A numerical study of crack tip constraint in ductile single crystals

In this work, the effect of crack tip constraint on near-tip stress and deformation fields in a ductile FCC single crystal is studied under mode I, plane strain conditions. To this end, modified boundary layer simulations within crystal plasticity framework are performed, neglecting elastic anisotropy. The first and second terms of the isotropic elastic crack tip field, which are governed by the stress intensity factor K and T-stress, are prescribed as remote boundary conditions and solutions pertaining to different levels of T-stress are generated. It is found that the near-tip deformation field, especially, the development of kink or slip shear bands, is sensitive to the constraint level. The stress distribution and the size and shape of the plastic zone near the crack tip are also strongly influenced by the level of T-stress, with progressive loss of crack tip constraint occurring as T-stress becomes more negative. A family of near-tip fields is obtained which are characterized by two terms (such as K and T or J and a constraint parameter Q) as in isotropic plastic solids.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Crystal structures and photocatalysis of the triclinic polymorphs of BiNbO4 and BiTaO4

The high-temperature polymorphs of two photocatalytic materials, BiNbO4 and BiTaO4 were synthesized by the ceramic method. The crystal structures of these materials were determined by single-crystal X-ray diffraction. BiNbO4 and BiTaO4 crystallize into the triclinic system P (1) over bar (No. 2), with a = 5.5376(4) angstrom, b = 7.6184(3) angstrom, c = 7.9324(36) angstrom, alpha = 102.565(3)degrees, beta = 90.143(2)degrees, gamma = 92.788 (4)degrees, V = 326.21 (5) angstrom(3). Z = 4 and a = 5.931(1) angstrom, b = 7.672(2) angstrom, c = 7.786(2) angstrom, alpha = 102.94 (3)degrees, beta = 90.04(3)degrees gamma = 93.53(3)degrees, V = 344.59(1) angstrom(3) and Z = 4, respectively. The structures along the c-axis, consist of layers of [Bi2O2] units separated by puckered sheets of (Nb/Ta)O-6 octahedra. Photocatalytic studies on the degradation of dyes indicate selectivity of BiNbO4 towards aromatics containing quinonic and azo functional groups

Crystal structure of 2-thiophene-2-yl-3(thiophene-2-carboxylideneamino)-1,2-dihydroquinazolin-4(3H)-one and the synthesis, spectral and thermal studies of its transition metal(II) complexes

The synthesis of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of a new ligand 2-thiophene-2-yl-3(thiophene-2-carboxylidene-amino)-1,2-dihydroquinazolin-4(3H)-one (TTCADQ) is described. The ligand and metal complexes were characterized by elemental analysis, conductivity measurements, spectral (u.v.-vis., i.r., 1D n.m.r., 2D hetcor and e.p.r.) and thermal studies. The formation of 1,2-dihydroquinazolin-4(3H)-one rather than hydrazone, in the reaction of aromatic aldehyde and o-aminobenzoylhydrazide is proved by single crystal X-ray diffraction and 2D hetcor n.m.r. studies. On the basis of elemental analysis, u.v.-vis.spectroscopy and magnetic moment studies, six coordinate geometry for all the complexes was proposed. The i.r. spectral studies reveal the bidentate behaviour of the ligand.

Crystal and molecular structure of the ammonium salt of the dinucleoside monophosphate d(CpG)

The crystal and molecular structure of the ammonium salt of deoxycytidylyl-(3'-5')-deoxyguanosine has been determined from 0.85 A resolution single crystal X-ray diffraction data. The crystals obtained by acetone diffusion technique at -20 degrees C, are orthorhombic, P212121, a = 12.880(2), b = 17444(2) and c = 27.642(2) A. The structure was solved by high resolution Patterson and Fourier methods and refined to R = 0.136. There are two d(CpG) molecules in the asymmetric unit forming a mini left handed Z-DNA helix. This is in contrast to the earlier reported forms of d(CpG) where the molecules form self base paired duplexes. There are two ammonium ions in the asymmetric unit. The major groove NH+4 ion interacts with N7 of guanines through water bridges besides making H-bonded interactions directly with the phosphate oxygen atoms. A second NH+4 ion is found in the minor groove interacting directly with the phosphate oxygen atoms. Symmetry related molecules pack in such a way that the cytosine base stacks on cytosine and guanine base on guanine. Our structure demonstrates that alternating d(CpG) sequences have the ability to adopt the left handed Z-DNA structure even at the dimer level i.e., in a sequence which is only two base pairs long.

