bluuebunny/crossref_metadata_2025 huggingface dataset:
Der quasibinäre Schnitt La3In5 – La3Pb5: Synthesen, Strukturchemie, Phasenbreiten und chemische Bindung
Authors: Dürr Ines , Röhr Caroline
Published: January 2010

The synthetic, crystallographic, and bond theoretical study of the ternary mixed lanthanum indides/plumbides of the quasibinary section La3In5 – La3Pb5 allows to explore the crystal chemistry of 3:5 polar intermetallic compounds in the electronic region between 24 and 29 valence electrons per formula unit (v.e./f.u.). All compounds of this nearly continuous series exhibiting two different structure types were prepared in pure phase from stoichiometric melts of the elements. The Pu3Pd5 structure type (orthorhombic, space group Cmcm, Z = 4) with slightly distorted nido type square pyramidal (In/Pb)5 clusters is stable from the known binary compound La3In5 (24 v.e./f.u., electron precise clusters In59– after Wade) up to the composition La3In3.8Pb1.2 (25.2 v.e./f.u.) [a = 1049.99(8), b = 838.76(7), c = 1053.74(6) pm, R1 = 0.0528]. The stability range of the second structure type, La3In4Ge (tetragonal, space group I4/mcm, Z = 4), starts at slightly higher lead proportions at the composition La3In3.7Pb1.3 [a = 873.4(2), c = 1214.6(4) pm, R1 = 0.0585]. Several crystals with increasing lead content La3In2.3Pb2.7 [a = 874.32(8), c = 1227.56(8) pm, R1 = 0.0226], La3In1.3Pb3.7 [a = 876.61(6), c = 1226.69(9) pm, R1 = 0.0755], La3InPb4 [a = 878.72(6), c = 1237.44(6) pm, R1 = 0.0339] up to the border composition La3In0.8Pb4.2 [a = 880.05(7), c = 1238.2(1) pm, R1 = 0.0553] have also been characterized by single crystal structure analysis. According to the anionic building blocks of this structure type, isolated [Ge/Pb]4– anions and heavily puckered 4.82 nets of three‐bonded In/Pb atoms (i.e. [In2–(Pb–)3] after Zintl), this border composition exactly fits the Zintl electron count. A final compound of this series, the binary phase La3Pb5 is not known. Simple electron counting rules (Zintl concept, together with Wade’s rules) hold only for the border compounds of the two structure types, La3In5 and La3InPb4. Their validity and the details of the chemical bonding are thus evaluated in an accompanying computational study, where the electronic band structures of the binary compounds La3In5 and La3Sn5 (Pu3Pd5 structure type) and the model system “La3Pb5” (calculated using the crystal data of La3InPb4) are calculated using FP‐LAPW band structure methods.
Description of Anhydrous (Black) Dioptase as a S = 1/2 Uniform Antiferromagnetic Chain System
Authors: Law Joseph M. , Hoch Constantin , Whangbo Myung‐Hwan , Kremer Reinhard K.
Published: January 2010

The structural and magnetic properties of anhydrous (black) dioptase, CuSiO3, were investigated by carrying out single‐crystal X‐ray diffraction, specific heat, and magnetic susceptibility measurements as well as by performing spin dimer analysis based on extended Hückel tight‐binding calculations. Our spin dimer analysis indicates that black dioptase is a S = 1/2 uniform antiferromagnetic chain system with the interchain spin exchange weaker than the intrachain exchange by three orders of magnitude. Specific heat and magnetic susceptibility measurements show that the intrachain exchange is –174(2) K, and the interchain exchange is of the order of ~2 K. They lead to long‐range magnetic ordering at about 5 K as evidenced by a broad anomaly in the specific heat.
Static and Ultrasonic‐assisted Aging Effects on the Synthesis of Analcime Zeolite
Authors: Azizi Seyed Naser , Yousefpour Maryam
Published: January 2010

The synthesis of zeolite ANA under static hydrothermal conditions was performed accompanied by an additional static and ultrasonic‐assisted aging of the reaction mixture prior to crystallization. The aging process was compared with stirring‐assisted aging, microwave‐assisted aging and syntheses without any aging. The influence of aging time on the crystallization time of zeolite ANA was investigated. The static and ultrasonic‐assisted aging can shorten the crystallization time of the ANA phase. Moreover, ultrasonic‐assisted aging leads to altered morphologies of the particles. The products were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM).
The [U2I10]2– Anion: Synthesis and Structure of [Ta7(Se2)14][U2I10]2
Authors: Wells Daniel M. , Ibers James A.
Published: January 2010

The new anion [U2I10]2– has been isolated in the compound [Ta7(Se2)14][U2I10]2. This compound was synthesized from the elements at 1173 K. It crystallizes in space group Cccm of the orthorhombic system with four formula units in a cell of dimensions a = 21.5134(9) Å, b = 22.1619(9) Å, and c = 16.7834(6) Å. The crystal structure comprises infinite [Ta(Se2)2]n cationic chains charge balanced by [U2I10]2– anions. The new [U2I10]2– anion is formed by two edge‐sharing UI6 octahedra. The U–I bond lengths are normal for tetravalent uranium. For charge balance, the [Ta7(Se2)14]4+ cation must contain three TaIV and four TaV atoms. Charge is delocalized over this cation as the Ta···Ta interactions differ minimally.
Zigzag Chains of Alternating Atoms in A2AuBi (A = Na, K) and K2AuSb. Synthesis, Structure, and Bonding
Authors: Kim Sung‐Jin , Miller Gordon J. , Corbett John D.
Published: January 2010

