A paraelectric-ferroelectric phase transition of an organically templated zinc oxalate coordination polymer.

Water-presence dependent switchable ferroelectricity was discovered in the hybrid organic-inorganic zinc oxalate 1D coordination polymer (DABCOH2)[Zn(C2O4)2]·3H2O (DZnOH, where DABCOH2: diprotonated 1.4-diazoniabicyclo[2.2.2]octane). The compound undergoes a reversible para-ferroelectric phase transition at 207 K from room temperature centrosymmetric phase I (space group P21/n) to low-temperature non-centrosymmetric phase II (space group P21). The microscopic mechanism of the phase transition is directly associated with the reconstruction of the hydrogen-bond network. On heating, the crystals exhibit a reversible single-crystal to single-crystal transformation concerned with the removal of all water molecules giving anhydrous DABCO zinc oxalate (DABCOH2)[Zn(C2O4)2] (DZnO). The dehydrated compound does not show ferroelectric properties.

Order-disorder phase transition in an anhydrous pyrazole-based proton conductor: the enhancement of electrical transport properties.

The crystal structure of 1H-pyrazol-2-ium hydrogen oxalate has been studied at 100 K. It consists of two-dimensional layers built with one-dimensional chains that contain pyrazolium and oxalate acids bonded by N-HO and O-HO hydrogen bonds. According to the X-ray data and the Quantum Theory of Atoms in Molecules, it was shown that weak and moderate hydrogen bonds are present in the crystal at room temperature. The thermal stability was studied with the DSC, TGA, and DTG methods: three endothermic peaks are observed at 384, 420, and 469 K. Conductivity measurements have been performed in the temperature range from 300 to 433 K. At 383 K the pyrazole-oxalic acid framework loses its rigidity and the crystal undergoes an ordered-disordered phase transition. At this temperature, the value of the activation energy of proton conductivity changes from 1.14 to 2.31 eV. The proton conduction pathways and the transport mechanism have been studied with theoretical methods.

Structural, vibrational and theoretical studies of anilinium trichloroacetate: new hydrogen bonded molecular crystal with nonlinear optical properties.

In this work, we report a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of the potential nonlinear optical (NLO) material anilinium trichloroacetate. The FT-IR and FT-Raman spectra of the compound have been recorded together between 4000-80 cm(-1) and 3600-80 cm(-1) regions, respectively. The compound crystallizes in the noncentrosymmetric space group of monoclinic system. The optimized molecular structure, vibrational wavenumbers, IR intensities and Raman activities have been calculated by using density functional method (B3LYP) with 6-311++G(d,p) as higher basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. DSC measurements on powder samples do not indicate clearly on the occurrence of phase transitions in the temperature 113-293 K. The Kurtz and Perry powder reflection technique appeared to be very effective in studies of second-order nonlinear optical properties of the molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, frontier orbitals and thermodynamic properties were also performed at 6-311++G(d,p) level of theory. For title crystal the SHG efficiency was estimated by Kurtz-Perry method to be d(eff)=0.70 d(eff) (KDP).

Crystal structure, differential scanning calorimetric, infrared spectroscopy and theoretical studies of C(NH2)2(NH)*CH2=CHCOOH noncentrosymmetric crystal.

The X-ray and vibrational spectroscopic analysis of a new molecular complex of guanidine and acrylic acid are reported. The crystal of C(NH(2))(2)(NH)(*)CH(2)=CHCOOH belongs to Pna2(1) space group of orthorhombic system with Z=4, a=9.9242(34) Å, b, c=8.3951(14) Å. In the crystal structure the macroscopic symmetry center is absent. The differential scanning calorimetric (DSC) experiment of powder sample indicates on continuous phase transition at 235.8K. The room temperature infrared spectrum of guanidine*acrylic acid powder sample has been measured. The spectrum is discussed on the basis of crystallographic data. The IR spectra for the powder sample were also measured at low temperatures (12-300 K). The temperature relationships of band position for obtained spectra are analyzed. Additionally, the results of theoretical calculation of vibrational spectra, equilibrium structure, HOMO, LUMO and first order hyperpolarizability are presented.

