bluuebunny/crossref_metadata_2025 huggingface dataset:
Transmissionsoptimierte Einkristallstrukturbestimmung und elektronische Struktur von Bi3Ni / Transmission-Optimized Single-Crystal Structure Determination and Electronic Structure of Bi3Ni
Authors: Ruck Michael , Söhnel Tilo
Published: February 2015

Crystals of Bi3Ni were synthesized using iodine as mineralizer. X-ray diffraction on a single-crystal including transmission-optimized measurement and optimized absorption correction (μ(Mo-Kα) = 1302 cm−1) results in a structure model (Pnma; a = 887.96(7), b = 409.97(3), c = 1147.8(1) pm) with significant deviations in interatomic distances compared with previous data from X-ray and neutron investigations. From quantum chemical calculations and from the structural chemistry of the subhalides related to Bi3Ni the chemical structure of the intermetallic compound can be derived. In the crystal structure the Ni atoms have a capped trigonal prismatic coordination of Bi atoms with strong bonds Ni-Bi and Ni-Ni. The prisms constitute rods 1
∞ [NiBi1/1Bi6/3] by sharing the non-capped square faces. The bonding between the intermetallic rods is clearly weaker than inside them, leading to a preservation of this structural fragment in the subhalides of Bi3Ni. In accordance with the low temperature superconductivity of the compound, its electronic band structure shows steep and flat bands at the Fermi level. DFT and ELF calculations reveal a separation of delocalized conduction electrons inside the prism rods and largely localized valence electrons between them.
Synthesis of a Benzothiazol-2-ylidene Complex of Tungsten(0) and Transfer of the Ylidene Ligand to Rhodium(I)
Authors: Hahn F. Ekkehardt , Meier Nicole , Pape Tania
Published: February 2015

2-Lithiobenzothiazole reacts with freshly generated [W(CO)5(THF)] to give the anionic ylidene complex (1). Treatment of 1 with allyl bromide yields complex [W(CO)5(1-allylbenzothiazolin-2- ylidene)] (2) while the reaction in wet CH2Cl2 leads to the formation of a mixture of 2 (major) and [W(CO)5(1-H-benzothiazolin-2-ylidene)] (3) (minor). Complex 2 reacts in a transmetallation reaction with [Rh(coe)2(μ-Cl)]2 (coe = cyclooctone) to give the dicarbene complex [Rh(Cl)(η1- NHC)(η2-NHC)] (NHC = 1-allylbenzothiazolin-2-ylidene) with one carbene ligand coordinated via the C2 carbon atom and the other one coordinating with both the C2 carbon atom and the allyl group.
Organozinc Siloxide-Hydrazide Aggregates [(RZn)4(NHNMe2)x(OSiMe3)(4 – x)]
Authors: Jana Surajit , Fröhlich Roland , Mitzel Norbert W.
Published: February 2015

The reaction of dialkylzinc compounds R2Zn (R = Me, Et) with N,N-dimethylhydrazine and trimethylsilanol in a 4 : 2 : 2 ratio leads to the formation of tetra(alkylzinc) tris-siloxide monohydrazide aggregates, [(RZn)4(NHNMe2)(OSiMe3)3] [R = Me (1) and Et (2)]. These compounds are aggregates of mirror symmetry, containing the novel Zn4N2O3 core. Both compounds have been characterised by 1H, 13C and 29Si NMR and IR spectroscopy, by mass spectrometry and by elemental analysis, and 2 also by X-ray crystallography. The structure can be derived from a heterocubane, in which one anionic vertex is replaced by an NHNMe2 group contributing two N atoms to the core constitution. By applying a ratio of hydrazine : silanol of 2 : 1 in a reaction with R2Zn (R = Me, Et, iPr), compounds of the general formula [(RZn)4(NHNMe2)2(OSiMe3)2] [R = Me (3), Et (4), iPr (5)] are obtained. These aggregates contain a Zn4N4O2 core. Upon employing a hydrazine : silanol ratio of 5 : 1 in a reaction with diisopropyl zinc, the compound [(iPrZn)4(NHNMe2)3(OSiMe3)] results, containing a Zn4N6O unit. Compounds 3 - 6 have been characterised by 1H, 13C and 29Si NMR and IR spectroscopy, by mass spectrometry and by elemental analysis. The topologic relationship between the pure hydrazides [(RZn)4(NHNMe2)4], the mixed aggregates [(RZn)4(NHNMe2)3(OR’)], [(RZn)4(NHNMe2)2(OR’)2] and [(RZn)4(NHNMe2)3(OR’)3] and the pure alkoxides [(RZn)4(OR’)4] is discussed.
[Me4N]3[(WOS3)2Ag]·MeCN – An Acetonitrile Solvate with Linear Complex Anions
Authors: Dilshad Rahima , Boller Herbert , Klepp Kurt O.
Published: February 2015

The title compound was prepared by the reaction of [Me4N]2WOS3 with AgCN in MeCN at room temperature and slow crystallisation in the refrigerator. It was characterized by IR and mass spectroscopy. It crystallizes in the orthorhombic space group Pnma (No. 62) with unit cell dimensions a = 19.648(7), b = 27.878(12), c = 11.494(3) Å , Z = 8. The crystal structure was determined from single crystal diffractometer data (Mo-Kα radiation) and refined to R = 0.077. The structure is composed of mixed double layers containing the linear trinuclear anion [(WOS3)2Ag]3− and cations separated by a layer formed by cations and solvating acetonitrile molecules.
Crystal Structure and Physical Properties of New Ternary Gallides Eu2Rh3Ga9 and Eu2Ir3Ga9
Authors: Sichevych Olga , Schnelle Walter , Prots Yurii , Burkhardt Ulrich , Grin Yurii
Published: February 2015

The compounds Eu2Rh3Ga9 and Eu2Ir3Ga9 were synthesized by melting the elements in sealed tantalum tubes with subsequent annealing at 600 °C. Both gallides are isotypic with Y2Co3Ga9 (space group Cmcm, Pearson symbol oC56, Z = 4) as evidenced by single crystal structure analysis: a = 12.9902(6), b = 7.6141(4), c = 9.7433(5) Å , RF = 0.025, 617 structure factors, 42 variable parameters for Eu2Rh3Ga9, and a = 13.0371(7), b = 7.6017(4), c = 9.6972(6) Å , RF = 0.032, 645 reflections, 42 variables for Eu2Ir3Ga9. Magnetic susceptibility measurements as well as X-ray absorption spectra indicate the 4f7 electronic configuration of europium (Eu2+) with significant admixture of the 4f6 state in both compounds.
Polysulfonylamine, Clxxv [1]. Intermolekulare Wechselwirkungen In Kristallinen Di(Organosulfonyl)Aminen. Teil 3 [2]. Supramolekulare Strukturen Von Di(Benzolsulfonyl)Amin, (Benzolsulfonyl)(Methansulfonyl)Amin Und Di(Ethansulfonyl)Amin
Authors: Moers Oliver , Blaschette Armand , Latorre Violeta , Jones Peter G.
Published: February 2015