The polar intermetallic phases A2AuBi (A = Na (I), K (II)), and K2AuSb (III) were obtained by direct reaction of the elements at elevated temperatures in niobium ampoules. The three isotypic compounds extend the prominent A2MPn (M = transition metal; Pn = group 15) structure family. Single‐crystal X‐ray diffraction experiments show that these phases (I / II / III) crystallize in the orthorhombic space group Cmcm (No. 63), with a = 9.447(2) / 10.632(2) / 10.450(2) Å; b = 7.700(2) / 7.918(2) / 7.857(2) Å; c = 5.849(1) / 6.597(1) / 6.501(1) Å; V = 425.4(2) / 555.4(2) / 533.8(2) Å3, respectively, and Z = 4. The simple structures, which contain zigzag chains of linear two‐bonded gold atoms and acute angles (64 to 76°) at two‐bonded antimony or bismuth, can readily be rationalized with the Zintl‐Klemm concept. TB‐LMTO calculations show distinct band gaps at EF, and analyses of DOS and COHP curves show optimized Au–Pn bonding, appreciable Au–Au interactions across the chains, and covalent interactions between A and Pn atoms. The observed structural preference over an isoelectronic NaTl type structure, the cation influences, and site coloring were investigated with VASP and EHTB calculations.
Syntheses and Crystal Structures of CsCuNd2Se4 and CsCuGd2Te4: Two Non‐Isotypical Cesium Copper Lanthanide Chalcogenides with {}^1_\infty{[CuCh3]5–} Chains of Vertex‐Shared [CuCh4]7– Tetrahedra
Authors: Babo Jean‐Marie , Strobel Sabine , Schleid Thomas
Published: January 2010

The new chalcogenides CsCuNd2Se4 and CsCuGd2Te4 with analogous formulae were prepared from the elements by a flux method with CsCl as fluxing agent and cesium source. CsCuNd2Se4 crystallizes in the orthorhombic space group Cmcm (no. 63) with four formula units per unit cell (a = 424.69(3), b = 1475.81(8), c = 1465.42(8) pm), whereas CsCuGd2Te4 is monoclinic with the space group C2/m (no. 12) and twelve formula units per unit cell (a = 3764.75(19), b = 436.70(2), c = 2105.37(11) pm, β = 107.423(4)°). Both crystal structures feature three‐dimensional arrangements of the lanthanide and coinage metal cations along with the chalcogenide anions according to {}^3_\infty{[CuLn2Ch4]–} (Ln = Nd or Gd, Ch = Se or Te), leaving channels behind, in which the Cs+ cations are incorporated. Hereby, vertex‐linked [CuCh4]7– tetrahedra join to form {}^1_\infty{[CuCh3]5–} chains in both cases. Whereas for the CsCuNd2Se4 structure, these chains ({}^1_\infty{[CuSe3]5–}) are embedded into a three‐dimensional network, erected by edge‐ and vertex‐linked [NdSe6]9– octahedra, which form corrugated layers further connected by common edges, in CsCuGd2Te4 a different three‐dimensional {}^3_\infty{[Gd2Te4]2–} framework arises, comprising {}^1_\infty{[CuTe3]5–} chains, as well as vertex‐ and edge‐linked [GdTe6]9– octahedra. The major difference of the structures originates from the channels, in which the Cs+ cations are located. In the tunnels of CsCuNd2Se4, the Cs+ cations exhibit a bicapped trigonal prismatic selenide coordination, whereas in CsCuGd2Te4 with two Cs+ cations in one channel, they show bicapped trigonal prisms, as well as monocapped cubes of telluride anions as coordination spheres.
Analysis of Electronic Structures and Chemical Bonding of Metal‐rich Compounds. 2. Presence of Dimer (T–T)4– and Isolated T2– Anions in the Polar Intermetallic Cr5B3‐Type Compounds AE5T3 (AE = Ca, Sr; T = Au, Ag, Hg, Cd, Zn)
Authors: Lee Changhoon , Whangbo Myung‐Hwan , Köhler Jürgen
Published: January 2010

First principles density functional calculations were carried out to probe the oxidation states of the transition‐metal and alkaline‐earth elements in the Cr5B3‐type compounds AE5T3 consisting of T2 dimers and isolated T atoms (i.e., Ca5Au3, Ca5Ag3, Ca5Hg3, Sr5Cd3, and Ca5Zn3). The electronic structures of all these AE5T3 compounds are best described as [(AE2+)5(T–T)4–(T2–)]+4e–. In the covalent bonding of the AE2+ ions with the transition metal anions T2–, the (n–1)d orbitals of AE2+ contribute more than the ns and np orbitals of AE2+.
NaSc[BP2O6(OH)3][(HO)PO3]: Synthesis and Crystal Structure of an Alkali‐Metal Scandium Borophosphate Hydrogenphosphate
Authors: Menezes Prashanth W. , Hoffmann Stefan , Prots Yurii , Kniep Rüdiger
Published: January 2010

The compound NaSc[BP2O6(OH)3][(HO)PO3] was prepared under mild hydrothermal conditions. The crystal structure was determined from single crystal X‐ray data: monoclinic, space group P21/c (No. 14), a = 5.0010(1) Å, b = 12.4271(9) Å, c = 15.8340(14) Å, β = 94.201(4), V = 981.41(11) Å3 and Z = 2. The crystal structure comprises of isolated borophosphate oligomers, [BP2O6(OH)3]2–, and isolated hydrogenphosphate groups, [(HO)PO3]2–, which are interconnected by ScO6 coordination octahedra by sharing common corners. The resulting three‐dimensional framework is characterized by channels running along [100] forming four‐, six‐, and twelve‐membered rings. Sodium ions reside within the six‐membered ring channels.
Tri‐ and Tetracoordinate Copper(I) Complexes of 1,1′‐Diisocyanoferrocene
Authors: Siemeling Ulrich , Klapp Lutz R. R. , Bruhn Clemens
Published: January 2010

Two homoleptic copper(I) complexes of the bidentate isocyanide 1,1′‐diisocyanoferrocene (1) were prepared and structurally characterised. The dications present in [Cu2(μ‐1)3][PF6]2 exhibit a paddle‐wheel‐like structure with trigonal‐planar CuI. These dications are connected in a chain‐like fashion by bridging ligands 1 in the coordination polymer [{Cu2(μ‐1)3}(μ‐1)]n(OTf)2n, which contains tetracoordinate CuI in a distorted tetrahedral coordination environment. The hexafluorophosphate analogue of the latter compound was also prepared.
$^3_\infty$[Tl2Zn(ADC)2(H2O)2]: the First Coordination Polymer with Acetylenedicarboxylate (ADC2–) as Bridging Ligand containing two Different Metal Ions
Authors: Ahlers Ruth , Ruschewitz Uwe
Published: January 2010

