bluuebunny/crossref_metadata_2025 huggingface dataset:
Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von trans-(Et4N)[OsF4Cl2] / Crystal Structure, Vibrational Spectra and Normal Coordinate Analysis of trans-(Et4N)[OsF4Cl2]
Authors: Lorenzen B. , Preetz W.
Published: February 2015

By careful oxidation of trans-tetrafluorodichloroosmate(IV) with PbO2/trifluoroacetic acid in dichloromethane the corresponding osmium(V) complex anion rran5 -[OsF4Cl2]- is for­ med. The X-ray structure determination on a single crystal has been performed of trans-(Et4N)[OsF4Cl2] (triclinic, space group P1̄a = 7.190(5), b = 7.205(5), c = 7.732(5) Å, a = 71.28(1), β = 71.32(1), 7 = 70.76(1)°, Z = 1). Based on the molecular parameters of the X-ray determination the IR and Raman spectra of the complex have been assigned by normal coordi­ nate analysis. The valence force constants are: fd(OsCl) = 2.13 and fd(OsF) = 3.81 mdyn/Å.
The Crystal Structures and Thermal Behaviour of the Mercury Arsenates Hg2(H2AsO4)2, Hg2As2O6 and HgAs2O6
Authors: Weil Matthias
Published: February 2015

Crystals of Hg2(H2AsO4 )2 , which are isotypic with the corresponding dihydrogenphosphate Hg2 (H2PO4)2 , were obtained from a concentrated arsenic acid solution. The crystal structure (P21/n, a = 6.1838(4), b = 15.0987(9), c = 4.7989(3) Å, β = 91.977(1)°, Z = 2, R = 0.045 for 1318 structure factors, 56 variables) contains a Hg2
2+ dumbbell with a distance d(Hg-Hg) = 2.5040( 10) Å and a symmetrical coordination of four oxygen atoms for each mercury atom. The oxygen atoms also belong to tetrahedral dihydrogenarsenate groups H2AsO4
−, which stabilize the structure by hydrogen bonding. On heating Hg2(H2AsO4)2 condenses to give the mercury(I) metaarsenate Hg2As2O6. Crystals of that compound were obtained under hydrothermal conditions at 165 °C starting from elemental mercury in 60 wt% aqueous H3AsO4 . The crystal structure (P3̄1m, a = 4.8411(2), c = 7.5961(9) Å, Z = 1, R = 0.037 for 376 structure factors, 13 variables) may be represented by sheets of edge sharing [AsO6] octahedra and layers of Hg2
2+ dumbbells, which alternate along the c axis. The dumbbells show a distance d(Hg-Hg) = 2.5190(10) Å and are coordinated symmetrically by six oxygen atoms at a distance d(Hg-O) = 2.374(4) Å. They are positioned above and below the vacant sites of adjacent [As2O6]2− layers. On further heating Hg2As2O6 disproportionates into elemental mercury and mercury(II) metaarsenate, HgAs2O6. Single crystals of HgAs2O6 were grown via chemical vapor transport from microcrystalline HgAs2O6 with HgCl2 as transport agent, using a temperature gradient of 650 → 550 °C. HgAs2O6 (P3̄1m, a = 4.8482(2), c = 4.9789(10) Å, Z = 1, R = 0.031 for 367 structure factors, 12 variables) crystallizes in the PbSb2O6 structure type, where anionic [Sb2O6]2− layers have the same arrangement. The divalent mercury atomsohave a pseudooctahedral environment of oxygen atoms with a distance d(Hg-O) = 2.353(3) Å.
Hydrido(acylenolato)cobalt(III)-Verbindungen mit Trimethylphosphan- Liganden: Insertionsreaktionen mit Alkinen und die ersten Carbonylcobalt(III)-Komplexe / Hydrido(acylenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands: Insertion Reactions with Alkynes and the First Carbonylcobalt(III) Complexes
Authors: Klein Hans-Friedrich , Li Xiaoyan , Flörke Ulrich , Haupt Hans-Jürgen
Published: February 2015

Formal insertion of phenylethyne into Co-H functions of mer-octahedral acyl(enolato)-cobalt(III) hydrides 1-3 proceeds under ambient conditions affording η1-vinylcobalt(III) compounds where the dianionic acyl(enolato) ligands are derived from 2-formyl-4-phenyl-cyclohexanone (4), 1-formyl-cyclohexan-2-one (5), and 3-hydroxo-2,3-diphenyl-propenal (6). Dissociation and association of trimethylphosphane results in a reversible transformation of penta-coordinate complexes 4 -6 into hexa-coordinate ones 7 -9, respectively, involving different tautomeric vinyl species. In toluene solution 9 rearranges by reductive C,C coupling into a 5,6-η2-olefin(enolato)cobalt(I) complex 10. Trimethylsilylethyne undergoes a hydrolytic desilylation reaction which is followed by reductive C,C-coupling reactions of acyl and vinyl functions selectively producing chelating η1-enolato-5,6-η2-olefin ligands in cobalt(I) com ­ pounds 13 -16 where the (ax,eq)chelating ligands are derived from 1-formyl-cyclohexan-2-one (13), 3-hydroxo-2,3-diphenyl-propenal (14), 2-formyl-α-tetralone (15), and 2-formyl-4-tert-butyl-cyclohexanone (16). An axial position of the enolato-O donor in the trigonal bipyramidal configuration of complex 15 has been confirmed by X-ray diffraction analysis. With 1,4-bis(trimethylsilyl)buta-diyne 1,2-addition in cobalt(III) hydrides 2, 3, 11 (as deriverd from 2-formyl-α-tetralone), and 12 (as derived from 2-formyl-4-tert-butyl-cyclohexanone) produces 2-metalated vinyl groups in compounds 17 -20. Dissociation of trimethylphosphane from 17 and 19 does not activate C,C coupling at the cobalt(III) centre of penta-coordinate 21 and 22. Steric congestion in compounds 17, 18, and 20 favours exchange of trimethylphosphine for carbon monoxide affording the first octahedral carbonyl complexes of cobalt (d6) (23 -25). In the crystal and in solution a meridional configuration is adopted by complex 23 with the CO group in a position opposite to the acyl function.
Spektroskopische Charakterisierung und Kristallstruktur von Trifluormethyliod(III)-bis(trifluoracetat) CF3I(OCOCF3)2 / Spectroscopic Characterisation and Crystal Structure of Trifluoromethyliodine(III) Bis-trifluoroacetate, CF3I(OCOCF3)2
Authors: Minkwitz Rolf , Berkei Michael
Published: February 2015

