Investigations on the polymorphism of K4CaSi6O15 at elevated temperatures.

In the present study, single crystals and polycrystalline material of K4CaSi6O15 were prepared from solid-state reactions between stoichiometric mixtures of the corresponding oxides/carbonates. Heat capacity (C p) measurements above room temperature using a differential scanning calorimeter indicated that two thermal effects occurred at approximately T 1 = 462 K and T 2 = 667 K, indicating the presence of structural phase transitions. The standard third-law entropy of K4CaSi6O15 was determined from low-temperature C p's measured by relaxation calorimetry using a Physical Properties Measurement System and amounts to S°(298K) = 524.3 ± 3.7 J·mol-1·K-1. For the 1st transition, the enthalpy change ΔH tr1 = 1.48 kJ·mol and the entropy change ΔS tr1 = 3.25 J·mol-1·K-1, whereas ΔH tr2 = 3.33 kJ·mol-1 and ΔS tr2 = 5.23 J·mol-1·K-1 were determined for the 2nd transition. The compound was further characterized by in-situ single-crystal X-ray diffraction between ambient temperature and 1063 K. At 773 K, the high-temperature phase stable above T 2 has the following basic crystallographic data: monoclinic symmetry, space group P21/c, a = 6.9469(4) Å, b = 9.2340(5) Å, c = 12.2954(6) Å, ß = 93.639(3)°, V = 787.13(7) Å3, Z = 2. It belongs to the group of interrupted framework silicates and is based on tertiary (Q3-type) [SiO4]-tetrahedra. Together with the octahedrally coordinated Ca-cations, a three-dimensional mixed polyhedral network structure is formed, in which the remaining K-ions provide charge balance by occupying voids within the net. The intermediate temperature modification stable between T 1 and T 2 shows a (3+2)-dimensional incommensurately modulated structure that is characterized by the following q-vectors: q1 = (0.057, 0.172, 0.379), q2 = (-0.057, 0.172, -0.379). The crystal structures of the high- and the previously studied ambient temperature polymorph (space group Pc) are topologically equivalent and show a group-subgroup relationship. The index of the low- in the high-symmetry group is six and involves both, losses in translation as well as point group symmetry. The distortion is based on shifts of the different atom species and tilts of the 4- and 6-fold coordination polyhedra. Actually, for some of the oxygen atoms, the displacements exceed 0.5 Å. A more detailed analysis of the distortions relating to both structures has been performed using mode analysis, which revealed that the primary distortion mode transforms according to the Λ1 irreducible representation of P21/c. However, other modes with smaller distortion amplitudes are also involved.

A Fluoroponytailed NHC-Silver Complex Formed from Vinylimidazolium/AgNO3 under Aqueous-Ammoniacal Conditions.

3-(1H,1H,2H,2H-Perfluorooctyl)-1-vinylimidazolium chloride [2126844-17-3], a strong fluorosurfactant with remarkably high solubility in water, was expediently converted into the respective doubly NHC-complexed silver salt with nitrate as counter ion in quantitative yield. Due to its vinyl substituents, [bis(3-(1H,1H,2H,2H-perfluorooctyl)-1-vinylimidazol-2-ylidene)silver(I)] nitrate, Ag(FNHC)2NO3, represents a polymerizable N-heterocyclic carbene transfer reagent, thus potentially offering simple and robust access to coordination polymers with crosslinking metal bridges. The compound was characterized by infrared and NMR spectroscopy, mass spectrometry as well as elemental analysis, and supplemented by X-ray single-crystal structure determination. It crystallizes in the monoclinic crystal system in the space group P21/c. With 173.3°, the geometry of the Ag-carbene bridge deviates slightly from linearity. The disordered perfluoroalkyl side chains exhibit a helical conformation.

Bacterial Catabolism of Biphenyls: Synthesis and Evaluation of Analogues.