Low-temperature X-ray structures of the following di(organosulfonyl)amines, HN(SO2R)(SO2R’), are compared in order to study the packing effects of group-specific intermolecular interactions: R = R’ = phenyl (1, monoclinic, P21/c, Z' = 1); R = phenyl, R’ = methyl (2, monoclinic, P21/n, Z' = 1); R = R’ = ethyl (3, monoclinic, P21/c, Z' = 1). The molecules of each compound are associated into catemers by N-H···O hydrogen bonds of graph set C(4). These catemers form molecular layers via distinctive cross-linking modes, which underline the specific propensity of the organic groups to establish directional intermolecular interactions. Thus, the packing of 1 displays striated layers constructed from polar strands of hydrogen-bonded HN(SO2)2 fragments, and apolar strands, in which (phenyl)4 supercycles based upon C-H···C(π) interactions are fused into a linear superpolymer by π ···π stacking-dimer motifs; moreover, C-H···O hydrogen bonds occur between adjacent intralayer strands and between adjacent layers. Molecule 1 features conformational anomalies induced by the high geometric demands of the supramolecular phenyl pattern. In contrast to 1, compound 2 forms lamellar layers comprising an internal polar lamella of N-H···O connected HN(SO2)2 fragments as well as inductively activated methyl groups, and apolar peripheral regions of phenyl rings. The methyl groups are engaged with all their hydrogen atoms in a two-dimensional C-H···O network, whereas the protruding phenyl rings of adjacent layers are interlocked in such a way that short C-H···O inter-layer contacts are created. On account of the reduced phenyl population as compared to 1, C-H···C(π) and π ···π stacking interactions are absent from the crystal structure of 2. Structure 3 finally consists of homogeneous layers, in which the N-H···O based catemers are both re-enforced and cross-linked by C-H···O bonds originating from the four activated methylene hydrogen atoms, whereas adjacent layers are separated by methyl-oxygen contacts with H···O distances longer than the van der Waals limit
New Indides Sc6Co2.18In0.82, Sc10Ni9In19.44 And Sccu4In – Synthesis, Structure, And Crystal Chemistry
Authors: Zaremba Roman I. , Kalychak Yaroslav M. , Rodewald Ute Ch. , Pöttgen Rainer , Zaremba Vasyl’ I.
Published: February 2015

New indides Sc6Co2.18In0.82, Sc10Ni9In- and ScCu4In have been synthesized from the elements by arc-melting. Single crystals were grown by special annealing modes. The thee indides were investigated via X-ray powder and single crystal diffraction: Ho6Co2Ga type, Immm, a = 886.7(3), b = 878.0(2), c = 932.1(3) pm, wR2 = 0.0517, 711 F2 values, 35 variables for Sc6Co2.18In0.82, Ho10Ni9In20 type, P4/nmm, a = 1287.5(2), c = 884.7(1) pm, wR2 = 0.0642, 1221 F2 values, 63 variables for Sc10Ni9In19.44, and MgCu4Sn type, F ¯43m, a = 704.03(7) pm, wR2 = 0.0267, 101 F2 values, and 7 variables for ScCu4In. The scandium rich indide Sc6Co2.18In0.82 contains two Co2 dumb-bells at Co-Co distances of 221 and 230 pm. Each cobalt atom within these dumb-bells has a tricapped trigonal prismatic coordination. The In1 site has a distorted cube-like coordination by scandium and shows a mixed occupancy (36%) with cobalt. The In2 atoms have distorted icosahedral scandium coordination. As a consequence of the small size of the scandium atoms, the In4 site in Sc10Ni9In19.44 shows defects and was furthermore refined with a split model leading to a new distorted variant within the family of Ho10Ni9In20 compounds. ScCu4In is an ordered version of the cubic Laves phase with scandium and indium atoms in the CN16 voids of the copper substructure. The Cu-Cu distances within the three-dimensional network of corner-sharing tetrahedra are 248.6 and 249.2 pm. The crystal chemical peculiarities of these three indide structures are briefly discussed
Indirect Nuclear Spin-Spin Coupling Constants 1J(17O,11B). First Observation And Calculation Using Density Functional Theory (Dft)
Authors: Wrackmeyer Bernd , Tok Oleg L.
Published: February 2015

Coupling constants 1J(17O,11B) of borates, borane adducts and boranes with boron-oxygen bonds have been calculated on the basis of optimised molecular structures using the B3LYP/6-311+G(d,p) level of theory. This indicates that such coupling constants can be of either sign and that their magnitudes can be rather small. Since both 11B and 17O are quadrupole nuclei, it is therefore difficult to measure representative data. In the cases of trimethoxyborane and tetraethyldiboroxanes, it proved possible to obtain experimental data 1J(17O,11B) (22 and 18 Hz) by measurement of 17O NMR spectra at high temperature (120 °C and 160 °C) respectively. The magnitude of these coupling constants is in reasonable agreement with calculated data. In the case of the diboroxane, this points towards a bond angle B-O-B more close to 180◦ than to 140°
Synthesis, Structure, Spectroscopic Studies And Ab-Initio Calculations On First Hyperpolarizabilities Of N,N’-Bis(2-Hydroxy-1-Naphthylmethylidene)- 1-Methyl-1,2-Diaminoethane-N,N’,O,O’-Copper(Ii)
Authors: Karakaş Asli , Elmali Ayhan , Ünver Hüseyin , Kara Hulya , Yahsi Yasemin
Published: February 2015

N,N’-Bis(2-hydroxy-1-naphthylmethylidene)-1-methyl-1,2-diaminoethane-N,N’,O,O’-copper(II) has been synthesized, and characterized by FT-IR and UV/vis spectroscopies. Its crystal structure has been determined by X-ray diffraction analysis. The maximum absorption wavelengths recorded by linear optical experiments are estimated in the UV region to be shorter than 450 nm, showing good optical transparency to the visible light. It may thus possess first hyperpolarizabilities with non-zero values for nonlinear optical (NLO) applications. Ab-initio quantum chemical calculations of the electric dipole moments (μ) and the first static hyperpolarizabilities (β ) were carried out. The computational results suggest that the complex may indeed have microscopic NLO behavior with non-zero values
Synthesis, Crystal Structure And Spectroscopic Studies Of A Mixed Ligand Copper (Ii) Complex: Trans-Bis(Succinimidato)-Bis(Benzylamino)Cu(Ii)
Authors: Taş Murat , Saraçoğlu Hanife , Bati Hümeyra , Çalışkan Nezihe , Büyükgüngör Orhan
Published: February 2015