Trifluoromethyliodine(III) bis-trifluoracetate [CF3I(OCOCF3)2] was obtained by reaction between CF3IF2 and (CH3)3SiOCOCF3 at -50 °C. It crystallises in the triclinic space group P1̄ with a = 520.8(1), b = 1042.9(1), c = 1087.5(1) pm, α = 65.22(0)°, β = 81.18(0)°, γ = 80.09(0)°, and two formula units per unit cell. The compound has also been characterised by its Raman and IR spectra.
Wechselwirkungen in Molekülkristallen, 156 [1, 2]. Kristallzüchtung und Strukturbestimmung von (Imidodiphosphat)-Alkalisalzen mit Kationen niedriger und hoher Koordinationszahlen / Interaction in Molecular Crystals, 156 [1, 2]. Crystal Growth and Structure Determination of Alkali(imidodiphosphate) Salts with Cations of Low and High Coordination Numbers
Authors: Bock Hans , Heigel Erik , Nagel Norbert
Published: February 2015

Imidodiphosphates ⊖N[PO(OR)2]2 and Imidodiphosphonates ⊖N[POR2]2 are effective chelating ligands for a variety of metal cations including even Na⊕, for which a lipophilically wrapped hexameric polyion cluster has been structurally characterized. The corresponding hexameric lithium and polyrubidium ion complexes reported here exhibit considerable structural differences: The rather small Li⊕ cations of coordination number five and tetraphenylimidodiphosphate form an isolated hexameric aggregate analogous to the Na⊕ one, whereas the larger Rb⊕ with coordination number seven and (3,4-dimethylphenyl)substituents crystallizes as a chain polymer. Based on the crystal structures, the dominant Coulomb attractions between cations and anions, the spatial requirement of the ligands and the essential phenyl/phenyl interactions in their lipophilic skin are discussed
New Indides EuAuIn2, EuPdIn4, GdRhIn2, YbRhIn4, and YbPdIn4
Authors: Hoffmann Rolf-Dieter , Pöttgen Rainer , Zaremba Vasyl’ I. , Kalychak Yaroslav M.
Published: February 2015

New intermetallic indium compounds EuAuIn2, EuPdIn4, GdRhIn2, YbRhln4, and YbPdIn4 were obtained by reaction of the elements. GdRhIn2 was synthesized in an arc-melting furnace, while EuAuIn2, EuPdln4, YbRhIn4, and YbPdIn4 were prepared in sealed tantalum tubes in a high-frequency furnace. The five compounds were investigated by X-ray diffraction both on powders and single crystals. EuAuIn2 and GdRhIn2 adopt the MgCuAl2 type structure with space group Cmcm. Single crystal X-ray data yielded a = 468.1(2), b = 1105.5(4), c = 753.5(4) pm, wR2 = 0.096, 343 F2 values for EuAuIn2 and a = 435.0(1), b = 1013.3(3), c = 783.6(2) pm, wR2 = 0.042, 608 F2 values for GdRhIn2 with 16 variables for each refinement. The two structures may be described as gold or rhodium filled versions of the host lattices Euln2 and GdIn2 . The three-dimensional indium networks of EuAuIn2 and GdRhIn2 resemble the lonsdaleite structure. Both structures are built up from three-dimensional [Auln2] and [Rhln2] poly anions in which the europium and gadolinium atoms occupy distorted hexagonal tubes. The modulations of the In-In distances within the indium networks are compared with other MgCuAl2 type indides. EuPdIn4 and YbPdIn4 crystallize with the YNiAl4 type, space group Cmcm: a = 454.8(2), b = 1703.2(8), c = 738.0(3) pm, wR2 = 0.044, 501 F2 values for EuPdIn4 and a = 445.8(2), b = 1666.0(4), c = 747.3(2) pm, wR2 = 0.050, 711 F2 values for YbPdIn4 with 24 variables for each refinement. In contrast, YbRhln4 adopts the LaCoAl4 type, space group Pmma: a = 863.7(2), b = 422.5(1), c = 743.1(1) pm, wR2 = 0.051, 467 F2 values and 24 variables. EuPdIn4, YbPdlIn4, and YbRhIn4 too consist of three-dimensional [Pdln4] and [Rhln4] polyanions in which the europium and ytterbium atoms are located in distorted hexagonal and pentagonal channels. Common structural motifs of these indides are distorted bcc-like indium cubes which are compared with the structures of Y2CoIn8, YCoIn5, EuRh2ln8, and elemental indium. Chemical bonding in these indides is briefly discussed
Darstellung und Charakterisierung des Silber(I,II,III)-oxidclathrates Ag7O8HCO3 / Synthesis and Characterization of the Silver(I,II,III) Oxide Clathrate Ag7O8HCO3
Authors: Jansen Martin , Vensky Sascha
Published: February 2015

The silver(I,II,III) oxide clathrate Ag7O8HCO3 was synthesized by anodic oxidation of silver(I) in a suspension of Ag2CO3 in an aqueous AgF solution. The title compound was characterized by single crystal X-ray diffraction (cubic, Fm3̄m, a = 9.8085(3) Å, Z = 4), scanning electron microscopy, thermal analysis, IR spectroscopy, 1H-solid state-NMR and measurement of the magnetic susceptibility
Tri(Terf-Butyl)plumbyl-phosphanes, Synthesis and Multinuclear Magnetic Resonance
Authors: Herberhold Max , Köhler Christian , Tröbs Volker , Wrackmeyer Bernd
Published: February 2015

The reaction of tri(tert-butyl)plumbyl-lithium (1) with various phosphorus chlorides was studied. With diphenyl- and amino(phenyl)phosphorus chlorides the formation of hexa(tertbutyl) diplumbane (2) and tetraphenyldiphosphane (3) or the respective 1,2-bis(am ino)-1,2-diphenyl- diphosphanes [e. g. 5: amino = PhCH2(tBu)N] was dominant. The presence of at least one tert-butyl group at the phosphorus atom gave access to tri(tert-butyl)plumbyl-di(tert-butyl) phosphane (4) and to tri(tert-butyl)plumbyl-amino(tert-butyl)phosphanes [amino = tBu(H)N (6), Me(Ph)N (7), PhCH2(Me)N (8), PhCH2(tBu)N (9)] via the reaction of 1 with the corresponding phosphorus chlorides. Side products were again 2 and the corresponding diphosphanes, unidentified compounds, and in two cases, bis(phosphanyl)-di(tert-butyl)plumbanes [phosphanyl = tBu(H)N(tBu)P (10), Me(Ph)N(tBu)P (11)]. Trimethylplumbyl-benzyl(methyl)- amino(tert-butyl)phosphane (12) was prepared for comparison. All compounds were characterized by their 1H , 13C, 15N (9 ),31P and 207Pb NMR data. The coupling constants 1J(207Pb,31P) are large and negative, whereas the coupling constants 1J(207Pb, 13C) are small and can be of either sign. The coupling constants 2J(31P-N-13C) of 6 - 12 indicate a preferred conformation of the substituents at phosphorus and nitrogen
Kristallstrukturen der Komplexe Von Quecksilber(Ii)Iodid und -Thiocyanat mit L,13-Bis(8-Chinolyl)-L,4,7,10,13-Pentaoxatridecan („Kryptand 5“)
Authors: Pickardt Joachim , Wiese Sven
Published: February 2015