A series of alkylated 2,3-dihydroxybiphenyls has been prepared on the gram scale by using an effective Directed ortho Metalation-Suzuki-Miyaura cross-coupling strategy. These compounds have been used to investigate the substrate specificity of the meta-cleavage dioxygenase BphC, a key enzyme in the microbial catabolism of biphenyl. Isolation and characterization of the meta-cleavage products will allow further study of related processes, including the catabolism of lignin-derived biphenyls.

New Insights into Solid Form Stability and Hydrate Formation: o-Phenanthroline HCl and Neocuproine HCl.

The moisture- and temperature dependent stabilities and interrelation pathways of the practically relevant solid forms of o-phenanthroline HCl (1) and neocuproine HCl (2) were investigated using thermal analytical techniques (HSM, DSC and TGA) and gravimetric moisture sorption/desorption studies. The experimental stability data were correlated with the structural changes observed upon dehydration and the pairwise interaction and lattice energies calculated. For 1 the monohydrate was identified as the only stable form under conditions of RH typically found during production and storage, but at RH values >80% deliquescence occurs. The second compound, 2, forms an anhydrate and two different hydrates, mono- (2-Hy1) and trihydrate (2-Hy3). The 2-Hy1 structure was solved from SCXRD data and the anhydrate structure derived from a combination of PXRD and CSP. Depending on the environmental conditions (moisture) either 2-Hy1 or 2-Hy3 is the most sable solid form of 2 at RT. The monohydrates 1-Hy1 and 2-Hy1 show a high enthalpic stabilization (≥20 kJ mol-1) relative to the anhydrates. The anhydrates are unstable at ambient conditions and readily transform to the monohydrates even in the presence of traces of moisture. This study demonstrates how the right combination of experiment and theory can unravel the properties and interconversion pathways of solid forms.

Mechanical Properties, Quantum Mechanical Calculations, and Crystallographic/Spectroscopic Characterization of GaNbO4, Ga(Ta,Nb)O4, and GaTaO4.

Single crystals as well as polycrystalline samples of GaNbO4, Ga(Ta,Nb)O4, and GaTaO4 were grown from the melt and by solid-state reactions, respectively, at various temperatures between 1698 and 1983 K. The chemical composition of the crystals was confirmed by wavelength-dispersive electron microprobe analysis, and the crystal structures were determined by single-crystal X-ray diffraction. In addition, a high-P-T synthesis of GaNbO4 was performed at a pressure of 2 GPa and a temperature of 1273 K. Raman spectroscopy of all compounds as well as Rietveld refinement analysis of the powder X-ray diffraction pattern of GaNbO4 were carried out to complement the structural investigations. Density functional theory (DFT) calculations enabled the assignment of the Raman bands to specific vibrational modes within the structure of GaNbO4. To determine the hardness (H) and elastic moduli (E) of the compounds, nanoindentation experiments have been performed with a Berkovich diamond indenter tip. Analyses of the load-displacement curves resulted in a high hardness of H = 11.9 ± 0.6 GPa and a reduced elastic modulus of Er = 202 ± 9 GPa for GaTaO4. GaNbO4 showed a lower hardness of H = 9.6 ± 0.5 GPa and a reduced elastic modulus of Er = 168 ± 5 GPa. Spectroscopic ellipsometry of the polished GaTa0.5Nb0.5O4 ceramic sample was employed for the determination of the optical constants n and k. GaTa0.5Nb0.5O4 exhibits a high average refractive index of nD = 2.20, at λ = 589 nm. Furthermore, in situ high-temperature powder X-ray diffraction experiments enabled the study of the thermal expansion tensors of GaTaO4 and GaNbO4, as well as the ability to relate them with structural features.

Nanoindentation, High-Temperature Behavior, and Crystallographic/Spectroscopic Characterization of the High-Refractive-Index Materials TiTa2O7 and TiNb2O7.