The molecules of the title compound, [Cu(C11H13N2O2)2], lie across centres of inversion in space group P21/c and are linked by intermolecular N-H···O and C-H···O hydrogen bonds. The central Cu atom has a slightly distorted square-planar coordination comprised of four N atoms. Cu-N bond distances are 1.975(2) and 2.020(2) Å . The interplanar angle between the phenyl and succinimidato ring is 87.34(10)°
Reversible Conversion In The Brassinosteroid Quartet Castasterone, Brassinolide And Their 3β-Epimers
Authors: Antonchick Andrey P. , Svatoš Aleš , Konstantinova Olga V. , Zhabinskii Vladimir N. , Khripach Vladimir A. , Schneider Bernd
Published: February 2015

The metabolism of deuterated brassinosteroids has been studied in excised leaves of Secale cereale, and in vitro in seedlings of Arabidopsis thaliana and cell suspension cultures of Lycopersicon esculentum. In addition to the known biosynthetic conversion of castasterone to brassinolide and epimerization to 3-epicastasterone, inversion of the 3α-configured hydroxyl group of brassinolide to a 3β -configured one in 3-epibrassinolide has been observed using liquid chromatography (HPLC) with electrospray ionization (ESI) and selected ion-monitoring mass-spectrometry (SIM-MS). Administration of deuterated 3-epicastasterone and 3-epibrassinolide to Arabidopsis and Secale seedlings resulted in the formation of castasterone and brassinolide, respectively, indicating conversion of configuration at C-3 of brassinosteroids is reversible
ζ-Y2[Si2O7]: Ein neuer Strukturtyp in der Yttrialit-Reihe / ζ -Y2[Si2O7]: A New Structure Type within the Yttrialite Series
Authors: Hartenbach Ingo , Meier Steffen F. , Schleid Thomas
Published: February 2015

During attempts of preparing yttrium oxotellurates(IV) using Y2O3 and TeO2 in YCl3 fluxes, the occasional reaction of these educts with the walls of the evacuated silica ampoules led to colourless, lath-shaped single crystals of Y2[Si2O7] in the new ζ -type structure as a minor by-product which was investigated by X-ray diffraction. The title compound crystallizes monoclinically in the space group P21/m (a = 503.59(5), b = 806.47(8), c = 732.65(7) pm, β = 108.633(6)°) with two formula units per unit cell. The crystallographically unique Y3+ cation is coordinated by seven oxygen atoms (d(Y-O = 221 - 248 pm) arranged in the shape of a slightly distorted monocapped octahedron. The isolated oxodisilicate units [Si2O7]6− consist of two Si4+ cations and seven O2− anions of which five are crystallographically independent. These pyroanions (d(Si-O) = 161 - 168 pm, ∢ (O-Si-O) = 91 - 117°, ∢ (Si-O-Si) = 156°) exhibit an almost perfectly eclipsed conformation built of a horseshoeshaped backbone with the two silicon and three of the oxygen atoms situated on the mirror planes of the unit cell. The remaining four oxide anions complete this [Si2O7]6− entity of two vertex-sharing [SiO4]4− tetrahedra as terminal ligands for silicon. Assembled in planar layers parallel to (−1 0 1), the [Si2O7]6− anions are packed with their wide basal faces of the tetrahedra pointing towards the small waist of the adjacent units and vice versa. The yttrium cations reside between these layers in order to interconnect them three-dimensionally.
Synthesis, Spectral and Thermal Studies, and Crystal Structure of cis-Bis(imidazole)bis(picolinato)copper(II) Dihydrate [Cu(pic)2(im)2] ·2H2O
Authors: Heren Zerrin , Keser Cem , Ersanlı C. Cüneyt , Yeşilel O. Zafer , Büyükgüngör Orhan
Published: February 2015

The mixed-ligand picolinato (pic) complex of Cu(II) with imidazole (im), [Cu(pic)2(im)2] ・2H2O, was synthesized and characterized by elemental analysis, magnetic susceptibility, spectral methods (UV/vis and FT-IR), simultaneous TG, DTA techniques, mass spectroscopy, and X-ray diffraction. The complex crystallizes in the monoclinic space group Cc with the following unit cell parameters: a = 16.381(1), b = 9.556(1), c = 5.177(1) Å , β = 119.074(5)°, Z = 4. In the octahedral complex, the picolinato ligands are coordinated to the copper(II) ion as bidentate N,O-donors forming chelate rings. The imidazole ligands are N-coordinated at cis positions. The thermal decomposition pathway of the complex has been studied by the help of thermal analyses data (TG and DTA) and of the mass spectroscopic fragmentation pattern. The volatile products observed in the thermal decomposition process were also observed in the mass spectrometer ionisation process, except for the molecular peak, and it was concluded that the ionisation and thermal decomposition pathways of the complex resemble each other.
Dimethyl Sulfoxide Containing Platinum(II) and Palladium(II) Chelate Complexes of Glyoxylic and Pyruvic Acid Thiosemicarbazones. A New Class of Cytotoxic Metal Complexes
Authors: Dodoff Nicolay I. , Kovala-Demertzi Dimitra , Kubiak Maria , Kuduk-Jaworska Janina , Kochel Andrzej , Gorneva Galina A.
Published: February 2015

The complexes [Pt(DMSO)(GT)]·DMSO (1), [Pt(DMSO)(PT)]· 1/2 DMSO (2) and [Pd(DMSO)- (PT)] (3), where DMSO = dimethyl sulfoxide, H2GT = glyoxylic acid thiosemicarbazone and H2PT = pyruvic acid thiosemicarbazone, have been synthesized and characterized by elemental analysis, molar electric conductivity, IR, electronic and NMR (1H and 13C) spectra. The single crystal X-ray diffraction analysis has revealed for 1 (orthorhombic, Pnma, a = 12.941(3), b = 7.108(2), c = 15.148(3) Å , Z = 4) that the doubly deprotonated thiosemicarbazone molecule is coordinated to Pt(II) via the carboxylato O, azomethine N and thiolato S atoms forming two condensed fivemembered chelate rings. The fourth coordination site of Pt(II) is occupied by the S atom of DMSO. All the atoms of the complex molecule are coplanar except the methyl groups. The O atom of DMSO is in cis-position towards the thiolato-S atom (point group Cs). A system of hydrogen bonds of the type N-H· · ·O links the complex molecules between them and with the lattice DMSO molecules. Similar structures have been deduced for the remaining two complexes on the basis of spectroscopic data. The three complexes and the ligand H2GT exhibit cytotoxic activity against F4N leukemia cells, whereas the ligand H2PT is inactive.
Recurvosides A and B, Antifungal Novel Steroidal Glucosides from Haloxylon recurvum
Authors: Sharif Ahsan , Ahmed Ejaz , Malik Abdul
Published: February 2015