Reactions of 1,13-bis(8-chinolyl)-1,4,7,10,13-pentaoxatridecane (“Cryptand 5”) with HgX2 (X = I, SCN) yield crystals of [(cryptand 5)(HgI2)2] (1) and [(cryptand 5 )2{Hg(SCN)2}4] (2), resp. In both complexes two molecules of HgX2 are bound to one ligand molecule. 1 has symmetry Ci with the oxygen atom O(3 ) of the ether chain on a center of symmetry of the unit cell, each Hg atom is bound to the two I atoms, the N atom of the chinolyl residue, and one oxygen atom, O(1) and O(l)i, resp. of the ligand; neighbouring complex units are connected via iodine bridges thus forming chains. In 2 also two formula units of HgX2 are bound to one ligand molecule, but contrary to 1 the complex is not centrosymmetric. The Hg atoms of the two Hg(SCN)2 groups are co-ordinated differently: both are bound via sulphur atoms to two SCN-groups, one being a terminal SCN group, the other acting as a bridge to the Hg atom of a neighbouring complex unit. The first Hg atom is connected to a chinolyl N atom and too oxygen atoms, the second to a chinolyl N atom and three oxygen atoms. There are two independent complex units per asymmetric unit which are related by a non-crystallographic twofold axis, and which are connected via two SCN bridges. These “double molecules” are also interconnected by thiocyanate bridges, thus forming a chain structure
One-Pot Preparation of O-Xylylene Diamine and its Related Amines
Authors: Kawahara Shun-ichi , Uchimaru Tadafumi
Published: February 2015

A method for one-pot preparation of o-xylylene diamine, 1,8-diaminomethylnaphthalene, and 1,2,4,5-tetrakis(aminomethyl)benzene has been developed. The procedure is simpler and the yield of the reaction is higher than by the conventional method
Notizen: Ca{Li2[Mn'N]2}: Kristallchemischer Brückenschlag Zwischen Lithium-Nitrido-Verbindungen und Borid-Carbiden des Typs M [B2C2]/ Ca{Li2[M nIN]2}: Link between Crystal Chemistry of Lithium Nitrido Compounds and Boride Carbides of the Type M [B2C2]
Authors: Klatyk Jens , Niewa Rainer , Kniep Rüdiger
Published: February 2015

The nitridom anganate(I) Ca{Li2[MnIN]2) (space group P4/mbm: a = 703.35(7), c = 383.19(6) pm; Z = 2) contains infinite linear chains 1
∞=[MnIN2/2
2-] running along the [001] direction. The nitride species of the chains are further linked via three coordinated lithium to form planar 4.82-nets 2
∞{Li2N2
4-} parallel (001). Ca2+ occupies the centers of the eight-membered rings of the planar nets. The 4.82-arrangement 2
∞{Li2N2
4-} together with the stacking sequence ...AA... along [001] exhibit strong topological similarities with the anionic substructure 2
∞[B2C2
2-] observed in the crystal structure of e.g. Ce[B2C2]
Carbacylamidophosphates: Synthethis and Structure of N,N'-Tetramethyl-N''-p-chlorobenzoyIphosphoryltriamide and N,N'-Tetramethyl-NM-o-fluorobenzoylphosphoryltriamide
Authors: Gubina Katerina E. , Amirkhanov Vladimir M.
Published: February 2015

N,N′-Tetramethyl-N″-p-chlorobenzoylphosphoryltriamide (I), N,N′-tetramethyl-N″-o-fluorobenzoylphosphoryltriamide (II) and their sodium salts were synthesized and characterized by means of IR and 1H , 31P NMR spectroscopy. The structures of both compounds were determined by X-ray diffraction (I triclinic, space group P1̄ with a = 12.073(2), b = 12.869(3), c = 12.854(4) Å, α = 56.93(2), β = 62.45(2), γ = 66.34(2)° V = 1453.7(6)Å3, ρ(caled.) = 1.324 mg/cm3, Z = 4 and R = 0.0545, wR2 = 0.1425; II monoclinic, space group P2(1)/n with a = 10.051(2), b = 13.093(2), c = 10.856(2) Å, β = 108.36(2)°, V = 1355.9(4) Å3, ρ(caled.) = 1.339 mg/cm3, Z = 4 and R = 0.0533, wR2 = 0.1263). In both structures the molecules are associated into dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups. In I the unit cell consists of two independent molecules connected into non-symmetric dimers, in II of centrosymmetric dimer molecules.
The Hydrogen Bond Networks in Nicinquinium Salts
Authors: Borowiak Teresa , Dutkiewicz Grzegorz , Thiel Jacek
Published: February 2015

Crystals of nicinquinium chloride and bromide incorporate water molecules due to the im­ balance of hydrogen bond donors and acceptors. The resulting intermolecular hydrogen bond system indicates a better proton accepting ability of chloride ions than bromide ions. The chlo­ ride anions accept four hydrogen bonds in an almost tetrahedral arrangement whereas only two are formed with the bromide anions. As a consequence in the crystal structure of the chloride a three dimensional network of hydrogen bonds is formed, while in that of the bromide only chains of hydrogen bonded species exist. Both cations retain the absolute configuration of all asymmetric carbon atoms as compared with the absolute configuration of the parent cinchonine.
Uniform Sidearm Derivatisations in a Tetrapodal Pentaamine: Ligands with NN4 O4 Donor Sets, and a Bis(Ferrocenecarbaldehyde Aminal)
Authors: Dietz Christian , Heinemann Frank W. , Grohmann Andreas
Published: February 2015

The tetrapodal pentaamine 2,6-C5H3N[CMe(CH2NH2)2]2 (pyN4, 1) readily reacts with four equivalents of 2-hydroxyphenyl-substituted carbonyl compounds, such as (i) 2-hydroxybenzaldehyde, (ii) 2,4-dihydroxybenzaldehyde, (iii) 3,5-di-rm-butyl-2-hydroxybenzaldehyde, and (iv) 2-hydroxyacetophenone, to give the corresponding Schiff base derivatives with N N 4O .1 donor sets (i: 2; ii: 3, iii: 4; iv: 5). With ligand 5, two transition metal complexes (M = Ni11 (6), Cu11 (7)) have been isolated, which are dinuclear and contain square-planar M(N2O2) units, linked by a pyridine-derived spacer whose nitrogen atom is uncoordinated. The reaction of 1 with ferrocenecarbaldehyde affords, under neutral conditions and irrespective of an excess of the aldehyde present, the bis(aminal) 8 as the major product, in which the two 1,3-propylenediamine subunits of 1 have condensed with two carbaldehyde moieties to give two 1,3-diazacyclohexane rings. All compounds have been characterised by IR spectroscopy and elemental analysis, as well as 1H and 13C NMR spectroscopy (except paramagnetic 7). The crystal structures of compounds 2, 6, 7, and 8 have been determined.
Die Kristallstrukturen von Phenylen-1,4-bis(4-nitrophenylsulfonamid) und seines Dinatrium(tetramethanol-dihydrat)-Salzes / Interaction in Molecular Crystals, 161 [1, 2]. The Crystal Structures of Phenylene-1,4- bis(4-nitrophenylsulfonamide) and of its Disodium(tetramethanol-dihydrate) Salt
Authors: Bock Hans , Heigel Erik
Published: February 2015