Using Water as a Design Element in Crystal Engineering. Host-Guest Compounds of Hydrated 3,5-Dihydroxybenzoic Acid

Thirteen host guest compounds of 3,5-dihydroxybenzoic acid (DHBA) have been structurally characterized. Water molecules occupy the peripheries of a hexagonal void, created with DHBA molecules, and act as ``hooks'' to connect the guest molecules with the host-framework via hydrogen bonding. The ``water hook'' is an OH group acting as a donor. Consequently, the guest molecules were chosen so that they contain good hydrogen bond acceptor functionalities. A number of multicomponent hydrates were isolated with stoichiometries (DHBA)(x)(H2O). (guest),. Of these, compounds with the following as guests were obtained as crystals that were good enough for single crystal work: ethyl acetate (EtOAc), diethyl oxalate, dimethyl oxalate, di(n-propyl) oxalate, diethyl malonate, diethyl succinate, chloroacetonitrile, N,N-dimethyl formamide (DMF), acetone, dimethyl sulfoxide (DMSO), 1-propanol, and 2-butanol. From 2-butanol, a hemihydrate, (DHBA)(2)(H2O), was also obtained concomitantly. Further to guest stabilization, water acts as a good mediator of effective crystal packing and also determines the topology of the host framework. En the present series of compounds, the role of water is wide ranging, and it is not easy to classify it specifically as a host or as a guest.

Mixed Azide and 5-(Pyrimidyl)tetrazole Bridged Co(II)/Mn(II) Polymers: Synthesis, Crystal Structures, Ferroelectric and Magnetic Behavior

The reaction of pyrimidine-2-carbonitrile, NaN3 in the presence of Co(NO3)(2)center dot 6H(2)O or MnCl2 center dot 4H(2)O leads to the formation of complexes Co(pmtz)(mu(1,3)-N-3)(H2O)](n) (1) and Mn(pmtz)(mu(1,3)-N-3)(H2O)](n) (2) respectively, under hydrothermal condition pmtz =5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T-c = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.

Synthesis and characterization of metal substituted AlxCr1-x(acetylacetonate)(3) single-source precursors for their application to MOCVD of thin films

A detailed study, involving the synthesis of a single-source precursor containing two metal ions sharing the same crystallographic site, has been undertaken to elucidate the use of such a single-source precursor in a CVD process for growing thin films of oxides comprising these two metals, ensuring a uniform composition and distribution of metal ions. The substituted complexes Cr1-xAlx(acac)(3), where acac = acetyl-acetonate, have been prepared by a co-synthesis method, and characterized using UV-Vis spectroscopy. TGA/DTA measurements, and single crystal X-ray diffraction at low temperature. All the studied compositions crystallize in the monoclinic space group P2(1)/c with Z = 4 in the unit cell. It was observed that the ratio (Al:Cr) of the site occupancy for the metal ions, obtained from single crystal refinement, is in agreement with the results obtained from complexometric titrations. All the solid state structures have the metal in an octahedral environment forming six-membered chelate rings. M-O acac bond lengths and disorder in the terminal carbon have been studied in detail for these substituted metal-organic complexes. One composition among these was chosen to evaluate their suitability as a single-source precursor in a LPMOCVD process (low-pressure metal-organic chemical vapour deposition) for the deposition of a substituted binary metal oxide thin film. The resulting thin films were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. (C) 2010 Elsevier Ltd. All rights reserved.

