist THF solution) 2 is converted into binuclear chalcogenido-bridged products, Tp*
2Mo2(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)l2. The molecular structure of Tp*Mo(NO)(Se5) (3b) has been determined; the complex contains a sixmembered MoSe5; metallacycle in the chair conformation and a linearly coordinated nitrosyl ligand (angle Mo-N-O 178.9(17)°).
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
Authors: Hörner Manfredo , Pedroso Antônio Gilberto , Beck Johannes , Strähle Joachim
Published: February 2015

Ag4[(PhN3)2C6H4]2(en)2 is obtained by the reaction of [Ag(NH3)2]+ with 1,2-bis- (phenyltriazeno)benzene and ethylenediamine. It crystallizes in the monoclinic space group P21/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 [(PhN3)2C6H4]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.
Na2ZnO2, ein neues Natriumzinkat / Na2ZnO2, a New Sodium Zincate
Authors: Trinschek D. , Jansen M.
Published: February 2015

By reacting Na2O, which was produced in situ from NaN3 and NaNO2, with reactive ZnO in the solid state, the synthesis of Na2ZnO2 has been achieved. Na2ZnO2 is metastable up to about 750°C. The novel sodium zincate crystallizes in the spaceogroup P21/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 Ln2S2O (Ln = Er, Tm, Yb, Dy) structure.
Synthese und Kristallstruktur von (TeCl3)2MoCl6 und β-(TeCl3)2ReCl6 / Synthesis and Crystal Structure of (TeCl3)2MoCl6 and β-(TeCl3)2ReCl6
Authors: Beck J. , Biedenkopf P. , Müller-Buschbaum K.
Published: February 2015

Single crystals of (TeCl3)2MoCl6 and β-(TeCl3)2ReCl6 are obtained by the reactions of TeCl4 with MoCl4 at 195 °C and of TeCl4 / Te with ReCl5 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, (TeCl3)2MoCl6: a = 1116,9(1), c = 3539,5(5) pm. 1966 unique reflections for 69 parameters, final R = 0.058; β-(TeCl3)2 ReCl6: a = 1113,3(3), c = 3546(2) pm. 1653 unique reflections for 70 parameters, final R = 0.034). The structures consist of octahedral MCl6
2- anions (with M=Mo,Re) and pyramidal TeCl3+ cations. The ions are interconnected through long Te-Cl bridges (291,1- 295,6 pm) to give distorted TeCl6 octahedra. MCl6 and TeCl6 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 (TeCl3)2ReCl6, only connections via corners are observed.
Notizen: Die Kristallstruktur von Calciumchromat(VI), CaCrO4 / The Crystal Structure of Calcium Chromate (VI), CaCrO4
Authors: Weber Gabriele , Range Klaus-Jürgen
Published: February 2015

The zircon-type structure of calcium chromate( VI), CaCrO4, has been confirmed and refined from single-crystal X-ray data. The compound crystallizes tetragonaly, space group I41/amd, with a = 7.222(2), c = 6.285(1) Å, c/a = 0.8703 and Z = 4. The structure comprises isolated, slightly distorted CrO4 tetrahedra ( C r-O = 1.646(3) Å ) which are connected with CaO8 dodecahedra ( = 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 CaCrO4
Metallkomplexe von N-(Pyrrol-l-yl)salicylaldiminen und deren Strukturbestimmung mittels Röntgendiffraktometrie und Röntgenabsorptionsspektroskopie (XANES) / Metal Chelates of N -(Pyrrol-l-yl)salicylaldim ines and their Structure D eterm ination by X-Ray Structure Analysis and X -R ay Absorption Spectroscopy (XANES)
Authors: Bach A. , Beyer L. , Gelbrich T. , Hallmeier K. H. , Hennig C. , Möbius M. , Richter R. , Szargan R. , Fernandez V. , Losada J.
Published: February 2015