Lipophilically wrapped polyion-aggregates of alkali salts are fascinating examples of selforganisation, which stimulate the design of novel ligands. Phenylene-1,4-bis(4-nitrophenylsulfonamide),. selected and structurally characterized, can be deprotonated by [NaH]∞ in THF to its dianion. Recrystallisation from methanol solution however, does not yield the polyion aggregate expected, but a disodium(tetramethanol-dihydrate) salt, for which a structure determination proves an intriguing three-dimensional network of Na⊕ ···O contacts to sulfonamide as well as nitro substituents and the small solvent molecules methanol as well as water. Ligand comparison between polyioncluster-forming tetraphenylimidodiphosphate and the title phenylene- 1,4-bis(4-nitrophenylsulfonamide) allows to specify the ligand properties necessary for the self-aggregation of alkali salts.
Wechselwirkungen in Molekülkristallen, 162 [1, 2]. Di(arylsulfonyl)amine – geeignete Liganden für lipophil umhüllte Polyionen-Aggregate mit Cs⊕ -Schichten variabler Dicke / Interaction in Molecular Crystals, 162 [1, 2]. Di(arylsulfonyl)amines – Ligands for Lipophilically Wrapped Polyion Aggregates with Cs⊕ -Layers of Variable Thickness
Authors: Bock Hans , Heigel Erik
Published: February 2015

Di(arylsulfonyl)amides are presented as novel anionic ligands for polycation aggregates. Starting from the structures of Ag⊕ and Na⊕ salts registered in the Cambridge Structural Database, the largest alkali cation Cs⊕ with high coordination number has been selected and in extreme low gradient crystallisation single crystals of both cesium-di(benzenesulfonyl)amide and cesium-di(4-toluenesulfonyl)amide were grown. Their structure determinations revealed that both polymeric salts contain cation layers (Cs⊕)∝: The one lipophilically wrapped by di(benzenesulfonyl)amide ligands exhibits hexagonal (Cs⊕)6 subunits, whereas the methylsubstituted di(4-toluenesulfonyl)amide ligands of the other one are interspersed within (Cs⊕)^ layers. The resulting lipophilically wrapped sheets with Cs⊕ cations of ten- and twelve-fold coordination to disulfonyl O and C centers vary in their overall thickness of 1.77 nm and 1.39 nm because the toluene substituents in the thinner one are tilted. The remarkable effects caused by the 4-methyl substitution of the phenyl rings determine the structures of the parent di(arylsulfonyl)amines as well: Contrary to the polymeric phenyl substituted derivative, the toluene homologue crystallizes in dimers. The single crystals grown of the closely related di(arylsulfonyl)amides with or without para methyl substituents and their poly(Cs⊕) aggregates without any solvent inclusion show hitherto unknown structural motifs and, therefore, further improve our knowledge of alkali salt self-organisation phenomena in crystals.
Crystal Structure and Magnetic Properties of a Binuclear Copper(II) Complex Bridged by an Alkoxo-oxygen Atom and an Acetate Ion
Authors: Zeyrek C. T. , Elmali A. , Svoboda I. , Fuess H.
Published: February 2015

[Cu4(L)2(O2CMe)2] H2O (L = 1,3-bis(5-bromo-2-hydroxybenzylidene)propan-2-ol) was synthesized and its crystal structure determined. (C38H34N4O10Br4Cu4)·H2O, monoclinic, space group P21/c, a = 21.072(5), b = 9.673(2), c = 21.934(4) Å, β = 109.73(2)°, V = 4208(2) Å3, Z = 4. The crystal structure consists of two independent binuclear copper(II) complexes and the non-coordinating water molecule in the asymetric unit. The Cu(II) ions are in a square-planar geometry and coordinated by donor atoms of the ligand (NO3).

The average Cu···Cu distance and average Cu-O-Cu angle are 3.491(2) Å and 132.0(1)°, respectively. Temperature-dependent magnetic susceptibility measurements of the complex show an intramolecular anti ferromagnetic coupling in the dimeric Cu(II) core. The fitting parameters are -2J = 174.4 cm-1, g = 1.98.
X-Ray Crystal Structure Analysis of Substituted 5-(2,3-Dihydro-7-benzofuryl)- 2-methylpyrazolo[4,3-d]pyrimidin-7-one (iso-Biagra) [1]
Authors: M. El-Abadelah Mustafa , Sabri Salim S. , Khanfar Monther A. , Voelter Wolfgang , Maichle-Mössmer Cacilia
Published: February 2015

X-ray crystal structure data for the substituted 5-(2,3-dihydro-7-benzofuryl)-2-methylpyrazolo[ 4,3-d]pyrimidin-7-one (3) reveal that the two bicyclic heteroaryl systems show no coplanarity along their joint C (5) - C (11) axis with an interplanar angle of 9.6°. Nonetheless, the spatial interatomic distance for O(17)-N(6), determined as 2.73 A, allows the formation of a relatively weak intramolecular hydrogen bond between the pyrimidinone N(6)-H and the O(17) lone pair of the dihydrobenzofuryl moiety.
Optical Outer-Sphere Charge Transfer in Ion Pairs with Peroxoborate as Donor
Authors: Kunkely Horst , Vogler Amd
Published: February 2015

Peroxoborate and the oxidizing cations [Co(NH3)6]3+, [Ru(NH3)6]3+ and N,N′-dimethyl-4,4′- bipyridinium2+ (paraquat2+) form ion pairs in aqueous solutions which display outer-sphere charge transfer (OSCT) bands in their absorption spectra. This CT involves an electronic transition from the peroxo substituents of peroxoborate to the cations. When 10,10′-dimethyl- 9,9′-biacridinium2+ (lucigenin2+, LG2+) is used as an electron acceptor an OSCT absorption is not observed owing to the instability of the ion pair LG2+ peroxoborate which undergoes a chemiluminescent conversion to N-methylacridone.
Properties of the Ternary (Dien)Pt(PMEA-N7) Complex Containing Diethylenetriamine (Dien) and the Antiviral 9-[2-(Phosphonomethoxy)ethyl]adenine (PMEA). Synthesis, Biological Screening, Acid-Base Behaviour, and Metal Ion-Binding in Aqueous Solution
Authors: Kampf Gunnar , Lüth Marc Sven , Müller Jens , Holý Antonín , Lippert Bernhard , Sigel Helmut
Published: February 2015