Recurvosides A (1) and B (2), new steroidal glucosides, have been isolated from the ethyl acetate soluble fraction of Haloxylon recurvum and their structures elucidated by spectroscopic techniques including two-dimensional NMR. Both the compounds exhibited potent antifungal activity.
A New Bioactive Steroidal Saponin from Leaves of Furcraea gigantea
Authors: Silva Bernadete P. da , Parente José P.
Published: February 2015

A new bidesmosidic furostanol saponin was isolated from leaves of Furcraea gigantea Vent. Its structure was established as 3-[(O-6-deoxy-α-L-mannopyranosyl-(1→4)-O-β -D-glucopyranosyl-( 1→3)-O-[O-β -D-glucopyranosyl-(1→3)-β -D-glucopyranosyl-(1→2)-O-β -D-glucopyranosyl- (1→4)-β -D-galactopyranosyl)oxy]-(3β ,5α,15α,22α,25R)-26-(β -D-glucopyranosyloxy)-15,22-dihydroxy- furost-12-one. Its structural identification was performed using detailed analyses of 1H and 13C NMR spectra including 2D NMR spectroscopic techniques (DEPT, COSY, HETCOR and COLOC) and chemical conversions. The steroidal saponin showed no haemolytic effects in the in vitro assays and demonstrated inhibition of the capillary permeability activity.
A Novel Route to 4-Aminopyrazoles and Aminopyrazolo[4,3-b]pyridines
Authors: Salaheldin Abdellatif M. , Abdallah Tayseer A. , Radwan Naglaa F. , Hassaneen Hamdi M.
Published: February 2015

3-Oxo-2-arylhydrazononitriles 6 are readily converted into 4-aminopyrazoles 1 via reaction with α-haloketones, chloroacetonitrile and ethyl chloroacetate. The aminopyrazoles are readily converted into aminopyrazolo[4,3-b]pyridines upon treatment with malononitrile. Compounds are readily diazotized to yield unstable diazonium salts that readily cyclized into pyrazolo[4,3-c]pyridazines.
Triterpene Saponins from Calendula arvensis
Authors: Kırmızıbekmez Hasan , Bassarello Carla , Piacente Sonia , Pizza Cosimo , Çalış İhsan
Published: February 2015

From the aerial parts of Calendula arvensis a new triterpene saponin arvensoside C (1) was isolated together with four known triterpene saponins. The aglycon moieties had the oleanane skeleton for all of them. Three known flavonol glycosides, isorhamnetin 3-O-β -D-glucopyranoside, quercetin 3-O-β -D-glucopyranoside and quercetin 3-O-β -D-galactopyranoside were also obtained and characterized. Their structures were elucidated by 1D and 2D NMR experiments including 1D-TOCSY, DQF-COSY, HOHAHA, HSQC and HMBC spectroscopy as well as HRESIMS analysis.
Kristallstrukturen komplexer Metalate mit dem sterisch anspruchsvollen 1,3,5-Tri(tert-butyl)tropylium-Kation / X-Ray Crystal Structures of Complex Metallates Containing the Sterically Demanding 1,3,5-Tri(tert-butyl)tropylium Cation
Authors: Tamm Matthias , Bannenberg Thomas , Urban Victoria , Pape Tania , Kataeva Olga
Published: February 2015

The X-ray crystal structures of anionic transition metal complexes containing the sterically demanding 1,3,5-tri-tert-butyltropylium cation, [1,3,5-C7H4tBu3]+, as the compensating ion are presented. Bis(1,3,5-tri-tert-butyltropylium) hexachlorodiferrate(II), [1,3,5-C7H4tBu3]2[Fe2Cl6] (4), was obtained from the reaction of the 1,3,5-tri-tert-butyltropylium hydrogendichloride, [1,3,5- C7H4tBu3][HCl2] (3), with FeCl2, whereas the 1,3,5-tri-tert-butyltropylium tetrabromooxomolybdate( V) [1,3,5-C7H4tBu3][trans-Mo(O)Br4(CH3CN)] (7) was isolated from the reaction of the cycloheptatrienyl complex [(η7-1,3,5-C7H4tBu3)Mo(CO)2Br] (6) with elemental bromine. The crystal structures of 3, 4, 7 and 7 · CH3CN show in each case well separated anions and cations and the absence of any covalent anion-cation interactions. However, close inspection of the crystal packing reveals that the 1,3,5-tri-tert-butyltropylium cation can act as a CH-proton donor towards the counterion leading to the formation of weak C-H· · ·Cl-M and C-H· · ·O=M hydrogen bonds in 4 and in 7 and 7 ·CH3CN, respectively.
Synthese und Kristallstrukturbestimmung von Cs([18]Krone-6)Au · 8NH3/ Synthesis and Crystal Structure Determination of Cs([18]crown-6)Au· 8NH3
Authors: Nuss Hanne , Jansen Martin
Published: February 2015

Cs([18]crown-6)Au ・ 8NH3 was synthesized from CsAu and [18]crown-6 in liquid ammonia. The extremely air- and temperature-sensitive colorless, block-shaped crystals were analyzed by single crystal X-ray diffractometry. The compound forms triclinic crystals of space group P1 (no. 1) with a = 8.765(2), b = 11.186(2), c = 13.997(3) Å , α = 86.180(6), β = 89.669(6), γ = 83.774(6)°, V = 1361.2(4) Å3. The crystal structure consists of ammonia nets extending perpendicular to [110] in which the Cs([18]crown-6) fragments and the auride anions are embedded
Two New Quadridentate Schiff Base Complexes of Nickel(II) and Cobalt(III): Synthesis, Structure and Spectral Characterisation
Authors: Chakraborty Joy , Singh Raj K. Bhubon , Samanta Brajagopal , Choudhury Chirantan Roy , Dey Subrata K. , Talukder Pritha , Borah Manob J. , Mitra Samiran
Published: February 2015