From an aqueous solution containing ZnCO3, Tl(CH3COO), and acetylenedicarboxylic acid (H2ADC: HOOC‐C≡C‐COOH) single crystals of $^3_\infty$[Tl2Zn(ADC)2(H2O)2] (1) were obtained. Compound 1 crystallizes in triclinic space group P$\bar{1}$ with Z = 1. A slightly distorted octahedral ZnO6 coordination and a very unsymmetric TlO6 coordination (Tl–O < 321 pm) are found, the latter probably caused by a stereochemically active lone pair at Tl+. These polyhedra are connected by the ADC2– linker to form a 3D network structure. Additionally, hydrogen bonds are formed, which involve the water molecules (O···O starting at 274 pm). These are only coordinated to Zn2+. Compound 1 is the first coordination polymer of ADC2–, which contains two different metal ions.
Synthesis and Structural Studies on Tetranuclear Tin Compositions Containing Tin {[R2Sn(LH)]2O}2 Moieties (R = Bu or Oct and LH = 4‐[((E)‐1‐{2‐Hydroxy‐5‐[(E)‐2‐(aryl)‐1‐diazenyl]phenyl}methylidene)‐ amino]benzoate)
Authors: Basu Baul Tushar S. , Das Pradip , Song Xueqing , Eng George , Quah Ching Kheng , Fun Hoong‐Kun
Published: January 2010

Diorganotin compounds containing tetranuclear tin compositions of the type {[R2Sn(LH)]2O}2 in which LH is deprotonated carboxylic acid LHH′ (H′ are the carboxylic and H the phenolic protons of the benzoic acid) HO2C–C6H4‐4‐{N=C(H)C6H3‐2‐OH‐5‐(N=N–C6H4X)} (X = H for L1H, X = 2‐CH3 for L2H, X = 3‐CH3 for L3H, and X = 4‐CH3 for L4H; R = Bu or Oct), were synthesized and characterized by FT‐IR, NMR, and 119Sn Mössbauer spectroscopy. One of the complexes, {[Oct2Sn(O2CC6H4{N=C(H)C6H3‐2‐OH‐5‐(N=NC6H4CH3‐2)})]2O}2 was characterized by single‐crystal X‐ray diffaraction, which revealed that the compound is a centrosymmetric tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complex with a planar Sn4O2 core. The two μ3‐oxo oyxgen atoms are connected to a Sn2O2 ring and to two exocyclic tin atoms. The four carboxylate ligands display two different modes of coordination. Both modes of coordination involve bridging two structurally distinct tin atoms. The solution structures of the complexes were unravelled by 119Sn NMR spectroscopy, and found to be identical to those of the crystalline state.
Carbon Dioxide Fixation with Dialkyltellurium(IV) Dihydroxides
Authors: Beckmann Jens , Bolsinger Jens , Duthie Andrew
Published: January 2010

Aqueous solutions of Me2Te(OH)2 and (CH2)4Te(OH)2 readily absorb carbon dioxide giving rise to the formation of the dialkyltelluroxane carbonates (Me2TeOTeMe2CO3)n (1) and HO(CH2)4TeOTe(CH2)4CO3Te(CH2)4OH·2H2O (2·2H2O), which were characterised by 13C MAS and 125Te MAS NMR spectroscopy as well as X‐ray crystallography. The spatial arrangement of the tellurium atoms is defined by C2O2 donor sets in the primary coordination sphere and one or two secondary Te···O contacts, which involve coordination of the carbonate moieties. In turn, the different Te–O coordination modes render a lack of symmetry to the carbonate moieties, which show significantly different C–O bond lengths, an important feature when contemplating the C–O bond activation in carbonates. The structural and spectroscopic parameters of 1 and 2 are discussed in comparison with other heavy p‐block element carbonates. In solution, electrolytic dissociation of 1 and 2 takes place.
Syntheses, Structures, and Photoluminescent and Magnetic Properties of Four Novel Complexes Constructed from 2,4,5‐Tri(4‐pyridyl)‐imidazole and Benzene‐1,3,5‐tricarboxylic Acid
Authors: Wang Li , Gu Wen , Deng Jun‐Xiu , Liu Mei‐Ling , Xu Na , Liu Xin
Published: January 2010

Four novel 2D complexes M2(Hptim)2(HBTC)2 [M = Co (1), Cd (2), Zn (3), Mn (4); Hptim = 2,4,5‐tri(4‐pyridyl)‐imidazole; HBTC2– = Benzene‐1,3,5‐tricarboxylic acid] were synthesized under solvothermal conditions. The four complexes are isomorphous and present a unique structure with a 1D ladder of [Co2(HBTC)2]n. The 2D network structure of 1 is achieved through bridging Hptim groups, which coordinate to the metal atoms of two adjacent 1D [Co2(HBTC)2]n ladders. Magnetic measurements reveal that dominant antiferromagnetic coupling was observed in compounds 1 and 4. Compounds 2 and 3 both exhibit strong fluorescent emissions in the solid state and may be suitable candidates for fluorescent materials.
The New Binary Tungsten Iodide W15I47
Authors: Ströbele Markus , Meyer H.‐Jürgen
Published: January 2010

The new tungsten iodide W15I47 was synthesized by reacting tungsten hexacarbonyl with iodine under elevated pressure and temperature conditions. The structure of W15I47 was refined by single‐crystal X‐ray diffraction with the non‐centrosymmetric space group C2 [Z = 2, a = 4088.3(4) pm, b = 952.3(1) pm, c = 1198.5(2) pm, and β = 103.97(1)°]. The characteristic motif in the structure is the square pyramidal tungsten cluster that may be constructed from an octahedral [(W6I8i)I6a]2– cluster by removing one tungsten atom together with its outer iodide ligand to yield [(W5I8i)I5a]n–. The formula W15I47 represents three square pyramidal tungsten clusters with two of them being distinguishable in [(W5I8i)Ia(I3)2a(I3)2/2a–a][(W5I8i)I2a(I3)3/2a–a]2, by different numbers of iodide and tri‐iodide ligands at the cluster vertices.
Two Coordination Polymers Constructed from Pillared M–O (M = Na+ or Ba2+) Subunits with 3‐Formyl‐4‐hydroxybenzenesulfonic Acid as Ligand
Authors: Li Shu‐Ni , Zhai Quan‐Guo , Hu Man‐Cheng , Jiang Yu‐Cheng
Published: January 2010