The synthesis of (Dien)Pt(PMEA-N7), where Dien = diethylenetriamine and PMEA2- = dianion of 9-[2-(phosphonomethoxy)ethyl]adenine, is described. No useful biological activity could be discovered for this complex which is in contrast to the known antiviral properties of PMEA itself. The acidity constants of the twofold protonated H2[(Dien)Pt(PMEA-N7)]2+ complex were determined (UV spectrophotometry and potentiometric pH titration): The release of the proton from the -P(O)2(OH)- group is only slightly affected by the N7-coordinated (Dien)Pt2+ unit, whereas the acidity of the (N1)H+ site is strongly enhanced. The stability constants of the M[(Dien)Pt(PMEA-N7)]2+ complexes with the metal ions M2+ = Mg2+, Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ were measured by potentiometric pH titrations in aqueous solution at 25 °C and I = 0.1 M (NaNO3). Application of previously determined straightline plots of log KM(R-PO3)
M versus KH(R-PO3)
H for simple phosph(on)ate ligands, R-PO3
2- where R represents a non-inhibiting residue without an affinity for metal ions, proves that the primary binding site of the complex-ligand, (Dien)Pt(PMEA-N7), with all the metal ions studied is the phosphonate group; in most instances the expected stability is actually reduced by about 0.4 log units due to the N7-bound (Dien)Pt2+ unit. Only for the Cu[(Dien)Pt(PMEA-N7)]2+ and the Zn[(Dien)Pt(PMEA-N7)]2+ systems the formation of some 5-membered chelates involving the ether oxygen atom of the -CH2-O-CH2-PO3
2- residue could be detected; the formation degrees are 52 ± 9% and 32 ± 14%, respectively. The metal ion-binding properties of (Dien)Pt(PMEA-N7) differ considerably from those of PMEA2-, yet they are relatively similar to those of pyrimidine-nucleoside 5'-monophosphates. The structures of the various complex species in solution are discussed and compared.
Structural and Spectroscopic Characterization of Two New Cu(II)-Dipeptide Complexes
Authors: Facchin Gianella , Torre María H. , Kremer Eduardo , Piro Oscar E. , Castellano Eduardo E. , Baran Enrique J.
Published: February 2015

Two new Cu(II) complexes of stoichiometry [Cu(L-dipept)], containing as ligands the dipeptides L-alanine-L-valine and L-alanine-L-phenylalanine were prepared. They were characterized by single crystal X-ray diffractometry, and infrared and electronic spectroscopy. Both crystallize in the orthorhombic space group P212121 with Z = 4. The Cu(II) ion has essentially the same elongated pyramidal coordination, being equatorially cis coordinated by a N2O2 arrangement of ligand atoms and axially by a carbonyl oxygen atom. The compounds show rather similar polymeric structures that differ from each other basically in the dihedral angle between adjacent N2O2 planes. The infrared and electronic spectra are briefly discussed on the basis of the structural characteristics of the complexes. Superoxide dismutase-like activity was tested for both compounds.
Furanoid and Furofuranoid Lignans from Daphne oleoides
Authors: Riaz Muhammad , Ullah Nisar , Mehmood Arshad , Nawaz Hafiz Rab , Malik Abdul , Afza Nighat
Published: February 2015

Furofuranoid lignan (1) and (2) and furanoid lignan (3) have been isolated from Daphne oleoides and their structures elucidated through chemical and spectroscopic studies as 2-(3'- methoxy-4′-O-α-D-galactopyranosylphenyl)-6-(3″-methoxy-4″-hydroxyphenyl)-3,7-dioxabicyclo[ 3.3.0]octane (1), 2-(3′,5′-dimethoxy-4′-O-a-D-galactopyranosylphenyl)-6-(3″-m ethoxy- 4″-hydroxyphenyl)-3,7-dioxabicyclo[3.3.0]octane (2), and 4,9′-dihydroxy-3,3′-dimethoxy-4′- O-β-D-glucopyranosyl-7′,9-epoxylignan (3). Two known lignans (4) and (5) have also been reported for the first time from this species.
Synthesis and Spectroscopic Investigations of New Linear Heterobimetallic Clusters [Me4N]3[(TOS3 )2Ag] (T = Mo, W). Crystal Structure of [Me4N]3[(MoOS3 )2Ag]
Authors: Shamsur Rahman A. B. M. , Boiler H. , Klepp K. O.
Published: February 2015

Red-brown crystals of a new bis(thiomolybdate) complex [Me4N]3[(MoOS3)2Ag] were formed at room temperature through the reaction of a solution of [Me4N]2[MoOS3] in MeCN with solid AgCN. They are monoclinic, space group P21/c with unit cell parameters a = 16.662(9), b = 9.464(3), c = 17.890(8) A, /3 = 101.87(2)°, Z = 4. The crystal structure was determined from single crystal diffractometer data (MoKα-radiation) and refined to R = 0.044 (3614 reflections, 236 variable parameters). The structure is characterized by trinuclear complex anions, [(MoOS3)2Ag]3-. According to Weissenberg investigations the homologous tungsten compound is isostructural.

The infrared spectrum of the molybdenum complex (KBr powder) shows absorption bands at 884 (vs) and 871 (w) cm-1 (terminal v(Mo-0)), 483 (vs) cm-1 (terminal v(Mo-S)), 451 (vs), and 435 (w) cm-1 (bridging v(Mo-S)). The tungsten complex showed bands at 901 (vs) cm-1 (terminal v(W-O)), 478 (vs) cm-1 (terminal v(W-S)), and 435 (vs) cm-1 (bridging v(W-S)). The anionic mass spectra shows molecular ion peaks at m/z 524 and 700 for [(MoOS3)2Ag]- and [(WOS3)2Ag]-, respectively, as well as peaks for other fragments.
Komplexe gemischter Siliciumhalogenide mit 3,4-Lutidin / Complexes of Mixed Silicon Halides with 3,4-Lutidine
Authors: Hensen Karl , Mayr-Stein Ralf , Spangenberg Björn , Bolte Michael , Rühl Stephan
Published: February 2015

The first single crystal X-ray investigations of 3,4-lutidine complexes with mixed silicon tetrahalides were carried out
Vierzähnige Benzamidin-Liganden in ein-und mehrkemigen Kupfer(II)-Komplexen / Quadridentate Benzamidine Ligands in Mono-and Oligonuclear Copper(II) Complexes
Authors: Leßmann F. , Beyer L. , Hallmeier K.-H. , Richter R. , Sieler J. , Strauch P. , Voigt A.
Published: February 2015