Two novel quadridentate Schiff base complexes, [NiIILH](ClO4)2・H2O (1) and [CoIIIL]- (ClO4)2・H2O (2) [LH, a Schiff base ligand: Ph(OH)C(Me)=NCH2CH2N(CH2CH2NH2)2] have been synthesised and characterised by elemental analyses, spectroscopic and electrochemical studies. The structures of both have been unequivocally established from single crystal X-ray diffraction studies. 1 and 2 crystallise in the monoclinic space group P21/n having cell parameters a = 8.536(1), b = 13.832(4), c = 18.194(2) Å , β = 100.00(10)°, Z = 4 for 1, and a = 10.819(5), b = 14.301(2), c=14.224(1) Å , β =97.04(2)°, Z =4 for 2. The complexes expose a square planar geometry around the metal centers chelated with three different types of nitrogen donor centers of the ligand.
Cyclisierung von Di(tert-butyl-methyl)ketazin zu 1,2-Diaza-3-bora- und 1,2-Diaza-3-sila-cyclopent-5-enen / Cyclization of Di(tert-butyl-methyl)ketazine to 1,2-Diaza-3-bora- and 1,2-Diaza-3-sila-cyclopent-5-enes
Authors: Armbruster Florian , Armbruster Nina , Klingebiel Uwe , Noltemeyer Mathias , Schmatz Stefan
Published: February 2015

The results of quantum chemical calculations on lithium ketazides suggest mainly four isomeric structures with different modes of lithium coordination (A-D). A monolithium ketazide thf-adduct (1) was isolated supporting the results of the quantum chemical calculations. In reactions of the lithiated di(tert-butyl-methyl)ketazine with BCl3 and Cl2BPh, 1,2-aza-azonia-3-borata-cyclopent-5-enes (2, 3) were isolated. Substitution of a chlorine atom of 2 and 3 with t-BuLi leads to the formation of derivatives 4 and 5. HCl elimination from 2 with Et3N gives - via a diazaboracyclopentene (6) - a bicyclus 7. In the reaction of the dilithiated ketazine with F2BN(SiMe3)2, the diaza-boracyclopentene 8 is obtained while with Cl4Si, F3SiN(SiMe3)2, and Cl2SiMe2 the diazasilacyclopentenes 9 - 11 are generated. SiF4 reacts with the dilithium ketazide to give a spirocyclus (12). The monolithium ketazide and Cl2SiMe2 react at 30 °C to give a four-membered ring isomer of the substitution product which is formed via a 1,3-chlorine shift from silicon to carbon (13). A tetrameric silanolate was isolated as a by-product in this reaction. It gives evidence for the structure of lithium ketazide A. Crystal structures of 5, 7, 10, and 14 are reported.
Mild and Convenient Method for Reduction of Carbonyl Compounds with the NaBH4/Charcoal System in Wet THF
Authors: Setamdideh Davood , Zeynizadeh Behzad
Published: February 2015

The NaBH4/C (charcoal) system reduces a variety of carbonyl compounds such as aldehydes, ketones, acyloins and α-diketones to their corresponding alcohols in high to excellent yields. Reduction reactions were carried out in wet THF at r. t. In addition, regioselective 1,2-reduction of α,β - unsaturated aldehydes and ketones was achieved perfectly with this reducing system. By decreasing the amount of aprotic solvent, all reductions took place fast and efficiently under solid-gel condition
New Helminthosporal Analogues with Plant-Growth Regulatory Properties Synthesized via Oxyallyl Cation
Authors: Chavez Fabio C. , Barbosa Luiz C. A. , Demuner Antonio J. , Silvac Antonio A.
Published: February 2015

Microorganisms are a rich source of bioactive molecules which serve as models for the synthesis of new commercial agrochemicals. In this work we present the synthesis of eleven new bioactive analogues of helminthosporal, a fungal secondary metabolite with plant-growth regulatory activity. The compounds were prepared via a [4+3] cycloaddition reaction between the oxyallyl carbocation generated from 2,4-dibromo-5-methylpentan-3-one and several substituted furans. The reactions yields revealed to be highly influenced by the bulkiness and electron withdrawing capacities of the substituents in the furans. The selective effect of all compounds 10a - f, 11 -14 on the radicle growth of Sorghum bicolor and Cucumis sativus were evaluated at the concentration of 10−3 M. All test compounds inhibited the sorghum roots growth (22 - 82%) and most of them stimulated the cucumber radicle growth (up to 127%).
Lignans from the Roots and Rhizomes of Clematis manshurica
Authors: Shi She-Po , Jiang Dan , Dong Cai-Xia , Tu Peng-Fei
Published: February 2015

Two new lignans, clemomanshurinane A and B, along with ten known compounds have been isolated from the roots and rhizomes of Clematis manshurica. The structures were elucidated on the basis of their physicochemical and spectroscopic evidence. Clemomanshurinane A and B, (+)-dihydrodehydrodiconiferyl alcohol and (+)-lariciresinol 4,4′-O-bis-β -D-glucopyranoside indicated inhibitory effects on COX-2 at final concentration of 10−5 mol/l, with the inhibition rates 65.8%, 71.8%, 53.3%, and 60.3%, respectively.
Nucleophilic Additions of Methanol to the Dichloropalladium(II) Complex with C-(2-Pyridyl)-N-methylnitrone
Authors: Doroschuk Roman O. , Petkova Elena G. , Lampeka Rostislav D. , Domasevitch Konstantin V. , Gorichko Marian V.
Published: February 2015

The additions of methanol to the dichloropalladium(II) complex with C-(2-pyridyl)-Nmethylnitrone led to the formation of the Pd(II)-coordinated α-methoxy-α-(2-pyridyl)-N,Ndimethylhydroxylamine. It has been demonstrated that the Pd(II) complexation is essential for the stabilization of α-alkoxyhydroxylamines.
Hydrothermal Syntheses and Crystal Structures of Two New Polyoxometalate-based Charge Transfer Salts
Authors: Zhang Chunhua , Li Fengyan , Xu Lin
Published: February 2015

Two new charge transfer salts based on Keggin polyoxoanions, [Hen]2[H2en][PMoVI
11MoVO40]・3.5H2O (1) and [Hpy]4[GeMoVI
12O40]・2H2O (2) (en = ethylenediamine, py = pyridine), have been synthesized and characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, UV/vis spectra, cyclic voltammograms and X-ray photoelectron spectra. The IR spectra and solid reflectance electronic spectra of the title compounds indicate that interactions exist between the polyanions and the organic substrates, which are probably caused by charge transfer.
Neue Koordinationspolymere auf der Basis der Naphthalin-1,4,5,8- tetracarboxylat-hydrate von Ca, Sr und Ba / New Coordination Polymers Based on Naphthalene-1,4,5,8-tetracarboxylate Hydrates of Ca, Sr, and Ba
Authors: Senkovska Irena
Published: February 2015