X-ray diffraction, vibrational and quantum chemical investigations of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid.

The structural investigations of the molecular complex of 2-methyl-4-nitroaniline with trichloroacetic acid, namely 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid (C(11)H(10)Cl(6)N(2)O(6)) have been performed by means of single crystal and powder X-ray diffraction method. The complex was formed with accompanying proton transfer from trichloroacetic acid molecule to 2-methyl-4-nitroaniline. The studied crystal is built up of singly protonated 2-methyl-4-nitroanilinium cations, trichloroacetate anions and neutral trichloroacetic acid molecules. The crystals are monoclinic, space group P2(1)/c, with a=14.947Å, b=6.432Å, c=19.609Å and Z=4. The vibrational assignments and analysis of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid have also been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings were added from the quantum chemical studies performed with DFT (B3LYP) method using 6-31G, cc-pVDZ, 6-31G and 6-31++G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of 2M4NATCA were also determined by the DFT methods.

Disordered La3Cu4.88Se7.

The crystal structure of copper(I) lanthanum selenide, La(3)Cu(4.88)Se(7), obtained from the La(2)Se(3)-Cu(2)Se quasi-binary system, has been investigated using X-ray single-crystal diffraction. The positions of the La and Se atoms are ordered and lie on mirror planes, whereas all positions for the Cu atoms are partially occupied. The crystal is built from edge-sharing [LaSe(6)] and [LaSe(7)] polyhedra. The five positions for the Cu atoms determine an ionic diffusion pathway in the structure.

FT NIR Raman studies of alginic acid-benzimidazole polymer composite.

New bio-inspired polymer composites of alginic acid and benzimidazole were created and characterized by FT NIR Raman spectroscopy. The obtained films with 1:0.5, 1:1 and 1:1.5 molar ratio are homogeneous, with good mechanical properties. Raman spectra recorded at room temperature revealed that the obtained films are a new compound with a different molecular structure and physical properties compared with pure substrates: alginic acid and benzimidazole. Raman band related to vibration of COOH entity at 1740 cm(-1) of alginic acid disappears in the alginic acid:benzimidazole composites, in which new Raman band related to COO(-) was found. Additionally, characteristic lines observed in polymer composites which may be associated with vibrations of NH groups, can be attributed to the linking of proton to deprotonated N atom in benzimidazole group. Possibility of such proton exchange is a promising property which might facilitate the application of obtained composites to anhydrous proton conducting electrolytes in fuel cells.

Multiferroic BiFeO3 nanoparticles studied by electron spin resonance, X-ray diffraction and transmission electron microscopy methods.

The properties of multiferroic BiFeO3 nanoparticles with core-shell structure produced by mechanically activated room temperature synthesis were studies by electron spin resonance spectroscopy and X-ray diffraction. The data reveal essential differences in ordered and disordered regions among as-prepared and annealed samples. The thermally-induced increase in the average size of the grains and disappearance of the disordered grain shell determined from the electron spin resonance and X-ray diffraction are in a good agreement and were confirmed by transmission electron microscopy observations. Ferro- and ferrimagnetic ordering was observed in as-prepared BiFeO3 nanograins, whereas antiferromagnetic order was apparent in the annealed material. The results show that the electron spin resonance spectroscopy can be considered as an useful method to determine the type of magnetic ordering in multiferroic nanoparticles.

Structural and vibrational properties of K(3)Fe(MoO(4))(2)(Mo(2)O(7))-a novel layered molybdate.