Bridged N-thiocarbamoyl substituted bis-benzamidines (C2H5)2N-C(S)-N=C(Ph)-NH-R-NH-C(Ph)=N-C(S)-N(C2H5)2 with different moieties R (H2L1 : R = diphenylmethane-2,2'-diyl, H2 L2: R = diphenylmethane-3,3'-diyl, and H2L3: R = diphenylmethane-4,4'-diyl) were synthe­sized by the reaction of N-(thiocarbamoyl)benzimidoyl chlorides with diamines. These quadri­ dentate ligands form neutral mononuclear (CuL1), dinuclear (Cu2L3
2) and trinuclear (Cu3L2
3) copper(II) chelates in dependence of the different bridging unit in the ligands. The compounds were characterized by NMR, IR, EPR and XPS spectroscopy and FAB mass spectrometry. The molecular structures of the ligand H2L3 and the complex CuL1 have been determined by X-ray methods.
Syntheses and Structures of Thorium(IV) Complexes with Bis(diphenylphosphino)ethane Dioxide, Ph2P(O)CH2CH2P(O)Ph2, and Bis(diphenylphosphoryl)amide, [Ph2P(O)NP(O)Ph2]
Authors: Bonfada Élida , Schulz-Lang Ernesto , Zan Renato André , Abram Ulrich
Published: February 2015

The cationic thorium(IV) complexes [Th{Ph2P(O)CH2CH2P(O)Ph2}2(NO3)3]NO3 and [Th{Ph2P(O)NP(O)Ph2}3(dmso)2]NO3 have been synthesized by reactions of Th(NO3)4 · 5H2O with bis(diphenylphosphino)ethane dioxide, Ph2P(O)CH2CH2P(O)Ph2 (L1), or ammonium bis(diphenylphosphoryl)amide, (NH4)[Ph2P(O)NP(O)Ph2] (NH4L2), and subsequent recrystallization from dimethyl sulfoxide. The products have been studied spectroscopically and by X-ray crystallography.

The thorium atom is ten-co-ordinate in the [Th(L1)2(NO3)3]+ cation with a coordination sphere which does not match one of the idealized polyhedra for ten-coordination. Th-O bonds have been found in the range between 2.342(3) (phosphine oxide) and 2.599(4) A (nitrate). An eight-coordinate thorium atom is found in the [Th(L2)3(dmso)2]+ cation. The almost ideal square-antiprismatic environment of the metal is occupied by oxygen atoms with Th-0 bond lengths between 2.363(6) and 2.392(11) Å
Polysulfonylamine, CXXV [1]. Neue Komplexe von Disulfonylaminen mit Kronenethern - im voraus entworfen oder zufällig entdeckt / Polysulfonylamines, CXXV [1]. New Complexes of Disulfonylam ines with Crown Ethers - Preconceived or Discovered by Serendipity
Authors: Henschel Dagmar , Wijaya Karna , Moers Oliver , Blaschette Armand , Jones Peter G.
Published: February 2015

In a study aim ed at the „deconstruction“ of the supramolecular aggregate 3(18C6) · 2HN( SO2Me)2 (1,18C6 = 18-crown-6), which is known to display a ladder structure with two isotactic [18C6 - Me SO2N(H)SO2Me···)∞ polymers forming the uprights and symmetrically N - H···O bonded 18C6 rings providing the rungs, the following crystalline complexes were isolated and (except for 2b) characterized by low-temperature X-ray diffraction: 18C6-ClN (SO2Me)2 (2a, triclinic, space group P1̅, Z = 2), 18C6-PhN (SO2Me)2 (2b), 18C6 -MeN(SO2Me)2 (3, monoclinic, P21/c, Z = 8), Bz18C6-HN(SO2Me)2 (4, Bz18C6 = benzo-18-crown-6, monoclinic, P21/n, Z = 4), 18C6-2 MeN (SO2Me)2 (5, triclinic, P1̅, Z = 1), 18C6-Me2SO- HN( SO2Me) (SO2Ph) (13, triclinic, P1̅, Z = 2), and 18C6-H2OMe2SO·2HN(SO2Me)2 (14, triclinic, P1̅, Z = 2). Each of the one-dimensional polymers 2a (syndiotactic), 3 (disyndiotactic) and 4 (isotactic) mimics a single upright of 1; in contrast to 1 and 2a, where the intra-catemer connectivity solely relies on S - Me ··· crow n and crown ··· O = S hydrogen bonds, this bonding system is reinforced in 3 by N -Me ··· crown and in 4 by N - H ··· crown hydrogen bonds. Complex 5 is monomeric and matches a fragment formally extruded from the catemer 3; moreover, 3 and 5 represent a rare case of two structurally characterized 18C6 complexes containing the same uncharged guest species in distinct molecular ratios. The surprising structure of the quaternary adduct 14 exhibits an [18C6 ··· MeSO2N(H)SO2Me ··· ]∞ chain, which can be regarded both as an isolated, though unmodified upright from the ladder 1 and, being syndiotactic, as a stereochemical analogue of 2a; the potentially rung-forming *NH functions in the chain are blocked by hydrogenbonded side chains of the type * N - H ··· water ··· sulfoxide ··· H - N (SO2Me)2. The ternary complex 13 consists of chains [18C6 ··· Me2SO ··· H - N (SO2Ph)SO2Me···]∞ and is not closely related to the other structures
Uber die Isolierung von Sitosterin-(6'-O-acyl)-β-D-glucopyranosiden aus Flacourtia indica und über unerwartete Gelbildungen durch das Triacetat / On the Isolation of Sitosterin-(6'-O-acyl)-β-D-glucopyranosides from Flacourtia indica and on Unexpected Formation of Gels by the Triacetate
Authors: Dehmlow Eckehard Volker , Guntenhoner Matthias , Ree Teunis van
Published: February 2015

A mixture of the title compound-(6′) stearate, margarate, palmitate, linolate, and linole- nate (2a-e) was isolated from shredded dried leaves and twigs of Flacourtia indica. The margarate was observed for the first time. 0.5% solutions of the triacetate mixture (1a-e) in methanol or ethanol give “solid" gels stable for months. From these the unchanged triacetates 1a-e can be recovered indicating that this low-molecular material is responsible for the formation of the gel.
Neue Pentaphosphaferrocene
Authors: Dielmann Fabian , Merkle Roger , Heinl Sebastian , Scheer Manfred
Published: February 2015

By cothermolysis of [CpRFe(CO)2]2 [CpR = η5-C5(CH2Ph)5 (Cpbn) (1) and η5-C5Me4C2H4SMe (CpS) (2)] with P4 phosphorus two novel pentaphosphaferrocenes of the formula [CpRFe(η5-P5)] [CpR = CpS (3), Cpbn (4)] have been synthesised and comprehensively characterised. These two products represent the first derivatives of this class of compounds with a functionalised as well as a sterically bulky adjacent cyclopentadienyl ligand. The pentabenzylcyclopentadienyl derivative 4 as well as both of the starting materials [CpRFe(CO)2]2 1 and 2 have been additionally characterised by X-ray diffraction structure determinations. The pentaphosphaferrocene 4 represents in the crystal lattice highly aggregated units via intra- and intermolecular π-stacking interactions of the phenyl rings of the Cpbn ligand.
69/71Ga and 115In NMR Spectroscopy of Lithium Tetra(tert-butyl)gallate and -indate: Spin-Spin Coupling Constants 1J(69/71Ga,13C) and 1J(115In,13C)
Authors: Wrackmeyer Bernd , Klimkina Elena V.
Published: February 2015