Two new coordination polymers, [Na(H2L)(H2O)2]n (1) and [Ba(H2L)2(H2O)]n (2) (H3L = 3‐formyl‐4‐hydroxybenzenesulfonic acid) were synthesized and structurally characterized. The H2L– ligand shows three different bridging modes, μ3 in 1, μ3 and μ4 in 2. Compound 1 presents a 2D pillared structure, whereas 2 forms a 3D framework. Both 1 and 2 show blue luminescence at 380 nm in aqueous solution, however, their solid state emissions are at 406 and 446 nm, respectively.
Assembly of a Novel Dumbbell‐type Dinuclear Copper(II) Complex: Synthesis, Structure and Properties
Authors: Sun Wen Wu , Li Shi Rong , Zhou Hong , Pan Zhi Quan , Huang Qi Mao , Hu Xue Lei
Published: January 2010

A new dumbbell‐type 4,4′‐bipy‐bridged dinuclear copper(II) complex, [Cu2(4,4′‐bipy)L2(H2O)2](ClO4)4·8CH3OH·10H2O, where L = 1‐[bis(3‐aminopropyl)amino]‐2‐ propanol and bipy = bipyridine, has been synthesized and characterized, X‐ray crystallographic analysis shows that the [Cu2(4,4′‐bipy)L2(H2O)2]4+ cations and water molecules generate layer structures extending parallel to bc planes through hydrogen bonding interactions of O–H···O and C–H···O. The layers are also connected by hydrogen bonding interactions involving methanol, water, and perchlorate anions. These interactions lead to the formation of rectangular channels of 12.3 Å × 6.0 Å along the crystallographic c axis. Perchlorate anions fill in each channel in a sandwich‐like packing mode, they are joined with the adjacent layers by water heptamers. Magnetic susceptibility measurements show that the magnetic exchange interaction is weak although it has a regular π‐type electron transfer pathway. Furthermore, the electrochemical and thermogravimetric properties of the complex were also investigated.
Structure and Magnetic Properties of Two Lanthanide 1,4‐Phenylenediacetate Compounds
Authors: Chen Zilu , Xiong Wei , Zhang Zhong , Liang Fupei
Published: January 2010

The reactions of Ln(NO3)3 with 1,4‐phenylenediacetic acid (H2PDA) under hydrothermal conditions produced two isostructural lanthanide coordination polymers with the empirical formula [Ln2(PDA)3(H2O)]·2H2O [Ln = Nd (1), Sm (2)]. Single‐crystal X‐ray diffraction analyses revealed that both contain one‐dimensionalmetal carboxylato chains, which are further connected by the–CH2C6H4CH2– spacers of PDA2– ligands to yield a three‐dimensional metal‐organic framework. Magnetic susceptibilities of 1 and 2 were measured. The experimental χmT value of both compounds decreases continuously with decreasing temperature over the whole temperature range. The best least‐squares fit of the experimental data of 1 to a theoretical equation in the temperature range of 70–300 K gives the zero‐field splitting parameter Δ = 2.21 cm–1 and the magnetic interaction between the NdIII ions 2zJ′ = –1.97 cm–1, which indicates the presence of antiferromagnetic interaction between the NdIII ions. The experimental χmT value of 2 at 2 K is much smaller than the expected value for two free SmIII ions (6H5/2, g = 2/7) in the ground state, indicating that an antiferromagnetic interaction possibly exists between SmIII ions at low temperature. Fitting the magnetic data of 2 above 110 K based on an equation deduced from the SmIII ion in a monomeric system with free‐ion approximation gave a spin‐orbit coupling parameter λ = 192(2) cm–1
GeSb4Te4 – a New 9P‐Type Phase in the System Ge/Sb/Te
Authors: Schneider Matthias N. , Oeckler Oliver
Published: January 2010

9P‐GeSb4Te4 is a new germanium antimony telluride that can be obtained from the elements as a homogeneous phase by quenching a stoichiometric melt and subsequently annealing the sample at 500 °C. The crystal structure consists of alternating antimony layers similar to those in elemental antimony and rocksalt‐type blocks similar to those in GeSb2Te4. Although not thermodynamically stable according to the phase diagram, GeSb4Te4 is remarkably stable up to 540 °C, where it starts to melt incongruently according to DSC and DTA measurements. The crystal structure has been refined from single‐crystalX‐ray data [P$\bar{3}$m1, a = 4.2466(2) Å, c = 17.483 Å, R1 = 0.0355]. Its diffraction patterns are very similar to those of other 9P‐type tellurides like Ge2Sb2Te5 and Sb2Te, which tend to occur as very pronounced false minima in structure refinements. The electrical conductivity is low (33 S·cm–1) but exhibits metallic temperature dependence.
The Structural Anomaly of Zinc: Evolution of Lattice Constants and Parameters of Thermal Motion in the Temperature Range of 40 to 500 K
Authors: Nuss Jürgen , Wedig Ulrich , Kirfel Armin , Jansen Martin
Published: January 2010

The crystal structure of elemental zinc deviates from the ideal hexagonal close packing by a significantly increased c/a ratio. We determined the evolution of the lattice constants and thermal displacement parameters in the temperature range of 40 to 500 K by accurate single‐crystal X‐ray diffraction. The c axis varies linearly within the whole temperature range, whereas the a lattice constant stays constant below ≈︁ 160 K, which indicates that at lower temperatures the Zn–Zn distances are no longer thermally contractible in the ab plane. As a further significant observation, the thermal expansion coefficient along the c direction exceeds the one in a direction by a factor of ~10, and consequently the c/a ratio slightly reduces, but stays unusually high (c/a = 1.826, extrapolated for T = 0 K). The thermal motion of zinc shows a striking anisotropy as expressed by a ratio U33/U11 of ≈︁ 2.6 at 500 K. This ratio decreases significantly towards lower temperatures and reaches almost 1.6 at 40 K. The thermal behavior as observed is thus reflecting the structural and bonding anisotropy of zinc at ambient conditions, but thermal motion turns isotropic at cooling, in contrast to the atomic equilibrium structure.
Synthesis and Crystal Structure of Tetrakis(tetramethylammonium) Bis[decabromotetraselenate(II)]‐bis[dibromodiselenate(I)], [(CH3)4N]4[(Se4Br10)2(Se2Br2)2], the Salt of a Mixed‐Valence Bromoselenate(II/I) Anion
Authors: Janickis Vitalijus , Necas Marek
Published: January 2010