Crystal and molecular structure of sym-homospermidine monohydrate

Sym-homospermidine, [formula; see text] is a naturally occurring rare-polyamine found in relatively large concentration in sandal leaves. As part of our studies on structure and interactions of polyamines, ym-homospermidine was purified from sandal leaves and its structure was determined by single crystal X-ray diffraction technique. The phosphate salt of the molecule crystallized in the triclinic space group P1- with a = 8.246(1)A, b = 8.775(1)A, c = 15.531(2)A, alpha = 74.20(1) degrees, beta = 88.36(1) degrees and gamma = 65.41(1) degrees. The structure was determined by direct methods and refined to a final R factor of 5.4% for 2087 reflections with magnitude of F(obs) greater than 5 sigma [F(obs)]. The amine exists in its most favourable all trans conformation. For each amine molecule three phosphate groups exist in the crystal structure, suggesting that two of the oxygens of each phosphate group are protonated. There is also a single water molecule in the asymmetric unit in contrast to that of spermidine phosphate which has 3 water molecules. These differences probably reflect the hydrogen bonding properties of mono-ionic and di-ionic phosphate groups. The structure is predominantly stabilized by a network of hydrogen bonds.

Crystal Chemistry of the Noncentrosymmetric Eulytites: A(3)Bi(XO4)(3) (X = V, A = Pb; X = P, A = Ca, Cd, Sr, Pb)

Eulytite compounds, A(3)Bi(XO4)(3) (X = P, A = Ca, Cd, Sr, Pb), belong to the noncentrosymmetric space group l (4) over bar 3d (No. 220) as determined by single-crystal X-ray diffraction studies. The crystals were grown from the melt-cool technique with considerable difficulty as the compounds melt incongruently at their melting temperature, except for the compound Pb3Bi(PO4)(3). The unit cell parameter a is 9.984(5), 9.8611(3), 10.2035(3), and 10.3722(2) angstrom for Ca3Bi(PO4)(3), Cd3Bi(PO4)(3), Sr3Bi(PO4)(3), and Pb3Bi(PO4)(3) respectively, and there are four formula units in the unit cell. The structure of Pb3Bi(VO4)(3), a unique eulytite with vanadium substitution, is compared with all these phosphorus substituted eulytites. The A(2+) and Bi3+ cations occupy the special position (16c) while the O anions occupy the general Wyckoff position (48e) in the crystal structure. Only one O position has been identified for Pb3Bi(PO4)(3) and Pb3Bi(VO4)(3), whereas two O atom sites were identified for Ca3Bi(PO4)(3), Cd3Bi(PO4)(3), and Sr3Bi(PO4)(3). The UV-vis diffuse reflectance spectra indicate large band gaps for all the phosphate eulytites while a lower band gap is observed for the vanadate eulytite. The feasibility of the use of these compounds in optoelectronic devices has been tested by measuring the second-harmonic generation (SHG) values which have been found to be of a magnitude equivalent to the commercially used KDP (KH2PO4).

Novel coordination behaviour of gem-bis (pyrazolyl) cyclotriphosphazenes as tridentate NNN-donor ligands: The crystal structure of [Mo(CO)3{N3P3Ph4(3,5-Me2C3HN2)2}]

Reactions of group 6 metal carbonyls with bis(pyrazolyl) phosphazenes yield metal tricarbonyl complexes, [M(CO)3.L] [L = N3P3Ph4 (3, 5-Me2C3HN2)2 (1) or N3P3(MeNCH2CH2O)2 (3,5-Me2C3HN2)2(4)]. The structure of the complex [Mo(CO)3.1], determined by single-crystal X-ray analysis, shows that the (pyrazolyl) phosphazene acts as a tridentate ligand; the two pyridinic pyrazolyl nitrogen atoms and a phosphazene ring nitrogen atom are coordinated to the metal. A similar structure is proposed for the complexes [M(CO)3.4] (M = Mo or W] on the basis of their spectroscopic data.