The 13C, 69/71Ga and 115In NMR spectra of lithium tetra(tert-butyl)gallate and -indate were measured under various conditions. It proved possible to determine for the first time the coupling constants 1J(69/71Ga,13C) = 182 Hz/232 Hz and 1J(115In,13C) = 310±10 Hz for these metallates under conditions for solvent-separated ions. DFT calculations [B3LYP/6-311+G(d,p)] were carried out for organogallium compounds such as tri(tert-butyl)gallium, trimethylgallium and tetramethylgallate in order to predict and confirm coupling constants 1J(Ga,13C).
Trifluoromethylated Compounds with SiNN and SiON Backbone, and the Crystal Structures of Trimethyl- and Trichloro(trifluoromethyl)silane
Authors: Woski Markus , Mitzel Norbert W.
Published: February 2015

The reaction of (F3C)Cl2SiCl3 with the lithiated hydrazine LiN(Me)NMe2 gives the compound (F3C)Cl2SiN(Me)NMe2 (1) and in traces Cl3SiN(Me)NMe2 (2). The reactions with LiN(SiMe3)NMe2 and LiONMe2 give (F3C)Cl2SiN(SiMe3)NMe2 (4) and (F3C)Cl2SiONMe2 (5), respectively. The compounds were characterised by multinuclear solution NMR, gas-phase IR spectroscopy and mass spectrometry. Information about conformational preferences of 1 and 4 can be extracted by comparing experimental IR spectra with those calculated by quantum chemical methods (B3LYP/6-311G**). The former show the gas phase of the β -donor-acceptor silanes 1 and 4 to be dominated by the anti conformations, while the calculations show a preference for the gauche conformers. The crystal structure of Cl3SiN(Me)NMe2 (2) has been determined. The solid-state structures of the Ruppert reagent F3C-SiMe3 (1) and its chlorine analogue F3C-SiCl3 (2) have also been determined by X-ray diffraction of single crystals grown by in situ techniques.
New Hydrogen Peroxide Adducts of Alkali Metal Tetracyanoplatinates A2[Pt(CN)4] ·H2O2 (A = K, Rb, Cs)
Authors: Mühle Claus , Peters Eva-Maria , Jansen Martin
Published: February 2015

The title compounds have been synthesized by adding hydrogen peroxide to an aqueous solution of A2[Pt(CN)4] (A = K, Rb, Cs). They grow as yellow needles after concentrating and cooling to 4 °C. The structures were elucidated from single crystal analysis. The isostructural compounds crystallize monoclinically, in space group C2/c with Z = 4. K2Pt(CN)4 ·H2O2: a = 13.3751(7), b = 11.2713(6), c = 6.5461(3) Å, β = 105.432(1)◦, V = 951.3(3) Å3. Rb2Pt(CN)4 ·H2O2: a = 13.6103(2), b = 11.6759(1), c = 6.5683(7) Å, β = 106.588(2)0, V = 1000.3(2) Å3. Cs2 Pt(CN)4 ·H2O2: a = 13.9569(2), b = 12.2023(2), c = 6.5857(9) Å, β = 107.590(3)0, V = 1069.1(2) Å3. As a remarkable feature, the hydrogen bonds O-H···N vary significantly with the cation size: in the Cs compound the O-H bonds are weakest, and the N· · ·H interactions are strongest. All three compounds were characterized by differential thermal analysis, thermogravimetry and infrared spectroscopy.
Thianthrene Radical Cation Hexafluorophosphate
Authors: Beck Johannes , Bredow Thomas , Tjahjanto Rachmat Triandi
Published: February 2015

In the presence of [NBu4][PF6] as the electrolyte, thianthrene (TA) is transformed by electrochemical oxidation to thianthrenium hexafluorophosphate containing the TA•+ radical cation. The reactions were performed in CH2Cl2, H3CCN, and liquid SO2 as solvents. In CH2Cl2, TA[PF6] is sparingly soluble and is deposited directly in crystalline form on the platinum electrode. In H3CCN and liquid SO2, TA[PF6] is highly soluble and gives dark blue solutions from which it can be crystallized upon concentration of the solutions. The air sensitive crystals are black with bronze metallic luster. They belong to the monoclinic system (C2/m, a = 12.4345(8), b = 10.5318(6), c = 11.1303(7) Å , β = 112.565(3)◦) and are built up of almost planar TA•+ cations and octahedral [PF6]− anions. The F atoms of the anions are disordered over two positions. The radical cations are associated to form dimeric units (TA•+)2 with the planar molecules stacked with two weak S· · ·S bonds (3.06 Å ). In the crystal these dimers are separated by the [PF6]− anions. Electrical conductivity measurements show TA[PF6] to be a small-gap semiconductor. Conductivity is low at r. t. but reaches 2.5 · 10−5 S m−1 at 110 °C, the activation energy in the high-temperature region amounts to 1.2 eV. Periodic quantum-chemical calculations at hybrid density-functional level predict a strong coupling between neighboring (TA•+) spin centers, resulting in a singlet ground state. The calculated band gaps of both singlet (1.5 eV) and triplet (0.9 eV) states are small, consistent with the measured conductivity
Structure and Magnetic Properties of GdPt2In and GdPt2Sn
Authors: Heying Birgit , Rodewald Ute Ch. , Hermes Wilfried , Pöttgen Rainer
Published: February 2015

The platinum-rich intermetallic compounds GdPt2In and GdPt2Sn were synthesized by arc-melting of the elements and subsequent annealing. The structures were refined from single crystal X-ray diffractometer data: ZrPt2Al type, space group P63/mmc, a = 455.1(1), c = 899.3(3) pm, wR2 = 0.0361, 166 F2 values, 9 variables for GdPt2In, and a = 453.2(1), c = 906.5(2) pm, wR2 = 0.0915, 166 F2 values, 9 variables for GdPt2Sn. The platinum and indium (tin) atoms build up threedimensional [Pt2In] and [Pt2Sn] networks with short Pt-In (Pt-Sn) distances and Pt2 dumb-bells (290 and 297 pm in GdPt2In and GdPt2Sn). The gadolinium atoms have coordination number 14 with 8 Pt and 6 In (Sn) neighbors. Magnetic susceptibility measurements on GdPt2In show Curie-Weiss behavior with an experimental magnetic moment of 8.06(2) μB/Gd atom. GdPt2In orders ferromagnetically at 27.7(2) K
Ferromagnetic Ordering in CeZnSn
Authors: Hermes Wilfried , Matar Samir F. , Harmening Thomas , Rodewald Ute Ch. , Eul Matthias , Pöttgena Rainer
Published: February 2015