Brown crystals of [NMe4]4[(Se4Br10)2(Se2Br2)2] (1) were obtained from the reaction of selenium and bromine in acetonitrile in the presence of tetramethylammonium bromide. The crystal structure of 1 was determined by X‐ray diffraction and refined to R = 0.0297 for 8401 reflections. The crystals are monoclinic, space group P21/c with Z = 4 and a = 12.646(3) Å, b = 16.499(3) Å, c = 16.844(3) Å, β = 101.70(3)° (123 K). In the solid‐state structure, the anion of 1 is built up of two [Se4Br10]2– ions. Each shows a triangular arrangement of three planar SeBr4 units sharing a common edge through two μ3‐bridging bromine atoms, and one SeBr2 molecule, which is linked to the SeII atoms of two SeBr4 units; between the Se4Br102– ions a dimerized Se2Br2 molecule (Se4Br4) is situated and one SeI atom of each Se2Br2 molecule has two weak contacts [3.3514(14) Å and 3.3952(11) Å] to two bromine atoms of one SeBr4 unit. Four SeI atoms of a dimerized Se2Br2 molecule are in a almost regular planar tetraangular arrangement. Contacts between the SeII atom of the SeBr2 molecule and the SeII atoms of two SeBr4 units are 3.035(1) Å and 3.115(1) Å, and can be interpreted as donor‐acceptor type bonds with the SeII atoms of SeBr4 units as donors and the SeBr2 molecule as acceptor. The terminal SeII–Br and μ3‐Br–SeII bond lengths are in the ranges 2.3376(10) to 2.4384(8) Å and 2.8036(9) to 3.3183(13) Å, respectively. The bond lengths in the dimerized Se2Br2 molecule are: SeI–SeI = 2.2945(8) Å and 3.1398(12), SeI–Br = 2.3659(11) and 2.3689(10) Å.
Reactions of Metal Carbonyls with the Azide Ion and – vice versa – Reactions of Azido Complexes with Carbon Monoxide: Isocyanato Complexes. Analogous Reactions in NO+/N3– Transition Metal Chemistry [1]
Authors: Beck Wolfgang , Fehlhammer Wolf Peter
Published: January 2010

, Contents, 1. Introduction, 2. Reactions of Carbonyl Metal Complexes with the Azide Ion, 3. Reactions of Azido Metal Complexes with Carbon Monoxide, 4. Reactions of the Azide Ion with the NO+ Cation, 5. Reaction of Nitrosyl Complexes with the Azide Ion, 6. Nitrosation of the Coordinated Azide Ligand
Tetrapyridin‐Beryllium‐Polyiodid. Synthese und Kristallstruktur von [Be(Py)4]2(I3)2(I4)
Authors: Neumüller Bernhard , Dehnicke Kurt
Published: January 2010

Tetrapyridine‐beryllium polyiodide [Be(py)4]2(I3)2(I4) (1) was prepared from beryllium powder and iodine in pyridine suspension to give brown crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. 1 crystallizes monoclinically in the space group C2/c with four formula units per unit cell. Lattice dimensions at 100(2)K: a = 2044.1(1), b = 1524.5(1), c = 1843.8(1)pm, β= 103.65(1)°, R1 = 0.0301. The structure of 1 consists of distorted tetrahedral dications, triiodide ions without site symmetry, and centrosymmetric linear tetraiodide ions.
Synthesis and Characterization of N‐heterocyclic Carbene Complexes of Titanium(IV) and Titanium(III)
Authors: Li Jianfeng , Schulzke Carola , Merkel Sebastian , Roesky Herbert W. , Samuel Prinson P. , Döring Alexander , Stalke Dietmar
Published: January 2010

The synthesis and characterization of two N‐heterocyclic carbene (NHC) complexes of titanium (IPr)Ti(NMe2)2Cl2 (1) [IPr = 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene] and (IPr)2TiCl3 (2) are described. Reactions of one and two equivalents of IPr with Ti(NMe2)2Cl2 and TiCl3(thf)3 yield the mono‐NHC titanium(IV) complex 1 and the bis‐NHC titanium(III) complex 2, respectively. They feature distorted trigonal bipyramidal geometries. Short intramolecular Cl···CNHC contacts are observed in the X‐ray single‐crystal structures of 1 and 2.
A Temperature‐dependent Structural Study of anti‐ReO3‐type Na3N: to Distort or not to Distort?
Authors: Vajenine Grigori V. , Hoch Constantin , Dinnebier Robert E. , Senyshyn Anatoliy , Niewa Rainer
Published: January 2010

The rather open anti‐ReO3‐type crystal structure for sodium nitride is completely preserved in the temperature range between 20 K and its decomposition temperature at around 393 K according to temperature‐dependent X‐ray and neutron diffraction data collected on single crystals and microcrystalline powder of Na3N. Strong anisotropy of thermal displacement parameters even at low temperatures is attributed to purely dynamic effects. The tendency of ReO3‐type and anti‐ReO3‐type compounds towards an octahedron‐tilting distortion is compared theoretically by using cubic AlF3 and Li3N model compounds.
Investigation of the Coordination Behavior of P4S3 towards CuBr
Authors: Biegerl Andreas , Gröger Christian , Kalbitzer Hans Robert , Wachter Joachim , Zabel Manfred
Published: January 2010

The formation of coordination polymers from copper(I) bromide and P4S3, a potentially tetradentate P‐donor bridging ligand, was studied. Whereas (P4S3)3(CuBr)7 (1) formed in excellent yield, (P4S3)(CuBr)3 (2) and (P4S3)(CuBr) (3) crystallized as mixtures. The new compounds were characterized by X‐ray crystallography and solid‐state 31P MAS NMR spectroscopy. The structure of 1 consists of a 3D network of cylindrical (CuBr)n columns, castellated (CuBr)n chains and diatomic CuBr units. These building blocks are linked by tetradentate P4S3 molecules. The structure of 2 comprises undulated (CuBr)n layers, which are intra‐ and interlayer linked by tridentate P4S3 molecules. Compound 3 is a one‐dimensional polymer composed of four‐membered Cu2Br2 rings, which are bridged by the P3 bases of two P4S3 molecules.
Polymorphism of Eu8In3 and the Solid Solution (CaxEu1–x)8In3
Authors: Gäbler Frank , Niewa Rainer
Published: January 2010

