Band 66, Heft 1

A new compound of the composition Nb 0.84 N was prepared by ammonolysis of NbO 2 at 1100 °C. The crystal structure refinement was performed by the Rietveld method using X-ray and neutron powder diffraction data. Nb 0.84 N crystallizes in the trigonal space group R3m (no. 166) with the lattice parameters a = 298.5(2) and c = 2384.3(4) pm. The niobium atoms form a close packing with a layer sequence which can be described by the Jagodzinski symbol hhc. The nitrogen atoms fill all octahedral voids. Along [001] a sequence of two layers of trigonal NbN6 prisms and one layer of NbN 6 octahedra is formed. The nitrogen positions are fully occupied, the niobium positions only partially. Nb 0.84 N is part of a family of crystal structures between the anti-NiAs and the NaCl type consisting of close-packed metal layers with varying stacking sequences Graphical Abstract Synthesis and Crystal Structure of Nb 0.84 N

Needle-shaped crystals of the metal-rich phosphide Ce 4 Ir 13.55 P 9 were synthesized from the elements in a lead flux (starting composition 1 : 2 : 2 : 60) at 1370 K followed by slow cooling. Ce 4 Ir 13.55 P 9 crystallizes with a new orthorhombic structure type: Pnma, a = 1269.1(2), b = 399.1(1), c = 3349.9(7) pm, wR2 = 0.0722, 2025 F 2 values and 139 variables. Two of the 14 crystallographic iridium sites show small defects. All phosphorus atoms have slightly distorted tricapped trigonal prismatic metal coordination by cerium and iridium. The iridium and phosphorus atoms build up a threedimensional [Ir 13.55 P 9 ] δ− polyanion in which the cerium atoms fill distorted hexagonal cavities. Within the polyanion the phosphide anions are isolated, and one additionally observes a broad range of Ir-Ir bonding (Ir-Ir distances 278 - 298 pm). From a geometrical point of view the Ce4Ir13.55P9 structure can be considered as an intergrowth structure of distorted ThCr 2 Si 2 - and SrPtSb-related slabs Graphical Abstract The Metal-rich Phosphide Ce 4 Ir 13.55 P 9

Colorless needles of Ga 2−x Sc x O 3 (x = 0.83) were isolated during the crystal growth of La 3 Ga 3 Sc 2 O 12 in a K 2 WO 4 flux. The structure was refined from X-ray single-crystal data: β -Ga 2 O 3 type,C2/m, Z = 4, a = 12.716(4), b = 3.1566(6), c = 5.928(5) Å , β = 102.57(3)◦,V = 232.2 Å3, wR2 = 0.0618, 429 F 2 values, 32 variables. The structure is based on infinite double chains of edge-sharing Sc/GaO 6 octahedra running along the b axis. The GaO 4 tetrahedra connect these chains by sharing corners and form a three-dimensional framework. The oxygen atoms form a distorted ccp pattern. The 45 Sc NMR spectra confirm the presence of a single scandium site, while 71 Ga NMR data clearly prove the partial occupancy of the scandium site by gallium atoms. The nuclear electric quadrupolar parameters of 45 Sc and 71 Ga are discussed in relation to the crystallographic atomic environments Graphical Abstract Single-crystal Structure and Solid-state NMR of Ga 2–x Sc x O 3 (x = 0.83)

Single crystals of Sr 2 H 3 I andBa 5 H 2 I 3.9(2) O 2 were obtained by reacting Sr or Ba, respectively, with dried and sublimed NH 4 I in a 4 : 1 molar ratio in silica-jacketed Nb ampoules for 13 h at 1200 K. The crystal structures of the new compounds have been determined by means of single-crystal X-ray diffraction. Sr 2 H 3 I crystallizes in a stuffed anti-CdI 2 structure isotypic to Ba 2 H 3 Cl in the space group P3m1 (no. 164) with the lattice parameters a = 426.0(1) and c = 774.9(2) pm, while Ba 5 H 2 I 3.9(2) O 2 crystallizes in a new structure type in the space group Cmcm (no. 63) with the lattice parameters a = 1721.0(2), b = 1452.5(2) and c = 639.03(9) pm. The structural results for Sr 2 H 3 I are corroborated by EUTAX calculations. For the disordered compound Ba 5 H 2 I 3.9(2) O 2 , EUTAX calculations on an approximated, ordered structural model were used to find possible insights into the disorder Graphical Abstract AlkalineEarthMetal-Hydride-Iodide Compounds: Syntheses andCrystal Structures of Sr 2 H 3 I and Ba 5 H 2 I 3.9(2) O 2