The stannide CeZnSn was obtained in X-ray-pure form by induction-melting of the elements in a sealed tantalum ampoule. CeZnSn crystallizes with the YPtAs-type structure, space group P63/mmc, a = 456.7(3), c = 1673.8(5) pm, wR2 = 0.0862, 259 F2 values, and 12 variables. The zinc and tin atoms build up puckered Zn3Sn3 hexagons (Zn-Sn 271 pm) with weak interlayer Zn-Zn interactions (323 pm). Susceptibility measurements of CeZnSn reveal modified Curie-Weiss behavior above 50 K with an experimental magnetic moment of 2.77(1) μB / Ce atom. The cerium magnetic moments order ferromagnetically at TC = 5.2(1) K. 119Sn Mössbauer spectra show a single tin site at an isomer shift of δ = 1.967(4) mm/s subjected to a small quadrupole splitting of ΔEQ = 0.41(2) mm/s at 40 K. At 4.2 K a magnetic hyperfine field of 0.872(5) T is transferred to the tin site. From DFT scalar relativistic calculations of the electronic and magnetic structures, chemical bonding analysis reveals on one hand a weaker bonding of Zn than of Sn with the cerium substructures with a twice stronger Ce1-Sn bond compared to Ce2-Sn. On the other hand, a ferromagnetic ground state is identified from total energy differences in agreement with experiment
Supersilyliertes Ethen trans-(tBu3Si)HC=CH(SitBu3) und Ethin (tBu3Si)C≡C(SitBu3) / Supersilylated Ethene trans-(tBu3Si)HC=CH(SitBu3) and Ethyne (tBu3Si)C≡C(SitBu3)
Authors: Vitze Hannes , Wietelmann Ulrich , Murso Alexander , Bolte Michael , Wagner Matthias , Lerner Hans-Wolfram
Published: February 2015

The supersilylated ethene trans-(tBu3Si)HC=CH(SitBu3) (triclinic, P ī) is accessible from the reaction of tBu3SiCHBr2 with nBuLi at −78 °C in THF or Et2 O. The reaction of Li(H2NCH2CH2NH2)C≡CH with tBu3SiBr leads to the formation of (tBu3Si)C≡CH and (tBu3Si)C≡C(SitBu3). X-Ray quality crystals of (tBu3Si)C≡C(SitBu3) (triclinic, P ī) were obtained by recrystallization from hexane. In contrast to the structures of the disilane tBu3Si-SitBu3 and the disiloxane tBu3Si-O-SitBu3, the sterically crowded ethene trans-(tBu3Si)HC=CH(SitBu3) and ethyne (tBu3Si)C≡C(SitBu3) feature dihedral angles of 60° in the solid-state structures
Study on Chemical Constituents of the Vietnamese Medicinal Plant Fissistigma petelotii
Authors: Thao Tran Thi Phuong , Anh Nguyen Vu , Anh Ho Ngoc , Quan Tran Duc , Sung Tran Van
Published: February 2015

A new bisabolene derivative (1S*, 2R*, 4R*, 7R*, 10R*)-1,7,10,11-tetrahydroxy-1,7,11-trimethyl- 4,10(H)-2-O-cinnamoyl-bisabol-8(9)-ene (1), together with cinnamic acid (2), methyl cinnamate (3), sodium cinnamate (4) and methyl elaidate (5) have been isolated from the leaves and barks of Fissistigma petelotii. Sodium cinnamate (4) was isolated for the first time from the nature. The structures of these compounds were elucidated by analysis of their IR, MS, 1D and 2D NMR spectra.
Crystal Structure of 4-(1-Hydroxypropyl)- isochroman-1,3-dione
Authors: Abou Akoun , Goulizan Bi Severin D. , Kaboré Leopold , Djandé Abdoulaye , Saba Adama , Kakou-Yao Rita
Published: February 2015

The title compound (C12H10O4) crystallizes in the triclinic space group P1̄ with a = 7.367(3), b = 8.1188(3), c = 9.549(5) Å, α = 74.034(1)°, β = 84.374(2)°, γ = 64.581(3)°, Z = 2, and dcalc = 1.462 g cm−3. It exhibits a strong intramolecular O-H···

O hydrogen bond and exists as the exocyclic enolic tautomer as it has been observed in solution. The structure is stabilized by C-H···π, C-O···π and π-π stacking interactions between benzene and pyran rings.
Nano-TiO2: an Eco-friendly and Re-usable Catalyst for the One-pot Synthesis of β-Acetamido Ketones
Authors: Mirjalili Bi Bi Fatemeh , Akbari Ali
Published: February 2015

Nano-TiO2 as an efficient, eco-friendly and reusable catalyst was applied for the one-pot synthesis of β -acetamido ketones. In this improved procedure, an aryl aldehyde, an aryl ketone, acetyl chloride and acetonitrile were condensed in the presence of the catalyst at room temperature.
Synthesis and Analgesic-like Effect of (6R, 4S)-p-Mentha-1,8-dien-6-ylmethylene- p-toluenesulfonamide
Authors: Sousa Damião P. de , Nóbrega Franklin F. F. , Almeida Reinaldo N. de , Brocksom Timothy J.
Published: February 2015

The synthesis of a monoterpene-based para-toluenesulfonamide is reported starting from naturally occurring (R)- (−)-carvone (1), by 1,2-addition of HCN followed by reduction with lithium aluminum hydride to afford the amino alcohols 3a and 3b. Tosylation of thismixture with p-toluenesulfonyl chloride furnished sulfonamide 4 in 55% overall yield. Compound 4 was evaluated in behavior animal models to investigate its effects on the central nervous system. It showed low toxicity and sedative action in mice, indicating it to be psychoactive. It also caused a decrease in the spontaneous motor activity of mice. This depressant effect was confirmed in the acetic acid-induced writhing test, which demonstrated a significant antinociceptive response more potent than 1. The present results provide evidence that sulfonamide 4 has analgesic-like psychopharmacological activity.
{2}Metallocryptands of Iron and Gallium: Synthesis, Structure, and Properties [1]
Authors: Saalfrank Rolf W. , Reimann Uwe , Scheurer Andreas , Hampel Frank , Goebel Cornelia , Herbst-Irmer Regine
Published: February 2015

Starting from CH-acidic tetradentate ligands H2L (1) and triethylamine, the synthesis and characterisation of four dinuclear iron(III) and gallium(III) cryptands [M2(L)3] (3, 4) are reported. The structures of the ligand H2L (1a) and the triple helicate 3b were determined by X-ray diffraction analysis. The ferric complexes 3 were further characterised by Mössbauer spectroscopy and cyclic voltammetry. NMR spectroscopy proved the diamagnetic gallium(III) cryptands 4 to remain stable in solution for several days.
NMR Studies and Crystal Structure Determinations of CF3 Group-containing Bicyclic Phenolates
Authors: Mamat Constantin , Reinke Helmut , Langer Peter
Published: February 2015

Three new CF3-substituted bicyclic salicylate derivatives were synthesized by the TiCl4-mediated cyclization of trifluoromethyl-containing ketones with 1,3-bis(silyl enol ethers) and characterized by NMR and IR, spectroscopy, mass spectrometry and elemental analysis. The crystal structures of the bicyclic derivatives have been determined by single crystal X-ray analysis. All structures exhibit hydrogen bonding.