Crystals of [Ca(NTC)(H2O)2]·H2O (1) (NTC = naphthalene-1,4,5,8-tetracarboxylate-1,8-monoanhydride) and [Sr2(NTC)2(H2O)8]·H2O (3) were obtained by layering an aqueous solution of sodium naphthalene-1,4,5,8-tetracarboxylate with an aqueous solution of CaCl2 or SrCl2, respectively. Crystals of [Sr(NTC)(H2O)2]·2H2O (2) and [Ba(NTC)(H2O)2] (4) were obtained by gel crystallisation. The NTC in 1 and 2 is tridentate, and in 4 pentadentate, forming bonds to the cations using the oxygen atoms of the carboxylate and one oxygen atom of anhydride groups. In 3 the cations are associated only via the oxygen atoms of carboxylate groups. 1 and 2 have layer structures, 3 has a chain structure, and 4 forms a three-dimensional coordination network. The number of O atoms around the cations is eight for 1, 2 and 4, and nine for 3.
Butyrospermol Fatty Acid Esters from the Fruit of a Chinese Mangrove Xylocarpus granatum
Authors: Wu Jun , Li Minyi , Xiao Zhihui , Zhou Yuan
Published: February 2015

A mixture of four new butyrospermol and two known β -sitosterol fatty acid esters, was obtained from the fruit of a Chinese mangrove Xylocarpus granatum. The structures of these compounds were established on the basis of spectroscopic data and chemical means. The butyrospermol fatty acid esters were characterized as mainly comprising butyrospermol 3β -O-palmitate (1), butyrospermol 3β -O-oleate (2), butyrospermol 3β -O-stearate (3) and butyrospermol 3β -O-linoleate (4). The β - sitosterol fatty acid esters were identified as mainly containing β -sitosterol 3β -O-myristate and β - sitosterol 3β -O-oleate.
New Anthraquinones from a Marine Streptomyces sp. – Isolation, Structure Determination and Biological Activities
Authors: Poumale Hervé M. P. , Ngadjui Bonaventure T. , Helmke Elisabeth , Laatscha Hartmut
Published: February 2015

Two new anthraquinones were isolated from the marine Streptomyces sp. B8000, in addition to the known metabolites 3,8-dihydroxy-1-propylanthraquinone-2-carboxylic acid (1a), indole-3- carboxylic acid, 2-desoxythymidin, indole-3-acetic acid methyl ester, N-acetyltyramine, and nicotinic acid. The structures of the new compounds were established as 8-hydroxy-3-methoxy-1- propylanthraquinone (2a) and 3,8-dihydroxy-1-propylanthraquinone (2c) on the basis of extensive spectroscopic analyses. Some derivatives were prepared and their biological activities were studied.
Materials Chemistry under High Pressures – Some Recent Aspects
Authors: Demazeau Gérard , Huppertz Hubert , Alonso José A. , Pöttgen Rainer , Moran Emilio , Attfield J. Paul
Published: February 2015

Among the thermodynamic parameters governing the preparation of novel materials, temperature (T) and pressure (p) play an important role. In Materials Chemistry, the synthesis of materials needs energy in order to enhance the diffusion of atoms to the equilibrium positions required by the specific structure and to induce the formation of chemical bonds. The comparison of the energy conveyed by both parameters (p and T) underlines that high pressures can be associated - in liquid or solid media - with soft processes. Consequently this paper describes the main factors induced by the parameter pressure that are able to support new structural forms or generate novel materials. Two different approaches are presented: (i) for a given composition with characteristic chemical bonds, high pressures can induce structural transformations, (ii) high pressures lead to the formation of novel materials from different precursors through the formation of new chemical bonds.
High-pressure Synthesis and Structural, Electrical and Magnetic Properties of a New Filled Skutterudite TbFe4P12
Authors: Shirotani Ichimin , Takeda Keiki , Sekine Chihiro , Hayashi Junichi , Nakada Ryusuke , Kihou Kunihiro , Ohishi Yasuo , Yagi Takehiko
Published: February 2015

The new filled skutterudite TbFe4P12 has been prepared at around 4 GPa and 1050 °C. Powder X-ray diffraction of TbT4P12 (T = Fe and Ru) has been studied with synchrotron radiation at ambient pressure. The crystal structures of both compounds were refined by Rietveld methods at ambient pressure. The positional parameters, bond lengths and bond angles have been obtained for TbT4P12 (T = Fe and Ru). The electrical and magnetic properties of TbFe4P12 have been investigated at low temperatures. The susceptibility of this phosphide follows a Curie-Weiss behavior at higher temperatures. The linear slope of the χ−1 vs. T curve from 15 to 300 K yields an effective magnetic moment of 9.48 μB. This value is close to the magnetic moment of the Tb3+ ion calculated from Hund’s rule, 9.72 μB. The ferromagnetic transition of TbFe4P12 was observed at around 10 K, and an electrical anomaly based on the magnetic ordering was detected. The relationship between the crystal structure and the physical properties of TbT4P12 (T = Fe and Ru) is discussed.
High-pressure Synthesis of Strontium Hexasilicide
Authors: Wosylus Aron , Prots Yurii , Burkhardt Ulrich , Schnelle Walter , Schwarz Ulrich , Grin Yuri
Published: February 2015

The binary phase SrSi6 was prepared at a pressure of 10(1) GPa and a temperature of 1520(150) K. Single crystal refinements and powder diffraction data reveal that the compound crystallizes in the orthorhombic crystal system (Cmcm, a=4.4692(4), b=10.256(1), c=11.698(1)Å ) and is isopointal to EuGa2Ge4 and EuSi6. Exothermic decomposition of the compound into SrSi2 and Si at 797 K and ambient pressure indicates that the compound is a metastable high-pressure phase. Analysis of the chemical bonding using the electron localization function and calculated charge densities reveals covalent bonding within the polyanion of four-bonded silicon atoms. Strontium cations are enclosed in the 3D net resulting in an electron balance Sr2+[Si0]2−
6 . In the electronic density of states the excess electrons of the framework are assigned to a filling of antibonding bands. SrSi6 is a metallic conductor with an electrical resistivity of ρ ≈ 250 μΩ·cm at 300 K. Magnetization measurements indicate diamagnetic behaviour (χ0 = −50 · 10−6 emu·mol−1).
Structural Evolution of the Binary System Ba-Si under High-pressure and High-temperature Conditions
Authors: Yamanaka Shoji , Maekawa Shoichi
Published: February 2015