A series of three N-(pyrrol-l-yl)salicylaldim ines 1-3 has been prepared an d characterized. Their metal chelate complexes with Cu, Ni and Co are described. The molecular structures of bis[N-(pyrrol-l-yl)salicylaldim inato]copper(lI) la, bis{N-[3-(pyrrol-l-yl)propyl]- salicylaldiminato}nickel(II) 2b and tris{N-[3-(pyrrol-l-yl)propyl]salicylaldiminato}cobalt(III) 2d were determined by X-ray structure analysis. The chelates with tetracoordinated copper and nickel show a square planar coordination with the characteristic trans configuration. The chelate with hexacoordinated cobalt has a meridional coordination sphere. The complexes have also been investigated by X-ray absorption spectroscopy (X̲-ray A̲bsorption N̲ear E̲dge S̲tructure, XANES) at the K edges of the 3d metals. Analyzing the relative intensities of the Is → 3d prepeak and the K edges of the line shape, it was possible to distinguish between planar, tetrahedral and octahedral coordination of the chelates
Reaktive E=C(p-p)π-Systeme, XLIII [1] Darstellung und Charakterisierung P-Phosphino- oder P-Arsino-substituierter Fluorphosphaalkene des Typs R2E-P=C(F)NEt2 (R = Me, CF3, Me2N; E = P, As) / Reactive E=C(p-p)-π Systems XLIII [1] Synthesis and Characterization of P-Phosphino or P-Arsino Substituted Fluorophosphaalkenes of the Type R2E-P=C(F)NEt2 (R= Me, CF3, Me2N; E = P As)
Authors: Grobe Joseph , Van Duc Le , Winnemöller Jost , Krebs Bernt , Läge Mechtild
Published: February 2015

The easily accessible phosphaalkene HP=C(F)NEt2 (lb) reacts with halophosphanes or -arsanes R2EX (X = Cl, I) in the presence of NEt3 to give P-phosphino- or -P-arsino substituted fluorophosphaalkenes of the type RiE-P=C(F)NEti (2 - 6) in high yields (60 - 85 %) [R2E: (CF3)2P (2), Me2N(CF3)P (3), Me2P (4), (CF3)2As (5), Me2As (6)]. The analogous reaction of ib with CF3PI2 (molar ratio 1:2) unexpectedly leads to the triphosphetene Et2N - C=P-PCF3-PCF3 (7). The stability of compounds 2 - 6 as a function of R2E decreases from As to P and from CF3 to Me, respectively.

Compounds 2 - 6 generally show the Z-configuration and have been characterized by thorough spectroscopic investigations (MS,IR; 1H, 19F, 11C, 31PNMR). A single crystal X-ray diffraction study of 2 proves the π-type interaction of the nitrogen lone pair with the P=C bond thus enhancing the stability of the system and the PP bond order
The Stannides EuPdSn and EuPtSn
Authors: Pöttgen Rainer
Published: February 2015

EuPdSn and EuPtSn were prepared from the elements in tantalum tubes at 1070 K and investigated by X-ray diffraction on both powder as well as single crystals. They crystallize with the TiNiSi type structure of space group Pnma and with Z = 4 formula units per cell. Both structures were refined from single-crystal diffractometer data: a = 751.24(9), b = 469.15(6), c = 804.31(9) pm, V = 0.2835(1) nm3 for EuPdSn, and a = 753.38(7), b = 467.72(4), c = 793.08(7) pm, V = 0.2795(1) nnr for EuPtSn. The structures consist of three-dimensional [PdSn] and [PtSn] polyanionic networks in which the europium atoms are embedded. The crystal chemistry of these stannides is briefly discussed
Komplexe eines vierzehngliedrigen Tetraazadibenzo-Makrocyclus. Strukturen des freien und zweifach protonierten Liganden und seiner Nickel(II)-, Kupfer(II)-, Zink(II)- und Palladium(II)-Komplexe / Complexes of a 14-Membered N4 Dibenzo Macrocycle. Crystal Structures of the Free and Diprotonated Ligand and of its Nickel(II), Copper(II), Zink(II) and Palladium (II) Complexes
Authors: Feldhaus Ralf , Köppe Jens , Mattes Rainer
Published: February 2015

The synthesis and structural characterisation of complexes of the 14-membered macrocyclic trans-N4 dibenzo ligand 5,6,7,8,9,14.15,16,17,18-decahydrodibenzo[e,l][1,4, 8,11]-tetraazacyclotetradecine (L2) is described. The crystal structures of six compounds were determined by single crystal X-ray diffraction. The free ligand L2 has a saddle-shaped structure with short intramolecular hydrogen bonds. The N-N distances are 289 pm. The diprotonated species [H2L2]2+ has a different conformation due to intra- and intermolecular hydrogen bonds. The ligand is folded along an N-N axis in c/s-[Ni(L2)(H2O)2]2+, but displays a saddleshaped structure in the Cu(II), Zn(II) and Pd(II) complexes with a more or less planar arrangement of the four N donor atoms. The metal atoms are incorporated within the macrocyclic cavity in [Cu(L2)(CF3SO3)]+ and [Pd(L2)]2+. The metal-to-nitrogen bond lengths herein are rather small. Zn(II) is five-coordinate in [Zn(L2)(Cl)]+. The coordination polyhedron is intermediate between a trigonal bipyramid and a square pyramid. In all complexes the metalto- ligand distances originating at the nitrogen atoms in β-position (with respect to the aromatic ring) are significantly shorter then the donor bonds of the ‘anilinic’ N atoms