Rubidium hydrogen glutarate and ammonium hydrogen glutarate: X-ray studies of quasi-isostructural crystals involving very short hydrogen bonds

Rubidium and ammonium hydrogen glutarates (M ^{+ –}CO₂.C₃H₆.CO₂H) each crystallize with four molecules in orthorhombic unit cells of almost identical dimensions: (M = Rb)a = 18·55,b = 7·57,c = 5·29 Å; (M = NH₄)a= 18·59,b= 7·56,c= 5· 27 Å. They have very similar structures, but they are not isomorphous: space groupsCmma (Rb) andPmaa (NH₄).The crystal structures have been determined by three-dimensional X-ray analysis and refined with moderate precision. Both have infinite chains of glutarate residues, linked end-to-end by very short, symmetrical hydrogen bonds, with O···H···O = 2·40(2) (Rb) and O···H···O = 2·460(6) Å (NH₄).In the Rb salt, the glutarate residue has strict, crystallographicm symmetry. The difference in the NH₄ salt arises from small movements of the carbon and (especially) the oxygen atoms out of this symmetry plane. These are due to N-H···O bonding: two equivalent cations in the Rb salt, each making contact with eight oxygen atoms, become differentiated in the NH₄ salt by linkage to different sets of four oxygens.We wish to acknowledge financial support from the Science Research Council, and our indebtedness to Drs. J. G. Sime, K. W. Muir and others for help with KDF9 programs.     

Growth of single crystals of quasicrystalline phases

To study the mechanical and physical properties of quasicrystals, single-crystal samples of large size (several centimeters) are necessary. However, obtainment of such single crystals meets a number of difficulties related to the peritectic character of melting of quasicrystalline compounds, high volatility and oxidizability of the initial components, low growth rate in aperiodic directions, and metastability of the most quasicrystalline structures. In this study, criteria for stable growth of quasicrystalline phases have been determined. The growth mechanisms of icosahedral and decahedral single crystals are described and experimental techniques of single-crystal growth are reviewed.     

Valency tautomerism of triosereductone via hydrogen bonds

The strongly temperature-dependent¹H-nmr spectrum of prop-1-en-1,2-diol-3-one (triosereductone), C₃H₄O₃, can be explained on the basis of valency tautomerism. Intramolecular hydrogen bonding is responsible for this effect.The helpful support of the Deutsche Forschungsgemeinschaft is gratefully acknowledged.     

Intra- versus intermolecular hydrogen bonds in salicylamide derivatives

The crystal structures, solid-state infrared patterns, and thermal properties of two polymorphs of 4-nitrosalicylanilide are presented. In both polymorphs, intramolecular hydrogen bonds are found between the phenol oxygen and the amide proton, and intermolecular hydrogen bonds are found between the amide carbonyl oxygen and the phenol proton. These hydrogen bond patterns are compared to those found in other known salicylamide derivatives and an analysis is given of the factors contributing to preferences for intra- or intermolecular hydrogen bonds in these structures. Crystal data: polymorph, orthorhombic,Pbca,a=11.003(4),b=27.959(7),c=7.622(5) Å,Z=4,V=2345(3) ų, andR=0.038 (1351 reflections); polymorph, monoclinic,P2₁/a,a=28.36(1),b=11.64(1),c=7.293(8) Å,=90.68(6)°,Z=8,V=2408 ų, andR=0.043 (2425 reflections).     

Effect of foreign phases on the growth of NaBi(WO4)2 crystals

Single crystals of NaBi(WO₄)₂ (NBW) have been grown by Czochralski technique, employing differently synthesized starting charge and different axial temperature gradients. The causes behind inherent problems related to compositional changes and associated lowering in crystallization temperature have been probed by analyzing XRD and DTA patterns of post growth residual charge. Presence of low melting phases viz. Na₂WO₄ and hitherto unreported compound Na₅Bi(WO₄)₄ is thought to be responsible for the observed decrease in crystallization temperature. This problem was tackled by segregating pure phase material through re‐crystallization, under high axial temperature gradient. The use of re‐crystallized charge enabled transformation of almost the entire charge into a single crystal of high transparency. The effect of starting charge synthesis and temperature gradient on the optical transmission characteristics of NBW crystal has also been investigated. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of single crystals of the high-pressure ɛ-FeOOH phase

Single crystals of the high-pressure ?-FeOOH phase are grown from an aqueous solution at p = 7 GPa in the temperature range 580–350°C. Dark brown crystals of prismatic habit are obtained that have characteristic sizes of 0.1 × 0.1 × 0.7 mm. A region of the t-x phase diagram of the H₂O-Fe₂O₃ system at p = 7 GPa is constructed on the basis of the data obtained.     