Colorless single crystals, as well as polycrystalline samples of TiTa2O7 and TiNb2O7, were grown directly from the melt and prepared by solid-state reactions, respectively, at various temperatures between 1598 K and 1983 K. The chemical composition of the crystals was confirmed by wavelength-dispersive X-ray spectroscopy, and the crystal structures were determined using single-crystal X-ray diffraction. Structural investigations of the isostructural compounds resulted in the following basic crystallographic data: monoclinic symmetry, space group I2/m (No. 12), a = 17.6624(12) Å, b = 3.8012(3) Å, c = 11.8290(9) Å, ß = 95.135(7)°, V = 790.99(10) Å(3) for TiTa2O7 and a = 17.6719(13) Å, b = 3.8006(2) Å, c = 11.8924(9) Å, ß = 95.295(7)°, V = 795.33(10) Å(3), respectively, for TiNb2O7, Z = 6. Rietveld refinement analyses of the powder X-ray diffraction patterns and Raman spectroscopy were carried out to complement the structural investigations. In addition, in situ high-temperature powder X-ray diffraction experiments over the temperature range of 323-1323 K enabled the study of the thermal expansion tensors of TiTa2O7 and TiNb2O7. To determine the hardness (H), and elastic moduli (E) of the chemical compounds, nanoindentation experiments have been performed with a Berkovich diamond indenter tip. Analyses of the load-displacement curves resulted in a hardness of H = 9.0 ± 0.5 GPa and a reduced elastic modulus of Er = 170 ± 7 GPa for TiTa2O7. TiNb2O7 showed a slightly lower hardness of H = 8.7 ± 0.3 GPa and a reduced elastic modulus of Er = 159 ± 4 GPa. Spectroscopic ellipsometry of the polished specimens was employed for the determination of the optical constants n and k. TiNb2O7 as well as TiTa2O7 exhibit a very high average refractive index of nD = 2.37 and nD = 2.29, respectively, at λ = 589 nm, similar to that of diamond (nD = 2.42).

Solid state forms of 4-aminoquinaldine - From void structures with and without solvent inclusion to close packing.

Polymorphs of 4-aminoquinaldine (4-AQ) have been predicted in silico and experimentally identified and characterised. The two metastable forms, AH (anhydrate) II and AH III, crystallise in the trigonal space group [Formula: see text] and are less densely packed than the thermodynamically most stable phase AH I° (P21/c ). AH II can crystallise and exist both, as a solvent inclusion compound and as an unsolvated phase. The third polymorph, AH III, is exclusively obtained by desolvation of a carbon tetrachloride solvate. Theoretical calculations correctly estimated the experimental 0K stability order, confirmed that AH II can exist without solvents, gave access to the AH III structure, and identified that there exists a subtle balance between close packing and number of hydrogen bonding interactions in the solid state of anhydrous 4-AQ. Furthermore, the prevalence of void space and solvent inclusion in [Formula: see text] structures is discussed.

Insights into hydrate formation and stability of morphinanes from a combination of experimental and computational approaches.

Morphine, codeine, and ethylmorphine are important drug compounds whose free bases and hydrochloride salts form stable hydrates. These compounds were used to systematically investigate the influence of the type of functional groups, the role of water molecules, and the Cl(-) counterion on molecular aggregation and solid state properties. Five new crystal structures have been determined. Additionally, structure models for anhydrous ethylmorphine and morphine hydrochloride dihydrate, two phases existing only in a very limited humidity range, are proposed on the basis of computational dehydration modeling. These match the experimental powder X-ray diffraction patterns and the structural information derived from infrared spectroscopy. All 12 structurally characterized morphinane forms (including structures from the Cambridge Structural Database) crystallize in the orthorhombic space group P212121. Hydrate formation results in higher dimensional hydrogen bond networks. The salt structures of the different compounds exhibit only little structural variation. Anhydrous polymorphs were detected for all compounds except ethylmorphine (one anhydrate) and its hydrochloride salt (no anhydrate). Morphine HCl forms a trihydrate and dihydrate. Differential scanning and isothermal calorimetry were employed to estimate the heat of the hydrate ↔ anhydrate phase transformations, indicating an enthalpic stabilization of the respective hydrate of 5.7 to 25.6 kJ mol(-1) relative to the most stable anhydrate. These results are in qualitative agreement with static 0 K lattice energy calculations for all systems except morphine hydrochloride, showing the need for further improvements in quantitative thermodynamic prediction of hydrates having water···water interactions. Thus, the combination of a variety of experimental techniques, covering temperature- and moisture-dependent stability, and computational modeling allowed us to generate sufficient kinetic, thermodynamic and structural information to understand the principles of hydrate formation of the model compounds. This approach also led to the detection of several new crystal forms of the investigated morphinanes.