The monoanionic complexes (C 5 H 5 NH)[ZnBr 3 (C 5 H 5 N)] (1) and (n-CH 3 C 5 H 4 NH)[ZnBr 3 (n- CH 3 C 5 H 4 N)] (n = 2 (2), 3 (3), 4 (4)) were prepared by crystallization from ethanol solutions through redistribution reactions between the corresponding dianionic complexes (C 5 H 5 NH) 2 [ZnBr 4 ] (5) and (n-CH 3 C 5 H 4 NH) 2 [ZnBr 4 ] (n = 2, 3 (6), 4 (7)) and the neutral complexes [ZnBr 2 (C 5 H 5 N) 2 ] (10) and [ZnBr 2 (n-CH 3 C 5 H 4 N) 2 ] (n = 2 (8), 3, 4 (9)). The crystal structures of 1, 4, 9, and 10 were determined; 1: triclinic, P1, a = 7.6957(5), b = 7.7975(4), c = 12.4768(8) Å , α = 90.857(5), β = 95.917(5), γ = 107.899(6)°, Z = 2, 150 K; 4: monoclinic, P2 1 /c, a = 14.8369(6), b = 13.9504(5), c = 8.0041(3) Å , β = 96.318(4)°, Z = 4, 299 K; 9: monoclinic, P2 1 /c, a = 14.2883(5), b = 8.0269(3), c = 13.6031(5) Å , β = 100.581(4)°, Z = 4, 150 K; 10: monoclinic, P2 1 /c, a = 8.7388(5), b = 17.9730(10), c = 8.5452(5) Å , β = 100.024(6)°, Z = 4, 300 K. The cation and anion are paired up via bifurcated hydrogen bonds in the structure of 1 and via a normal N-H· · ·Br hydrogen bond in the structure of 4. 81 Br NQR resonance lines coinciding in number with the Br atoms in the chemical formulae were observed for the compounds 1 - 5 and 7 - 9 throughout the temperature range from 77 to ca. 320 K. The comparison between the net charges on the Br atoms obtained by the Townes-Daily analysis or by the Mulliken population analysis seems to indicate that the formation of the intermolecular N-H· · ·Br hydrogen bonds and the π-π and the CH 3 -π interactions in the crystal structures of the monoanionic complexes are the driving forces to the redistribution reactions Graphical Abstract Crystal Structure and NQR Studies of Compounds (RH)[ZnBr 3 (R)], (RH) 2 [ZnBr 4 ] and [ZnBr 2 (R) 2 ] (R = Py, n-MePy: n = 2, 3, 4); on the Dominant Stability of the Monoanionic Complexes over the Dianionic and Neutral Species

The structural properties of composites prepared by a hydrothermal method in high-pressure conditions and the role of pressure in the formation of hydroxylapatite-polyurethane (HAp-PU) materials with strong interactions between the two components were investigated. X-Ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), FT-IR and NMR analyses were used to characterize the composite powders from a structural, morphological and compositional point of view. Both FT-IR and NMR spectroscopies indicate interactions between hydroxylapatite and acid polyurethane Graphical Abstract A New Approach for the Synthesis of Nanostructured Polyurethane-Hydroxylapatite-based Hybrid Materials

A luminescent multilayer film has been fabricated from the polyoxometalate anion α- [PMo 12 O 40 ] 3− (α-PMo 12 ) and the cation Fuchsin Basic (FB) through an electrostatic layer-by-layer (LbL) self-assembly method and characterized by UV/Vis spectra, atomic force microscopy and X-ray photoelectron spectra. The fluorescence properties of the LbL film have also been investigated. Cyclic voltammetry measurements have demonstrated that the electrochemical properties of the polyoxometalate and FB are maintained in the multilayer film, which exhibits electrocatalytic activity for the reduction of bromate Graphical Abstract Fabrication and Characterization of LuminescentMultilayer Films Based on Polyoxometalates and Fuchsin Basic