Organometallic derivatives of diphosphazanes. 2. Seven-coordinated Group 6 metal tricarbonyl complexes of diphosphazane ligands. X-ray crystal structure of [WI2(CO)3{P(OPh)2}2NPh]

The reactions of the complexes [MI2(CO)3-(NCMe)2] (M = Mo, W) with the diphosphazane ligands RN{P(OPh)2}2 (R = Me, Ph) in CH2Cl2 at room temperature afford new seven-coordinated complexes of the type [MI2(CO)3{P(OPh)2}2NR]. The molybdenum complexes are sensitive to air oxidation even in the solid state, whereas the tungsten complexes are more stable in the solid state and in solution. The structure of the tungsten complex [WI2(CO)3{P(OPh)2}2NPh] has been determined by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system with the space group Pna 2(1), a = 19.372 (2) angstrom, b = 11.511 (1) angstrom, c = 15.581 (1) angstrom, and Z = 4. Full-matrix least-squares refinement with 3548 reflections (I > 2.5-sigma-(I)) led to final R and R(w) values of 0.036 and 0.034, respectively. The complex adopts a slightly distorted pentagonal-bypyramidal geometry rarely observed for such a type of complexes; two phosphorus atoms of the diphosphazane ligand, two iodine atoms, and a carbonyl group occupy the equatorial plane, and the other two carbonyl groups, the apical positions.

Impurity diffusion in bismuth single-crystals

Measurements of impurity diffusion of 86Rb, 90Sr, 133Ba, and 137Cs in single crystal Bi were carried out. Diffusion samples were prepared from single crystal Bi by ion implantation. About 1012-1013 ions were implanted, resulting in surface activities approx =104 cpm. After implantation, specimens were annealed for specified times at 220-265 deg C, and tracer penetration profiles were determined by an electrolytic method. A typical penetration profile for 137Cs in Bi showed a linear relationship for log C vs x in with Fick's law for volume diffusion. Laws of grain boundary diffusion were not obeyed and the order of magnitude of the penetration distances was much less than on a grain boundary mechanism. Results were interpreted in terms of a modified Fischer analysis using a kinetic trapping term. Effective half lengths for trapping at a twin boundary were determined for each impurity.

Structural features of B-DNA dodecamer crystal structures: Influence of crystal packing versus base sequence

We have analyzed the set of inter and intra base pair parameters for each dinucleotide step in single crystal structures of dodecamers, solved at high and medium resolution and all crystallized in P2(1)2(1)2(1) space group. The objective was to identify whether all the structures which have either the Drew-Dickerson (DD) sequence d[CGCGAATTCGCG] with some base modification or related sequence (non-DD), would display the same sequence dependent structural variability about its palindromic sequence, despite the molecule being bent at one end because of similar crystal lattice packing effect. Most of the local doublet parameters for base pairs steps G2-C3 and G10-C11 positions, symmetrically situated about the lateral twofold, were significantly correlated between themselves. In non-DD sequences, significant correlations between these positional parameters were absent. The different range of local step parameter values at each sequence position contributed to the gross feature of smooth helix axis bending in all structures. The base pair parameters in some of the positions, for medium resolution DD sequence, were quite unlike the high-resolution set and encompassed a higher range of values. Twist and slide are the two main parameters that show wider conformational range for the middle region of non-DD sequence structures in comparison to DD sequence structures. On the contrary, the minor and major groove features bear good resemblance between DD and non-DD sequence crystal structure datasets. The sugar-phosphate backbone torsion angles are similar in all structures, in sharp contrast to base pair parameter variation for high and low resolution DD and non-DD sequence structures, consisting of unusual (epsilon =g(-), xi =t) B-II conformation at the 10(th) position of the dodecamer sequence. Thus examining DD and non-DD sequence structures packed in the same crystal lattice arrangement, we infer that inter and intra base pair parameters are as symmetrically equivalent in its value as the symmetry related step for the palindromic DD sequence about lateral two-fold axis. This feature would lead us to agree with the conclusion that DNA conformation is not substantially affected by end-to-end or lateral inter-molecular interaction due to crystal lattice packing effect. Non-DD sequence structures acquire step parameter values which reflect the altered sequence at each of the dodecamer sequence position in the orthorhombic lattice while showing similar gross features of DD sequence structures