A new silicon-rich binary compound BaSi6 has been prepared by the treatment of the Ba8Si46 clathrate compound under a pressure of 15 GPa at 1000 °C, or from a stoichiometric mixture of BaSi2 and Si by treatment under similar high-pressure and high-temperature conditions. The Rietveld refinements revealed that BaSi6 is isomorphous with EuGa2Ge4, and crystallizes with space group Cmcm and the lattice parameters a = 4.485(1), b = 10.375(2), and c = 11.969(3) Å . Each Ba atom is surrounded by 18 Si atoms in an irregularly shaped polyhedron @Si18. The polyhedra are connected by sharing faces to form Ba containing tunnels along the a axis. All of the Si-rich compounds so far with atomic ratios Si/Ba > 2 in the binary system have been prepared only under high-pressure and high-temperature conditions. There is a general tendency that the Si/Ba ratio of the compounds increases with an increase of the pressure in the preparation.
High Oxygen Pressures and the Stabilization of the Highest Oxidation States of Transition Metals – Mössbauer Spectroscopic Characterization of the Induced Electronic Phenomena
Authors: Demazeau Gérard , Baranov Alexey , Presniakov Igor , Sobolev Alexey
Published: February 2015

High oxygen pressures are a fruitful tool for the stabilization of the highest formal oxidation states of transition metals (Mn+) leading to the strongest chemical bonds; the improvement of the Mn+-O bond covalency induces different electronic phenomena. Among the physical characterizations applied to investigate such phenomena, 57Fe and 119Sn Mössbauer spectra are evaluated for studying unusual electronic configurations, orbital ordering, charge disproportionation and insulator-metal transitions in the perovskites series of 57Fe doped RENiO3 nickelates (RE = rare earths, Y and Tl) and 119Sn doped AEFeO3 ferrates (AE = Ca, Sr).
Structural Transformation of Boron Nitride Nanoparticles in Benzene under Moderate Conditions
Authors: Lai Zefeng , Zhu Lingling , Yu Lili , Chen Zhi , Zhao Xian , Wang Qilong , Cui Deliang , Jiang Minhua
Published: February 2015

This work reports a new route for preparing cubic BN (c-BN) nanocrystals under moderate conditions. Considering the instability of BN nanoparticles, we have investigated the structural transformation of BN nanoparticles in benzene. The results revealed that a great deal of hexagonal BN (h-BN) nanoparticles had been converted into c-BN or wurtzitic BN (w-BN) at 280 °C and 50 MPa. As the temperature was increased from 280 to 300 °C, h-BN nanoparticles gradually disappeared, and the content of both c-BN or w-BN increased. Similarly, increase of pressure or hot-pressing time showed the same effect. These results may open up an opportunity for synthesizing other superhard nanomaterials such as diamond and cubic carbon nitride under moderate conditions.
High-pressure / High-temperature Behavior of the Methane-Ammonia- Water System up to 3 GPa
Authors: Kurnosov Alexander , Dubrovinsky Leonid , Kuznetsov Alexei , Dmitriev Vladimir
Published: February 2015

Melting phase relations in the methane-ammonia-water system up to 3 GPa have been obtained in a series of in situ experiments in externally heated diamond anvil cells. The melting temperature of methane clathrate hydrates increases rapidly above pressures of ~ 1.5 GPa, and does not appear to be significantly affected by the presence of ammonia. The reaction of the hydrate formation at pressures 2 - 3 GPa is kinetically impeded. Our data show that the high-pressure methane hydrate has the maximum melting temperature among the clathrate hydrates studied so far.
Compression Behavior of Zr-doped Nanoanatase
Authors: Holbig Eva , Dubrovinsky Leonid , Steinle-Neumann Gerd , Prakapenka Vitali , Swamy Varghese
Published: February 2015

The compression behavior of Zr-doped nano anatase Ti0.90Zr0.10O2 synthesized by the sol-gel method was studied using a diamond anvil cell (DAC) up to ~ 13 GPa. The compressibility parallel to the a axis decreases strongly at ~ 4 GPa and other structural parameters also change with pressure. The parameters of the third order Birch-Murnaghan equation of state were fitted to: V0 = 139.6(0) Å3, K0 = 213(9) GPa and K′ = 17.9(2). Ab initio electronic structure simulations indicate that the Zr atoms cluster in the crystal. The effects of chemical substitution as well as of microstructure, especially the crystallite size, on the mechanical properties are discussed.
Structure, Magnetic Properties and 151Eu, 119Sn Mössbauer Spectroscopy of Eu5Sn3S12 and Eu4LuSn3S12
Authors: Jakubcová Petra , Johrendt Dirk , Sebastian Peter , Rayaprol Sudhindra , Pöttgen Rainer
Published: February 2015

Eu5Sn3S12 and Eu4LuSn3S12 were synthesized and their structures refined from single crystal data (Pmc21, Eu5Sn3S12: a = 3.908(1), b = 20.115(4), c = 11.451(2) Å ; wR2 = 0.0519 for 3048 F2 and 122 parameters; Eu4LuSn3S12: a = 3.920(1), b = 20.132(4), c = 11.459(2) Å ; wR2 = 0.0737 for 3298 F2 and 122 parameters). The structures contain one-dimensional chains of edge-sharing SnS2S4/2 octahedra and corner-sharing SnS3S2/2 trigonal bipyramids, running parallel to [100]. Five europium sites are seven- or eightfold coordinated by sulfur atoms. Lutetium atoms in Eu4LuSn3S12 show a strong site preference for one of the two Eu3+ positions of Eu5Sn3S12 and no structural disorder was observed. Both compounds show static mixed valence according to Eu2+
3 Eu3+
2 Sn4+
3 S2−
12 and Eu2+
3 Eu3+Lu3+Sn4+
3 S2−
12 , which was confirmed by temperature dependent magnetic susceptibility measurements. The experimental magnetic moments of 14.6(1) (Eu5Sn3S12) and 14.1(1) (Eu4LuSn3S12) μB/f.u. indicate that each of the two sulfides contains three divalent europium atoms per formula unit. Magnetic ordering for Eu5Sn3S12 and Eu4LuSn3S12 sets in below 5 and 3 K, respectively. Both sulfides show metamagnetic or spin-flip transitions in the magnetization curves at 3 K (2 K) with full saturation of the europium magnetic moments at 3 K (2 K) and 80 kOe. 151Eu Mössbauer spectra fully confirm the Eu2+ and Eu3+ site occupancies. At 4.2 K an increase in line width indicates small hyperfine fields at the europium nuclei.
Crystal Structures and Thermal Behavior of Isostructural Bis(dibenzyldimethylammonium) Tetrachlorometallate [M = Mn(II), Co(II), Ni(II) and Zn(II)] Solvates Crystallized from Acetonitrile and/or Methanol Solutions
Authors: Busi Sara , Fröhlich Roland , Lahtinen Manu , Valkonen Jussi , Rissanen Kari
Published: February 2015