In the binary intermetallic system Eu/In, a new compound with the composition Eu8In3 was observed and the crystal structures of two polymorphs determined by single‐crystal X‐ray diffraction. The low‐temperature β‐modification crystallizes in the trigonal crystal system with the Yb8In3 structure type (R$\bar3$c (No. 167), a = 957.7(1) pm, c = 5674(1) pm, Z = 12, R(F) = 0.020, wR(F2) = 0.038), the high‐temperature α‐phase triclinic (P$\bar1$ (No. 2), a = 992.67(6) pm, b = 998.08(4) pm, c = 1007.89(5) pm, α = 99.140(4)°, β = 101.172(5)°, γ = 119.452(6)°, Z = 2, R(F) = 0.035, wR(F2) = 0.080) in the Ca8In3 structure type. The densities (ρtriclinic = 6.36 g·cm–1; ρtrigonal = 6.90 g·cm–1) as well as the synthesis conditions are compatible with the assignment as high‐ and low‐temperature phase. The two polymorphs can be rationalized as polytypes of close packings of In with occupation of all octahedral holes and 5/6 of the tetrahedral voids. In this description, indium atoms realize the motif of a double‐hexagonal stacking for the low‐temperature β‐modification and a cubic stacking for the high‐temperature α‐phase. Alternatively, both structures can be described by the occurring coordination polyhedra (tetrahedra for europium, cubes, icosahedra and cubicosahedra surrounding indium). α‐Eu8In3 is versatile to europium substitution by calcium, with little preference for either europium or calcium on the sites exhibiting the highest degree of distortion from tetrahedral shape (Ca4Eu4In3: P$\bar1$, a = 975.2(2) pm, b = 987.1(2) pm, c = 992.8(2) pm, α = 99.12(3)°, β = 101.06(3)°, γ = 119.59(3)°, Z = 2, R(F) = 0.023, wR(F2) = 0.044).
Synthesis, Structural Characterization and Luminescence Studies of Di‐ and Trinuclear Gold(I) Alkynyl‐phosphine Complexes
Authors: Koshevoy Igor O. , Koskinen Laura , Smirnova Ekaterina S. , Haukka Matti , Pakkanen Tapani A. , Melnikov Alexei S. , Tunik Sergey P.
Published: January 2010

Reactions of the polymer {AuIC2Ph}n with polyphosphine ligands [1,4‐bis(2‐diphenylphosphino‐1H‐imidazol‐1‐yl)‐benzene (dpib), 1,3,5‐tris(4‐diphenylphosphinophenyl)benzene (tppb), 2,2′‐bis(diphenylphosphanyl)‐4,4′‐bipyridine (dpbp), and 3,6‐bis(diphenylphosphanyl)pyridazine (dppz)] afforded four gold(I) alkynyl‐polyphosphine complexes [{AuC2Ph}2(μ‐dpib)] (1), [{AuC2Ph}3(μ3‐tppb)] (2), [{AuC2Ph}2(μ‐dpbp)] (3), and [{AuC2Ph}2(μ‐dppz)] (4) in nearly quantitative yield. The compounds obtained were characterized using elemental analysis, ESI‐MS, X‐ray crystallography, and polynuclear NMR spectroscopy. Intermolecular aurophilic interaction together with π–π and σ–π stacking build up the supramolecular 3D network of complex 3, whereas none of these intermolecular bondings were found in the crystal structures of compounds 1, 2, and 4. Complexes 1–4 are luminescent both in solution (CH2Cl2) and in solid state under laser irradiation (λex = 308 nm). In solution, the diphosphine complexes 1–4 display dual emission corresponding to ligand centered transitions (λem = 360–375 nm) along with weaker contribution from MLCT excited states at ca. 490 nm. The long wavelength component of the emission plays a dominant role in the solid state luminescence spectra of complexes 1, 3, and 4 (460, 544, 520 nm, respectively) whereas the triphosphine complex 2 shows dual luminescence (372 and 520 nm) with considerable contribution from ligand centered excited state.
Genetik der Nikotinabhängigkeit
Authors: Hartz S. , Bierut L.
Published: January 2010

Die körperliche Abhängigkeit von Nikotin ist eine genetisch bedingte Suchtkrankheit, die es den Betroffenen erschwert, mit dem Rauchen aufzuhören. Sie ist dadurch für die meisten mit dem Rauchen verbundenen Erkrankungen (mit)verantwortlich ist. In mehreren unabhängigen Studien wurde eine allelische Assoziation zwischen Nikotinabhängigkeit und DNA-Varianten einer Region auf Chromosom 15, die das Gencluster für die α5-, α3- und β4-Untereinheiten des Nikotinrezeptors beinhaltet, gefunden. Bemerkenswerterweise wurde auch eine Assoziation von Markern der gleichen Region mit Lungenkrebs und der Gruppe der chronisch-obstruktiven Atemwegserkrankungen detektiert. Dies unterstreicht, wie wichtig das Wissen um die genetischen Ursachen der Nikotinabhängigkeit für das Verständnis von Erkrankungen ist, die durch Rauchen verursacht werden.
L’anonymat dans l’insémination avec don de sperme: un regard éthique
Authors: Marzano M.
Published: January 2010

Quel rapport existe-t-il entre secret et anonymat dans le cadre d’une insémination avec don ? Est-il nécessaire pour un enfant né par don de sperme de connaître le nom de son donneur pour avoir accès à son histoire personnelle ? Qu’entend-on par « origines » ? Cet article vise à analyser ces questions d’un point de vue philosophique, en essayant de montrer l’existence d’une différence fondamentale entre le secret, qui concerne le mode de conception, et l’anonymat, qui concerne en revanche le nom du donneur de sperme.
A longitudinal examination of adolescent career planning and exploration using a social cognitive career theory framework
Authors: Rogers Mary E. , Creed Peter A.
Published: January 2010