Thortveitite-type Tm2Si2O7.

Single crystals of dithulium disilicate, Tm2Si2O7, were obtained in flux synthesis experiments in the system SiO2-Tm2O3-LiF at ambient pressure. The compound belongs to the group of sorosilicates, i.e. it is based on [Si2O7]-units and crystallizes in the thortveitite (Sc2Si2O7) structure type. The Tm(3+) cation (site symmetry .2.) occupies a distorted octa-hedral site, with Tm-O bond lengths in the range 2.217 (4)-2.289 (4) Å. Each of the octa-hedra shares three of its edges with adjacent [TmO6] groups, resulting in the formation of layers parallel to (001). The individual [SiO4] tetra-hedra are more regular, i.e. the differences between the bond lengths between Si and the bridging and non-bridging O atoms are not very pronounced. The layers containing the octa-hedra and the sheets containing the [Si2O7] groups (point group symmetry 2/m) form an alternating sequence. Linkage is provided by sharing common oxygen vertices.

K9Y3[Si12O32]F2.

Single-crystals of the title compound, nona-potassium triyttrium dodeca-silicate difluoride, were obtained from flux synthesis experiments in the system SiO2-Y2O3-KF. The crystal structure belongs to the group of single-layer silicates and is based on silicate sheets parallel to (110). A single layer contains secondary (Q (2)) and tertiary (Q (3)) silicate tetra-hedra in the ratio 1:2 and is build up from six-, eight- and twelve-membered rings. The linkage between neighboring layers is achieved by two crystallographically independent Y(3+) cations, which are coordinated by six oxygen ligands in form of distorted octa-hedra. Charge compensation is accomplished by incorporation of additional F(-) anions and K(+) cations in the structural channels, forming anion-centred [F2K7] groups. Apart from one K(+) and one Y(3+) cation (each with site symmetry -1), the 30 crystallographically independent atoms reside on general positions.

Rb2Lu[Si4O10]F, a tubular chain silicate.

Single crystals of Rb2Lu[Si4O10]F (dirubidium lutetium tetra-silicate fluoride) were obtained in flux-synthesis experiments in the system SiO2-Lu2O3-RbF. The compound belongs to the group of tubular chain silicates, i.e. it is based on multiple chains of condensed [SiO4] tetra-hedra forming closed columns. The periodicity of the unbranched multiple chains is four and corresponds to the length of the b axis. Adjacent columns are connected by Lu(3+) cations, which are coordinated by four oxide and two fluoride anions in the form of slightly distorted octa-hedra. By sharing common fluoride corners, the single octa-hedra are linked into chains running parallel to the silicate tubes. Electroneutrality is achieved by the incorporation of additional Rb(+) cations. All four symmetrically independent rubidium ions, four out of twelve oxide as well as the two fluoride anions are located on mirror planes. The remaining atoms reside on general positions.

Crystal structure of 4-amino-1-benzyl-1,2,4-triazolin-5-one.

The title compound, C9H10N4O, was obtained unintentionally by hydrolysis of 4-amino-1-benzyl-5-methyl-sulfanyl-1,2,4-triazolium tetra-fluoro-borate in the presence of sodium azide. In the crystal, alternating layers of polar amino-triazolinone and apolar benzene moieties are observed. N-H⋯O hydrogen bonds between the amino and carbonyl groups form infinite chains along [010]. These infinite chains are linked by additional C-H⋯O contacts.

Synthesis and Characterization of Single Crystal Zircon-Hafnon Zr(1-x)Hf(x)SiO4 Solid Solutions and the Comparison with the Reaction Products of a TEOS-Based Hydrothermal Route.