Five isostructural bis(dibenzyldimethylammonium) tetrachlorometallate solvate complexes [M = Mn(II), Co(II), Ni(II) or Zn(II)] were crystallized from acetonitrile and/or methanol solutions. The crystal structures are compared to those of the analogous, isostructural copper compounds (X = Cl or Br) reported earlier. The complexes crystallize in the monoclinic space group P21/n with Z = 4, and unit cell dimensions of a ≈ 14.1, b ≈ 16.1, c ≈ 15.7 °A and β ≈ 108 - 109°. The asymmetric unit of these compounds contains one MCl4
2− anion, two Bz2Me2N+ cations in theW-conformation and one half of a disordered solvent molecule (acetonitrile or methanol). The geometry of the MCl4
2− anion is close to tetrahedral, whereas the analogous copper anions appeared in distorted tetrahedral geometries with trans angles of 124.4° for X = Cl and 123.6° for X = Br. In addition to the ionic interactions between the cations and the anions, the components are connected by weak C-H· · · Cl− bonds. As a distinction between the two crystallographically independent cations in the asymmetric unit, one type of independent cations form long chains via weak edge to face π-π interactions along the crystallographic b axis, whereas the other type of cations are not tied together by such weak π-π interactions. The coordination around the N atoms is also nearly tetrahedral, and neither static nor dynamic disorder of the Bz2Me2N+ cations can be observed. The complexes are thermally stable and melt close to the decomposition temperatures in the range 170 - 205 °C.
Crystal Structures and Thermal Behavior of Bis(dibenzyldimethylammonium) Tetrabromometallates(II) [M = Mn(II), Co(II) and Zn(II)] and Their Solvates
Authors: Busi Sara , Fröhlich Roland , Lahtinen Manu , Sillanpää Reijo , Rissanen Kari
Published: February 2015

Six new A2MBr4 structures [A = dibenzyldimethylammonium cation,M = Mn(II), Co(II) or Zn(II)] were crystallized with or without solvent molecules from acetonitrile, methanol and/or aqueous solutions. The isomorphous compounds [(Bz2Me2N)2][MnBr4]·CH3CN·H2O (1) and [(Bz2Me2N)2]-[ZnBr4]·CH3CN·H2O (4) crystallize in the triclinic space group P1̄ from acetonitrile solutions. The solvent molecules participate in the hydrogen bonding network inside the crystal structure. [(Bz2Me2N)2][CoBr4]·0.5CH3CN (2) crystallizes from an acetonitrile solution in the monoclinic space group P21/c. The solvent molecules fill the voids of the crystal structure. Compound 2 is isostructural with the previously reported compounds [(Bz2Me2N)2][MCl4]·0.5CH3CN with M = Mn(II), Co(II), Ni(II), Cu(II) or Zn(II). [(Bz2Me2N)2][CoBr4] (3) and [(Bz2Me2N)2][ZnBr4] (5a) crystallize from a methanol solution in the monoclinic space group P21/c without solvents. A polymorph of compound 5a, [(Bz2Me2N)2][ZnBr4] (5b), was crystallized from aqueous solution in the monoclinic space group P21/c. The packing of the components of the two polymorphs differs clearly. One cation of 5a appears in the W-conformation whereas the other cation of 5a and both cations of 5b appear in twisted conformations. In addition to the ionic interactions between the ion pairs, the packing of the compounds is stabilized by hydrogen bonds and weak intermolecular π-π interactions in all cases. The compounds melt around 200 °C and decompose mainly in two steps just above the melting point. Slow evaporation of solvents is observed both in the TG and DSC diagrams of the solvates (1, 2 and 4) below 100 °C.
Distortions of [Sb2Cl10]4– Bioctahedra and Phase Transitions in the Chloroantimonate(III) (C3H5NH3)2[SbCl5] · (C3H5NH3)Cl
Authors: Zarychta Bartosz , Bujak Maciej , Zaleski Jacek
Published: February 2015

Bis(allylammonium)pentachloroantimonate(III) - allylammonium chloride, (C3H5NH3)2[SbCl5] · (C3H5NH3)Cl, belongs to the chloroantimonate(III) organic-inorganic salts family. The DSC studies of this compound showed two anomalies at 181 K and at 223 K. Both are associated with phase transitions, which mainly occur due to ordering-disordering processes of the organic cations. Between 181 and 223 K the structure is incommensurate. The crystal structure was determined at 298 and 86 K. At both temperatures the crystal structure consists of (C3H5NH3)+ cations, anionic distorted [Sb2Cl10]4− units and isolated Cl− ions. In the room-temperature phase two out of three, and in the low-temperature phase two out of six allylammonium cations were found to be disordered. The deformations of the [Sb2Cl10]4− moieties in both phases are discussed and explained by the deviation of the SbIII 5s electron lone pair from its spherical symmetry and the influence of N-H···Cl hydrogen bonds, which join together the organic and inorganic sublattices.
Synthesis, Crystal Structure and Thermal Decomposition Mechanism of a Dysprosium(III) p-Fluorobenzoate 1,10-Phenanthroline Complex
Authors: Xu Su-Ling , Zhang Jian-Jun , Yang Hui-Fang , Ren Ning , Zhang Hai-Yan
Published: February 2015

A dinuclear dysprosium(III) p-fluorobenzoate 1,10-phenanthroline complex, [Dy(p-FBA)3phen]2 was synthesized and characterized by elemental analysis, UV and IR spectroscopy, single crystal X-ray diffraction, molar conductance, and TG-DTG techniques. It crystallizes in the triclinic space group P1̄ with a = 9.895(5), b = 11.754(6), c = 14.756(10)Å ; α = 106.660(9)°, β = 107.956(9)°, γ =101.472(7)°; Z =1. The Dy(III) ions are eight coordinate including one terminal bidentate chelating carboxylate group, four bridging carboxylate groups and one 1,10-phenanthroline molecule. The thermal decomposition of [Dy(p-FBA)3phen]2 has been followed by thermal analysis. The lifetime equation at weight-loss of 10% was deduced as lnτ = −27.0798 +19010.2434/T by isothermal thermogravimetric analysis.