The new compound K(3)Fe(MoO(4))(2)(Mo(2)O(7)) was synthesized and characterized by a single-crystal x-ray structure determination, and IR and Raman spectroscopic studies. The crystal structure at room temperature and ambient pressure is monoclinic, space group C 2/c, with the unit cell dimensions a = 32.885(7), b = 5.7220(11), c = 15.852(3) Å, ß = 91.11°, Z = 8. The FeO(6) octahedra are joined by corners with MoO(4)(2-) tetrahedra and Mo(2)O(7)(2-) units. Some of the K(+) ions form layers in the b × c-plane. The origin of various Raman and IR vibrational modes is discussed. These results indicate that a clear energy gap exists between the stretching and remaining modes. High-pressure Raman scattering studies were also performed. These studies showed the onset of two reversible first-order phase transitions near 1.2 and 7.4 GPa, which are associated with strong distortion of the MoO(4)(2-) and Mo(2)O(7)(2-) units.

New 2-methylimidazole-dicarboxylic acid molecular crystals: crystal structure and proton conductivity.

Three new proton conducting molecular crystals, 2-methylimidazole glutarate, 2-methylimidazole suberate and 2-methylimidazole azelate, were obtained and their structure was determined by the x-ray diffraction method. The structure of the crystals was found to be of layer-type. A hydrogen bond network between the heterocycle, glutaric acid and water molecules was apparent in a single layer of 2-methylimidazole glutarate, whereas chains consisting of two heterocyclic molecules linked with hydrogen bonds with dicarboxylic acid were distinguished in a single layer of 2-methylimidazole suberate and azelate crystals. Thermal stability of the crystals was characterized by differential scanning calorimetry and the electrical conductivity was studied by the impedance spectroscopy method. The maximum conductivity of 2-methylimidazole glutarate pellets amounts to 3.3 × 10(-2) S m(-1) at 325 K, in the case of 2-methylimidazole suberate pellets the maximum conductivity is 2.4 × 10(-4) S m(-1) at 348 K and for 2-methylimidazole azelate pellets the maximum conductivity reaches 6.9 × 10(-4) S m(-1) at 353 K.

Hexacopper(I) phosphorus(V) bromide penta(selenide/sulfide), Cu6P(Se0.7S0.3)5Br.

This work illustrates possible diffusion paths for Cu(I) ions in a highly disordered structure of a superionic conductor of the argyrodite family. The Cu(6)P(Se(0.7)S(0.3))(5)Br cubic structure is built from a [P(Se(0.7)S(0.3))(5)Br] framework in which Cu(I) ions are distributed in various tetrahedral, triangular and linear sites. There are two types of disorder in the structure. The first type results from the fact that there are fewer Cu(I) ions than the number of positions available for them in the unit cell. The second type is due to the static distribution of Se and S atoms in the [P(Se(0.7)S(0.3))(5)Br] framework. The title compound is a solid solution of two efficient ionic conductors, namely Cu(6)PSe(5)Br and Cu(6)PS(5)Br, in which high ionic conductivity results from order-disorder phenomena in the copper substructure. To shed light on the distribution of Cu(I) ions in disordered Cu(6)P(Se(0.7)S(0.3))(5)Br, we refined their positions using a combination of a nonharmonic approach and a split-atom model. At room temperature, Cu(I) ions show strong anharmonic vibrations along the edge of the (Br)(4) tetrahedra. The probability density functions of the Cu(I) ions overlap and reveal possible diffusion paths.

Crystal structure and vibrational spectra of piperazinium bis(4-hydroxybenzenesulphonate) molecular-ionic crystal.

The piperazinium bis(4-hydroxybenzenesulphonate) crystallizes from water solution at room temperature in P2(1)/c space group of monoclinic system. The crystals are built up of doubly protonated piperazinium cations and ionized 4-hydroxybenzenesulphonate anions that interact through weak hydrogen bonds of O-H...O and N-H...O type. Mutual orientation of anions is determined by non-conventional hydrogen bonds of C-Hcdots, three dots, centeredpi type. Room temperature powder FT IR and FT Raman measurements were carried out. The vibrational spectra are in full agreement with the structure obtained from X-ray crystallography. The big single crystals of the title salt can be grown.