Single-crystal structures of high-pressure phases FeOOH,FeOOD, and GaOOH

The structures of the ?-FeOOH, ?-FeOOD, and β-GaOOH phases, which belong to the InOOH structure type (the distorted TiO₂ structure type), are determined using single-crystal X-ray diffraction analysis. The measurements are performed on Xcalibur CCD and CAD-4F diffractometers. The calculations are carried out in space group P2_1nm with the JANA2000 program. The crystals are twinned and form aggregates related by the rotation around the b axis through an angle close to 62°. In the same crystals, the merohedral twinning is characterized by the rotation around the c axis through an angle of 180°. The alternation of these twin domains in the bulk of the crystal determines the corresponding disordering of the hydrogen positions.     

Strain of interatomic bonds and multiple-well potential in crystals with perovskite structure

A method for determining the strain characteristics of interatomic bonds in crystals of ABX₃ compounds with perovskite structure is developed. The bond strain energy ΔU _s is estimated. This energy is responsible for the formation of ordered lattice distortions related to the rotation of octahedra and/or the cooperative displacement of cations. It is shown that ΔU _s correlates with the characteristics of ordered distortions and the temperature of the phase transition of compounds to the cubic structure. It is ascertained that the interatomicinteraction potential in crystals with strained bonds is a local multiple-well potential, the form of which depends on the nature of interacting atoms. It is shown that the occurrence of the ferroelectric state in the noted crystals may be due to the presence of bond strains and the anisotropy of the covalent component of the cation-anion interaction.     

Tracing of dislocations in ammonium hydrogen tartrate single crystals

Sparingly soluble ammonium hydrogen tartrate (AHT) crystals are grown by the gel method, derived from the diffusion of ammonium chloride into the set gel containing tartaric acid. Crystals up to 23 × 5 × 3 mm³ in size are grown at room temperature. AHT crystals are cleaved along (010) planes and the cleavage surfaces are studied by using multiple beam interferometry. The interferograms have revealed that the cleavages are quite flat. An attempt is made to trace the trajectory of dislocations of isolated as well as matched pairs of (010) cleavages of AHT when etched in a mixture of formic acid and methyl alcohol (2:1) and 1.0 M SrCl₂ solutions. Optical and transmission electron micrographs of dislocations show oblique, parallel and continuous line characteristics. Rows of equally spaced dislocation pits are observed and the implications of this are discussed.     

Thermal and optical studies on induced smectic phases of inter molecular hydrogen bonded liquid crystals between decyloxy benzoic acid and citric acid

Hydrogen bonded liquid crystal complex (HBLC) is prepared from mesogenic 4-decyloxy benzoic acid (10OBA) and aliphatic nonmesogenic citric acid (CA). Liquid crystal (LC) phases are investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) studies. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR) validate the intermolecular complementary, cyclic type of hydrogen bond (HB) and molecular environment in the designed HBLC complex. Mesomorphic phases like nematic, smectic X (Sm X) and smectic G (Sm G) are characterized by various textures and using different techniques such as POM, DSC and optical tilt angle measurements. Thermal span width and thermal stability factor for the observed phase is calculated. The complexes are prepared in different mole ratio and their corresponding influences on the phase transitions are discussed. Also it is observed that the HB units play a vital role in stabilizing the new Sm X phase. The variation in thermal stability of smectic phases due to the influence of aromatic cores and length of end chain in the different mole ratio of the present HBLC complexes are also discussed. The variation of tilt angle with respect to temperature in the smectic phase has been experimentally calculated and analyzed. The lowered melting and clearing transition temperatures and extended thermal span width in the Sm X phase are also reported.     

Electrical conduction in ferroelectric lead hydrogen phosphate single crystals

Single crystals of LHP (Lead Hydrogen Phosphate) have been grown using the controlled reaction between lead nitrate and orthophosphoric acid solution by diffusion process in silica gel medium. Transparent crystals upto 6 × 4 × 3 mm³ in size have been grown at room temperature. The d.c. electrical conductivity of both single crystals and pelletized samples of LHP have been studied in the temperature range from 313 to 968 K. It has been observed that: (i) the d.c. conductivity of the crystalline sample is greater than that of thepellet sample, (ii) three distinct electrical conductivity processes have been observed and are interpreted as extrinsic, intrinsic, phase changes, and (iii) the activation energy for the conduction in the crystalline sample is greater than that of the pellet sample. The magnetic susceptibility measurements reveal that the paramagnetic characteristic of these materials and the implications are discussed.     