A reduced ferric molybdophosphate, (H 2 en) 3 (Hen)[Fe III 3 Mo V 12 O 24 (OH) 8 (HPO 4 ) 4 (PO 4 ) 4 ] ·3H 2 O (1) has been hydrothermally synthesized and characterized. In compound 1, a sandwich-shaped cluster [Fe(Mo 6 P 4 ) 2 ] is connected to eight peripheral {FeO 5 (OH)} octahedra through its eight {PO 4 } tetrahedra to form a three-dimensional framework with channels which are filled by water and protonated ethylenediamine molecules. The compound exhibits a 4,8-connected 3-D network with a (4 12 6 12 8 4 )(46)2 topology. The DC susceptibility measurement has shown an antiferromagnetic character of the exchange interactions. Additionally, the electrochemical properties of 1-CPE were studied in detail Graphical Abstract A Three-dimensional Ferric Molybdenum(V) Phosphate Network with Tunnels: Synthesis, Structure, Magnetic and Electrochemical Properties

The synthesis and full characterization of [Be 2 Cl 2 (μ-Cl) 2 (PCy 3 ) 2 ], which results from the reaction of [Pd(PCy 3 ) 2 ] and BeCl 2 with concomitant precipitation of elemental palladium, is reported Graphical Abstract Synthesis and Structural Characterization of the Dinuclear Beryllium Species [Be 2 Cl 2 (μ-Cl) 2 (PCy 3 ) 2 ]

When the product of the reaction of 2,6-di-tert.-butylphenol with TiCl 4 in a 3:1 ratio is treated with Na[HBEt 3 ], the isolated product is not (2,6-tert.-Bu2C6H3O)3Ti(HBEt3) but the isomerized ester (2,4-tert.-Bu 2 C 6 H 3 O) 4 Ti with molecular S 4 symmetry. This rearrangement of the R substituents does not occur upon reacting 2,6-diisopropylphenol with TiCl 4 and Na[HBEt 3 ]. An unexpected result is also observed for the product of the reaction of tris(2,6-diisopropylphenolato)titanium(IV) chloride with lithium bis(pentafluorophenolato)dihydridoborate. The isolated product proved to be dimeric tris(pentafluorophenolato)(2,6-diisopropylphenolato)titanium(IV) with two bridging pentafluorophenolato groups generating pentacoordinated Ti atoms Graphical Abstract Unusual Formation of Two New Titanium(IV) Tetraphenolates

The reaction of dithio-o-carborane with diphenyldiselenide (PhSeSePh) affords the title compound, closo-1,2-(PhSe) 2 C 2 B 10 H 10 (1), which has been characterized by IR and NMR ( 1 H, 11 B) spectroscopy and by single-crystal X-ray diffraction. The phenylselenyl groups are bonded to the cage carbon atoms of the o-carborane cluster with a C cage -C cage distance of 1.751(6) Å and an Se-C cage - C cage -Se torsion angle of 10.1(3) ° . Compound 1 displays a violet emission on excitation with UV light. For comparison the photoluminescence of the known analog closo-1,2-(PhS) 2 C 2 B 10 H 10 (2) was also studied Graphical Abstract Synthesis, Crystal Structure and Photoluminescence of 1,2-Bis(phenylselenyl)-1,2-dicarba-closo-dodecaborane(12)

We have performed density functional calculations with the B3LYP functional and a 6-311G** basis set to obtain the vibrational spectra in harmonic approximation of the anti-leprosy drug Dapsone and the parent compound diphenylsulfone. Although the chemical difference between the two molecules is not that pronounced (Dapsone has amino groups in the para positions in the phenyl rings), Dapsone is an active drug, while to our knowledge diphenylsulfone shows no medical activity. We compared the theoretical results to experimental vibrational spectra found in the literature. With the help of the program GAUSSVIEW we were able to assign the experimentally found spectral lines to specific atomic motions. The remarkable difference between the two molecules, regarding their structural behavior, is that the drug Dapsone has a more flexible structure of the phenyl ring than the parent molecule has. This might contribute to a greater ability of the drug to fit into receptor sites in a cell membrane although one has to be well aware that this plays most propably only a minor role in the drug activity of Dapsone Graphical Abstract A DFT Analysis of the Molecular Structures and Vibrational Spectra of Diphenylsulfone and 4,4'-Sulfonyldianiline (Dapsone)