Hydrogen-bonded network in biphenyl-4,4'-diphosphonic acid.

The crystal structure of the title compound, C(12)H(12)O(6)P(2), displays two different regions alternating along the a axis: a hydrogen-bonded region encompassing the end-positioned phosphonic acid groups and a hydrophobic region formed by the aromatic spacers. The asymmetric unit contains only half of the biphenyl-4,4'-diphosphonic acid (4,4'-bpdp) molecule, which is symmetric with an inversion centre imposed at the mid-point between the two aromatic rings. The periodic organization of the molecules is controlled by two strong O-H...O interactions between the phosphonic acid sites. Weak C-H...pi interactions are established in the aromatic regions.

Dy(8)SnS(13.61)O(0.39) from single-crystal data.

Crystals of the title dysprosium tin sulfide oxide, Dy(8)SnS(13)S(1-x)O(x) [x = 0.39 (4)], were obtained unintentionally from the Dy-Sn-S system. A statistical mixture of sulfur and oxygen was assumed for one position in the structure. S and O atoms surround each of the eight symmetrically non-equivalent dysprosium atoms. The Sn atoms are located in tetra-hedral surroundings of sulfur atoms. Trigonal prisms and tetra-hedra are connected to each other by their edges. All atoms are situated in mirror planes.

X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid complex: temperature, isotope, and pressure effects.

The x-ray diffraction studies of the title complex were carried out at room temperature and 14 K for H/D (in hydrogen bridge) isotopomers. At 82 K a phase transition takes place leading to a doubling of unit cells and alternation of the hydrogen bond lengths linking tetramethylpyrazine (TMP) and chloranilic acid molecules. A marked H/D isotope effect on these lengths was found at room temperature. The elongation is much smaller at 14 K. The infrared isotopic ratio for O-H(D)...N bands equals to 1.33. The four tunnel splittings of methyl librational ground states of the protonated complex required by the structure are determined at a temperature T=4.2 K up to pressures P=4.7 kbars by high resolution neutron spectroscopy. The tunnel mode at 20.6 microeV at ambient pressure shifts smoothly to 12.2 microeV at P=3.4 kbars. This is attributed to an increase of the strength of the rotational potential proportional to r(-5.6). The three other tunnel peaks show no or weak shifts only. The increasing interaction with diminishing intermolecular distances is assumed to be compensated by a charge transfer between the constituents of deltae/e approximately 0.02 kbar(-1). The phase transition observed between 3.4 and 4.7 kbars leads to increased symmetry with only two more intense tunneling bands. In the isotopomer with deuterated hydrogen bonds and P=1 bar all tunnel intensities become equal in consistency with the low temperature crystal structure. The effect of charge transfer is confirmed by a weakening of rotational potentials for those methyl groups whose tunnel splittings were independent of pressure. Density functional theory calculations for the model TMP.(HF)2 complex and fully ionized molecule TMP+ point out that the intramolecular rotational potential of methyl groups is weaker in the charged species. They do not allow for the unequivocal conclusions about the role of the intermolecular charge transfer effect on the torsional frequencies.

Field-dependent ordered phases and Kondo phenomena in the filled skutterudite compound PrOs4As12.

Electrical resistivity, specific heat, and magnetization measurements to temperatures as low as 80 mK and magnetic fields up to 16 T were made on the filled skutterudite compound PrOs4As12. The measurements reveal the presence of two ordered phases at temperatures below approximately 2.3 K and in fields below approximately 3 T. Neutron-scattering experiments in zero field establish an antiferromagnetic ground state < 2.28 K. In the antiferromagnetically ordered state, the electronic-specific heat coefficient gamma approximately 1 J/mol x K2 below 1.6 K and 0 < or = H < or = 1.25 T. The temperature and magnetic-field dependence of the electrical resistivity and specific heat in the paramagnetic state are consistent with single-ion Kondo behavior with a low Kondo temperature on the order of 1 K. The electronic-specific heat in the paramagnetic state can be described by the resonance-level model with a large zero-temperature electronic-specific heat coefficient that decreases with increasing magnetic field from approximately 1 J/mol x K2 at 3 T to approximately 0.2 J/mol x K2 at 16 T.