This study used social cognitive career theory (Lent, Brown, & Hackett, 1994), as a framework to investigate predictors of career choice actions, operationalised as career planning and career exploration. The model was tested cross‐sectionally and longitudinally with 631 high school students enrolled in Grades 10–12. Students completed measures of self‐efficacy, outcome expectations, goals, supports and personality. Results of the hierarchical regression analyses indicated strong support for self‐efficacy and goals predicting career planning and exploration across all grades at T1, and predicting change in career planning and exploration from T1 to T2. Whilst support for pathways among other predictor variables (personality, contextual influences and biographic variables) to choice actions was found, these pathways varied across grades at T1, and also from T1 to T2. Implications for social cognitive career theory, career counselling practice and future research are discussed.
Long‐term facilitation of nociceptive withdrawal reflexes following low‐frequency conditioning electrical stimulation: A new model for central sensitization in humans
Authors: Manresa José A. Biurrun , Mørch Carsten D. , Andersen Ole K.
Published: January 2010

Central sensitization is believed to be one of the key mechanisms behind chronic pain conditions, and several models have been developed in order to characterize this phenomenon in humans. One of these models relies on conditioning electrical stimulation to elicit long‐lasting effects on the nociceptive system. The aim of this study was to evaluate these effects using an objective electrophysiological measurement, the nociceptive withdrawal reflex (NWR). Long‐term changes in spinal nociception after high‐ and low‐frequency conditioning electrical stimulation were assessed in 13 healthy volunteers. Perceptual intensity ratings to mechanical stimuli and blood flow variations were assessed in the conditioned area (dorsum of the foot) and surroundings. To evaluate the excitability of the nociceptive system, the NWR was elicited within the same innervation area (superficial peroneal nerve) at graded stimulation intensities and recorded in the hamstrings. Following low‐frequency stimulation, an intensity‐independent long‐lasting facilitation of the NWR was observed, with a significant increase in the reflex size (average of 31 ± 4%,p< 0.001) and in the number of reflexes (average increase of 22 ± 10%,p< 0.01), accompanied by a significant increase in the blood flow (average increase of 40 ± 10%,p< 0.001). These findings suggest that activity‐dependent central sensitization can be elicited using conditioning electrical stimulation with a stimulation frequency that lies within the physiological firing range of primary afferents, and that it can be objectively assessed in humans using the NWR.
Understanding the effect of a numerical anchor
Authors: Russo J. Edward
Published: January 2010

Wegener et al. extended the investigation of the anchoring phenomenon to include the manipulation of cognitive load and several traditional factors in persuasion such as source credibility. To this breadth strategy might be added approaches that focus more on depth. By depth is meant an understanding of the underlying mechanisms of anchoring and the forces driving those mechanisms.
Use does not wear ragged the fabric of friendship: Thinking of objects as alive makes people less willing to replace them
Authors: Chandler Jesse , Schwarz Norbert
Published: January 2010

Anthropomorphic beliefs about objects lead people to treat them as if they were alive. Two experiments test how anthropomorphic thought affects consumers' product replacement intentions. Consumers induced to think about their car in anthropomorphic terms (i) were less willing to replace it and (ii) gave less weight to its quality when making replacement decisions. Instead, they (iii) attended to (experimentally induced connotations of) the car's “warmth,” a feature usually considered relevant in the interpersonal domain. While anthropomorphic beliefs about brands are often seen as advantageous by marketers because they increase brand loyalty, similar beliefs about products may be less desirable.
A petition to a woman at the Fatimid court (413–414a.h./1022–23c.e.)
Authors: Rustow Marina
Published: January 2010

The Genizah of the Ben Ezra synagogue in Fustat preserved dozens of petitions addressed to the Fatimid and Ayyubid chanceries in Cairo and decrees that they issued in response. This article provides an edition, translation, and discussion of a petition housed among the Genizah documents of the Bodleian Library directed to Sitt al-Mulk, half-sister of the caliph al-Ḥākim (386–411/996–1021) and head of the Fatimid state between his death and her own in 414/1023. Geoffrey Khan had previously identified two petitions to a Fatimid princess housed in Cambridge and New York; it is likely that they, too, were addressed to Sitt al-Mulk. Such documents elucidate Sitt al-Mulk's role in government after her brother's death and provide evidence for the chronicler al-Musabbiḥī's claim that she received and responded to petitions from subjects. The article offers possible explanations as to why petitions such as this one, which concerns an Ismaili mosque, should have found their way to the Jewish community of Fustat whose members reused and preserved them. It also suggests some broader conclusions about the dispersal, survival, or disappearance of pre-Ottoman Middle Eastern archives and documents.
Revisiting the language factor in Zionism: The Hebrew Language Council from 1904 to 1914
Authors: Aytürk İlker
Published: January 2010

The role of language and linguistic-philological studies in the nationalist movements of the nineteenth century received much attention. The aim of this article is to focus on the language factor in Zionism and the revival of Hebrew as a spoken language in the Yishuv between 1904 and 1914. Founded in 1904, the Hebrew Language Council was expected to enhance the process of revival and, from the very beginning, an unmistakably nationalist attitude to its subject matter marked the Council's agenda. However, the authority of the Council to make binding decisions on linguistic matters was contested by a number of other Zionist institutions, a development which ruined the prestige and effectiveness of the Council. The controversy resulted less from a turf war or quarrels over scarce resources than a deeper question of which institution represented the “true” Hebraic spirit. The World Zionist Organization's decision to de-align from cultural matters, including the revival of Hebrew, worsened the conditions under which the Council operated. From a comparative perspective, thus, the Hebrew case provides an unusual case of linguistic nationalism, which should be of interest to students of both nationalism and sociolinguistics.
The poetic forms and two longer poems in the Manju gisun i yobo maktara sarkiyan
Authors: Toh Hoong Teik
Published: January 2010