An efficient method for the synthesis of 1,4-disubstituted triazoles has been developed with the help of ultrasound irradiation in water at room temperature. Under the optimized conditions, a novel series of 1,4-disubstituted 1,2,3-triazoles was synthesized in high yields Graphical Abstract An Efficient Ultrasound-assisted Method for the Synthesis of 1,4-Disubstituted Triazoles

The X-ray crystal structures of the three compounds N,N’-dibenzylterephthalamide, 1, N,N’-dibenzyl- N,N’-dimethylterephthalamide, 2, and N,N,N’ ,N’-tetrabenzylterephthalamide, 3, were determined. Compound 1 fits into the general pattern of disubstituted terephthalamides, with crystallographic inversion symmetry and classical hydrogen bonds linking the molecules into chains parallel to the short axis. Compound 2 also displays inversion symmetry, but the packing only involves two weak hydrogen bonds of the form C-Hmethyl ・ ・ ・ O. The complex packing of compound 3, which possesses no crystallographic symmetry, involves only two C-H・ ・ ・O contacts; these are augmented by three C-H・ ・ ・π interactions Graphical Abstract Crystal Structures of Three Di- and Tetrabenzylterephthalamides

Hexasubstituted guanidinium moieties have been used as ionic liquid tags for organocatalyts for the first time. Such conjugates were obtained in the (S)-proline and (S)-pyrrolidine-2-ylmethyl series by alkylation reactions of pentasubstituted guanidines. The resulting guanidinium-tagged organocatalysts were applied to asymmetric direct aldol reactions providing high stereoselectivities and yields and good recyclability, and thus performed better than (S)-proline itself Graphical Abstract Guanidinium-tagged Organocatalysts for Direct Aldol Reactions

A straightforward synthesis for the anticoagulant rodenticide chlorophacinone is described. The short synthesis uses commercially available mandelic acid and 1,3-indanedione as staring materials Graphical Abstract An Alternative and Efficient Route to Chlorophacinone

Triethylborane reacts with trimethyl(methoxypropargyl)- silane via 1,1-ethylboration to give quantitatively a 90 : 10 mixture of (E)- and (Z)-3-diethylboryl-2-trimethylsilyl-pent- 2-yl-methyl ethers. In contrast, the reaction of triethylborane with chloro(dimethyl)methoxypropargylsilane affords the novel 1,2,5-oxasilaborolane [2,2-dimethyl-5-ethyl-3-(1- ethylpropylidenyl)-1-oxa-2-sila-5-boracyclopentane] by 1,1- ethylboration, rearrangement and ether cleavage Graphical Abstract 1,1-Ethylboration of Trimethyl(methoxypropargyl)- and Chloro(dimethyl)methoxypropargylsilane. A Novel 1,2,5-Oxasilaborolane

The novel coordination polymer, [Pb(1,4-chdc)(L)], 1, (1,4-H 2 chdc = cyclohexane-1,4-dicarboxylic acid and L = 11-fluoro-dipyrido[3,2-a:2' ,3'-c]phenazine), has been synthesized using a hydrothermal method and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data: C 26 H 19 FN 4 O 4 Pb, triclinic, space group P1, a = 9.074(5), b = 9.499(5), c = 13.853(5) Å , α = 85.640(5), β = 76.127(5), γ = 74.730(5)°, V = 1118.2(9)°A3, Z = 2. The 1,4-chdc ligands link the Pb(II) atoms to form a 1D chain structure. The L ligands are attached on both sides of the chains. Further, π-π interactions among neighboring chains lead to a two-dimensional supramolecular layer Graphical Abstract Hydrothermal Synthesis and Crystal Structure of a Novel Pb(II) Coordination Polymer