Structure of N6-furfurylaminopurine (kinetin) dihydrogenphosphate.

The crystal structure of kinetin dihydrogenphosphate has been determined at 115 and 293 K. Kinetin dihydrogenphosphate undergoes a polymorphic phase transition at 291.1 K. In both phases the crystal belongs to the triclinic system with the symmetry described by the space group P\bar 1. In the low-temperature phase, the unit cell is doubled along the a axis. There is a dynamic equilibrium between different tautomeric forms of the adenine residue, determined by the distribution of H atoms within the network of hydrogen bonds.

Structural and vibrational investigation of para-nitraminopyridine N-oxide. A combined experimental and theoretical studies.

The X-ray and vibrational spectroscopic analysis of para-nitraminopyridine N-oxide are reported. The crystals of investigated compound belong to P2(1) of the monoclinic system, Z=4, a=3.735 A, b=11.767 A, c=14.679 A and beta=93.27 degrees . Room temperature powder infrared and Raman spectra of the title compound and its deuterated analogue were measured. The molecular structure of p-nitraminopyridine N-oxide has been calculated with the aid of density functional (B3LYP) method with the extended 6-311++G(d,p) basis set. The calculated geometrical parameters of investigated molecule in gas phase were compared with experimental X-ray data. The harmonic frequencies, potential energy distribution (PED) and IR intensities of p-nitroaminopyridine N-oxide and its deuterated analogue were calculated with B3LYP method. The assignment of the experimental spectra has been made on the basis of the calculated PED. The time depend Hartree-Fock (TDHF) method was used for calculations of hyperpolarizability beta coefficient.

Diguanidinium hydrogenarsenate monohydrate and its deuterated analogue vibrational, DSC and X-ray investigations.

The crystal structure of diguanidinium hydrogenarsenate monohydrate has been found to belong to the P42(1)/c space group of the tetragonal system, with Z = 8, a = 17.114(2) A, c = 7.3500(10) A. In this complex, a network of hydrogen bonds links water molecules and hydrogenarsenate ions. The hydrogenarsenate ions form hydrogen-bonded chains along the crystallographic c-axis. Detailed vibrational studies have been carried out (FTIR and FT-Raman on powder samples, polarized FTIR microscope on a small single crystal at room temperature). The vibrational spectra are discussed in relation to the crystal structure. Calorimetric (DSC) studies have been performed, but no phase transition was found in the temperature range 100-350 K.

Diffuse scattering and ordering in the short-range modulated paraelectric phase of sodium nitrite, NaNO2.

The incommensurately modulated antiferroelectric phase of sodium nitrite, NaNO2, transforms at T(N) = 437.7 K to the short-range modulated paraelectric phase. The apparently discontinuous phase transition is accompanied by characteristic changes in the diffraction pattern. Contrary to the well known modulated structures with sharp satellite reflections, the diffraction pattern of a short-range modulated structure contains diffuse satellite reflections. The short-range modulated crystal structure of the paraelectric phase of sodium nitrite has been analysed by the Reverse Monte Carlo (RMC) simulation of X-ray diffuse scattering. The crystal structure of sodium nitrite may be regarded as consisting of [Na+NO2-]infinity rows running along the polar b axis. One can expect long fragments of rows with uniform polarity The assumption that single [Na+NO2-]infinity rows are polar with uniform polarity proved to be a convenient approximation which is in good agreement with the observed diffraction pattern. The distribution of (+)- and (-)-[Na+NO2-]infinity polar rows crossing the (010) plane of short-range modulated NaNO2 revealed by RMC shows nanodomains consisting of distorted fragments of a sinusoidally modulated crystal structure. The size of the nanodomains and the degree of order in paraelectric NaNO2 decreases with temperature.