It is generally assumed that, throughout the Qing dynasty, there was only translated literature in the Manchu language and that, by the nineteenth century, the Manchu literati had become too “sinicized” to unleash literary creativity in their native language. Nevertheless the discovery of a mid-nineteenth-century manuscript of Manchu literary verse, penned by the well-known prose translator Jakdan, points to the fact that Manchu belles-lettres existed even at a time when the role of Manchu in practical arenas was much in decline within the Qing empire in China. In addition to a preliminary account of the poetic forms found in Jakdan's Manju gisun i yobo maktara sarkiyan (“Transcript of bantering in Manchu language”), a supplementary volume to the Jabduha ucuri amtanggai baita (“Leisurely delights”), two intricate poems from the collection of Manchu verse are here presented (in transcription), translated and annotated for the first time.
The Meroitic script and the understanding of alpha-syllabic writing
Authors: de Voogt Alexander J.
Published: January 2010

At the time of its decipherment by Griffith (1911), the Meroitic writing system was considered an alphabet. This alphabet was found to have a rather limited vowel notation. It was not until 1970 that the system was understood to have a more complex vowel notation. This system of vowel notation is comparable to what is found in an alpha-syllabary, a term used to describe the scripts of the Indian sub-continent, such as Brahmi and Devanagari. Since alpha-syllabaries were rare when the Meroitic writing system was in use (c. 200 bce–c. 500 ad), it is tempting to suggest a possible historical connection between the Meroitic kingdom in Sudan and the then existent scripts in India. A systematic analysis, as opposed to a description of alpha-syllabic writing, indicates that the structure of this type of script is less regionally confined. Rather, it places Meroitic writing among scripts that were created in the presence of alphabetic writing both in modern and in ancient times.
Social Security and the Transition to Adulthood
Authors: Harris Neville
Published: January 2010

Social security provision for young people has been cut back by a succession of reforms since 1980 culminating in the almost complete withdrawal of income support from 16 and 17 year olds by the Social Security Act 1988. Conservative government policy seems to indicate a desire that families assume greater responsibility for young people until either they find work or reach their mid-twenties. It is assumed that until young unemployed people reach this stage they are dependants, to be treated as such by the social security system (and, to a large extent, by the training schemes). But the twentieth century has seen a progressive growth of young people's independence and expectations of it among young people and their families. The enforced dependency produced by recent government policy runs counter to this trend. More importantly, it may be having a profound effect on the progress of the transition to adulthood.
The evolution of misbelief
Authors: McKay Ryan T. , Dennett Daniel C.
Published: January 2010

From an evolutionary standpoint, a default presumption is that true beliefs are adaptive and misbeliefs maladaptive. But if humans are biologically engineered to appraise the world accurately and to form true beliefs, how are we to explain the routine exceptions to this rule? How can we account for mistaken beliefs, bizarre delusions, and instances of self-deception? We explore this question in some detail. We begin by articulating a distinction between two general types of misbelief: those resulting from a breakdown in the normal functioning of the belief formation system (e.g., delusions) and those arising in the normal course of that system's operations (e.g., beliefs based on incomplete or inaccurate information). The former are instances of biological dysfunction or pathology, reflecting “culpable” limitations of evolutionary design. Although the latter category includes undesirable (but tolerable) by-products of “forgivably” limited design, our quarry is a contentious subclass of this category: misbeliefs best conceived as design features. Such misbeliefs, unlike occasional lucky falsehoods, would have been systematically adaptive in the evolutionary past. Such misbeliefs, furthermore, would not be reducible to judicious – but doxastically1noncommittal – action policies. Finally, such misbeliefs would have been adaptive in themselves, constituting more than mere by-products of adaptively biased misbelief-producing systems. We explore a range of potential candidates for evolved misbelief, and conclude that, of those surveyed, onlypositive illusionsmeet our criteria.
Misbelief and the neglect of environmental context
Authors: Dunning David
Published: January 2010

Focusing on the individual's internal cognitive architecture, McKay & Dennett (M&D) provide an incomplete analysis because they neglect the crucial role played by the external environment in producing misbeliefs and determining whether those misbeliefs are adaptive. In some environments, positive illusions are not adaptive. Further, misbeliefs often arise because the environment commonly fails to provide crucial information needed to form accurate judgments.
God would be a costly accident: Supernatural beliefs as adaptive
Authors: Johnson Dominic D. P.
Published: January 2010

I take up the challenge of whyfalsebeliefs are better than “cautious actionpolicies” (target article, sect. 9) in navigating adaptive problems with asymmetric errors. I then suggest that there areinteractionsbetween supernatural beliefs, self-deception, and positive illusions, rendering elements of all such misbeliefs adaptive. Finally, I argue that supernatural beliefs cannot be rejected as adaptive simply because recent experiments are inconclusive. The great costs of religion betray its even greater adaptive benefits – we just have not yet nailed down exactly what they are.
(Not so) positive illusions
Authors: Kruger Justin , Chan Steven , Roese Neal
Published: January 2010

We question a central premise upon which the target article is based. Namely, we point out that the evidence for “positive illusions” is in fact quite mixed. As such, the question of whether positive illusions are adaptive from an evolutionary standpoint may be premature in light of the fact that their very existence may be an illusion.
Pathological and non-pathological factors in delusional misbelief
Authors: Langdon Robyn
Published: January 2010

In their pursuit of adaptively biased misbelief-making systems, McKay & Dennett (M&D) describe a putative doxastic shear-pin system which enables misbeliefs to form in situations of extreme psychological stress. Rather than discussing their argument, I consider how this shear-pin system might combine with both pathological belief-making (“culpable” breakdowns caused by neuropathy) and normal belief-making to explain a spectrum of delusions.
The evolution of religious misbelief
Authors: Norenzayan Ara , Shariff Azim F. , Gervais Will M.
Published: January 2010

Inducing religious thoughts increases prosocial behavior among strangers in anonymous contexts. These effects can be explained both by behavioral priming processes as well as by reputational mechanisms. We examine whether belief in moralizing supernatural agents supplies a case for what McKay & Dennett (M&D) call evolved misbelief, concluding that they might be more persuasively seen as an example of culturally evolved misbelief.
The (mis)management of agency: Conscious belief and nonconscious self-control
Authors: Randolph-Seng Brandon
Published: January 2010

McKay & Dennett (M&D) identify positive illusions as fulfilling the criteria for an adaptive misbelief, but could there be other types of beliefs that may qualify as adaptive misbeliefs? My commentary addresses this and other questions through identifying belief in free will as a potential candidate as an adaptive misbelief.