Microstructures of gel-grown ammonium hydrogen tartrate single crystals

Single crystals of ammonium hydrogen tartrate (AHT) have been grown in silica gels by employing the controlled reaction between ammonium chloride and tartaric acid. Transparent AHT crystals upto 24 × 4 × 3 mm³ in size have been grown at room temperature. Optical and electron-optical studies have been made on the various surface structures of {010} faces of the grown crystals. A variety of growth striations and growth hillocks have been observed. Growth layers modified by the presence of misaligned microcrystals have been illustrated. It has been suggested that two-dimensional nucleation, spreading and pilling up of growth layers is mainly responsible for the growth of these crystals and the implications are discussed.     

Microhardness studies of ammonium hydrogen tartrate single crystals

Single crystals of ammonium hydrogen tartrate AHT NH₄HC₄H₄O₆ have been grown employing the controlled reaction between NH₄Cl and (CHOHCOOH)₂ by slow diffusion process in silica gels. The variation in the microhardness of AHT crystals has been determined using Vicker's microhardness indentor. The effects of annealing and quenching on the mechanical properties of these crystals have been studied. It is observed that: (i) irrespective of the relative orientation of the indentor and the crystal, the median vents initiated at the sharp indentation edges, (ii) the microhardness of the crystals depends on the applied load, (iii) the microhardness of the crystal is independent on the duration of loading, and (iv) maximum plasticity is observed in quenched crystals. The implications of this behaviour are discussed.     

A comparison between predicted and measured structural parameters in symmetric hydrogen bonds

The distance between two equilibrium proton sites in symmetric OHO bonds and its isotopic variation, determined from precise neutron-diffraction data, has been compared with the predicted values which were derived previously by the author using correlation curves in hydrogen-bond parameters. It is shown that a fairly good agreement was obtained between the observed and the predicted values, indicating the validity of the empirical relations.     

Domain structure in CsDSO4 crystals

A complex study of domain structure of CsDSO₄ crystals has been performed over a wide temperature range. The effect of internal and external stresses and the PO₄ impurity on the kinetics of domain growth is considered. The behavior of the domain structure of the CsDSO₄ crystals is compared with martensite phase transformations. A model of crystal-lattice transformations in various phases is suggested, including an intermediate phase with the unknown symmetry of CsDSO₄ crystals.     

Dielectric properties of ferroelectric lead hydrogen phosphate single crystals

The ferroelectric lead hydrogen phosphate (LHP) single crystals have been grown by employing the gel technique. The controlled reaction between lead nitrate and orthophosphoric acid solutions by diffusion process in gel medium has been used. The dielectric constant (ϵ′) and the dielectric loss (ϵ″) have been measured for the first time as a function of frequency in the range 10² to 10⁴ Hz. They have also been determined as a function of temperatures in the range 300 to 680 K. The polarisation effect contributing to the dielectric constant has been studied. It has been observed that the mechanism of the dielectric behaviour is different in the lower and higher temperatur and frequency ranges. The activation energy of the oscillators has been calculated and found to be 1.12 eV. Attempt has been made to draw some qualitative conclusions, taking in view, the existing theories of various kinds of polarization and implications have been discussed.     

Numerical simulation of the LEC-growth of GaAs crystals with account of high-pressure gas convection

The influence of the inert gas pressure on the growth of 4 GaAs crystals by the liquid encapsulated Czochralski method (LEC) process is studied for a range of the Ar gas pressure up to 10 bar by using our finite-volume computer code STHAMAS. Up to the pressure of 0.6 bar we are considering laminar convection. For the pressure range from 5 to 10 bar we are using the buoyancy extended standard k-ε turbulence model with wall functions to simulate the gas flow. The numerical results show that the Argon gas pressure has a strong influence on the consumption of heater power in qualitative agreement with our experimental results. The convex curvature of the growth interface and the maximum thermal stress (von Mises criterion) are found to increase with increasing gas pressure both in the laminar and turbulent evaluations.     

Synthesis and characterization of ferroelectric magnesium hydrogen phosphate single crystals

Ferroelectric Magnesium Hydrogen Phosphate MgHPO₄ (MHP) single crystals are grown by slow diffusion of magnesium chloride in sodium metasilicate gels impregnated with orthophosphoric acid. Bright and transparent prismatic, tabular, and isometric habit MHP crystals upto 3 × 2 × 1 mm³ are obtained. Results of chemical, X-ray diffraction, EDAX, microhardness and magnetic analysis are reported. The average etch pit density is determined by chemical etching to be 7 × 10³ cm⁻². Microtopographic investigations revealed the mechanism of crystal growth.