Two synthesis routes of the zircon-hafnon solid solution series were carried out. The high-temperature route uses the growth of single crystals via a flux mixture that has been cooled down slowly from 1400 °C over 4 weeks. The reaction products were colorless and idiomorphic without byproducts. The hydrothermal tetraethoxysilane (TEOS)-based route represents the low-temperature method at 200 °C for approximately 7 days. The hydrothermal route yielded a white powder and scanning electron microscopy analysis thereof did not reveal any specific idiomorphic properties. However, the synthesis also featured some byproducts besides the zircon-hafnon solid solutions. Thermogravimetric analysis coupled with differential scanning calorimetry, and mass spectroscopy indicated, that hydrothermal reaction products feature the presence of organic residues originating from the starting materials. However, a specific dependency on the hafnium content could not be observed due to the data scatter. Infrared (IR) analysis revealed the presence of Zr/Hf-oxides. The structural characterization demonstrated that properties change constantly with the hafnium amount, however, gradual variations of some properties related to the composition of the solid solution series depend in part on the synthesis route, considering the c/a ratio and IR modes. Furthermore, analyses of the single crystals by Raman spectroscopy and µXRF suggested a nonequilibrated crystal growth based on the starting composition.

Structural, spectroscopic, and computational studies on Tl4Si5O12: a microporous thallium silicate.

Single crystals of the previously unknown thallium silicate Tl4Si5O12 have been prepared from hydrothermal crystallization of a glassy starting material at 500 °C and 1 kbar. Structure analysis resulted in the following basic crystallographic data: monoclinic symmetry, space group C2/c, a = 9.2059(5) Å, b = 11.5796(6) Å, c = 13.0963(7) Å, ß = 94.534(5)°. From a structural point of view the compound can be classified as an interrupted framework silicate with Q(3)- and Q(4)-units in the ratio 2:1. Within the framework 4-, 6-, and 12-membered rings can be distinguished. The framework density of 14.4 T-atoms/1000 Å(3) is comparable with the values observed in zeolitic materials like Linde type A, for example. The thallium cations show a pronounced one-sided coordination each occupying the apex of a distorted trigonal TlO3 pyramid. Obviously, this reflects the presence of a stereochemically active 6s(2) lone pair electron. The porous structure contains channels running along [110] and [-1 1 0], respectively, where the Tl(+) cations are located for charge compensation. Structural investigations have been completed by Raman spectroscopy. The interpretation of the spectroscopic data and the allocation of the bands to certain vibrational species have been aided by DFT calculations, which were also employed to study the electronic structure of the compound.

Telaprevir: helical chains based on three-point hydrogen-bond connections.

The crystal structure of the title compound [systematic name: (1S,3aR,6aS)-2-((2S)-2-{[(2S)-2-cyclohexyl-2-(pyrazine-2-carbonylamino)acetyl]amino}-3,3-dimethylbutanoyl)-N-[(3S)-1-(cyclopropylamino)-1,2-dioxohexan-3-yl]-3,3a,4,5,6,6a-hexahydro-1H-cyclopenta[c]pyrrole-1-carboxamide], C(36)H(53)N(7)O(6), contains two independent molecules, which possess distinct conformations and a disordered cyclopenta[c]pyrrolidine unit. In the crystal, molecules are linked into helical chains via three-point N-H···O hydrogen-bond connections in which three NH and three carbonyl groups per molecule are utilized. The chiralities of the six stereocentres per molecule inferred from this study are in agreement with the synthetic procedure.

Alogliptin and its benzoate salt.

The crystal structure of the free base of the antidiabetic drug alogliptin [systematic name: 2-({6-[(3R)-3-aminopiperidin-1-yl]-3-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl}methyl)benzonitrile], C18H21N5O2, displays a two-dimensional N-H···O hydrogen-bonded network. It contains two independent molecules, which have the same conformation but differ in their hydrogen-bond connectivity. In the crystal structure of the benzoate salt (systematic name: (3R)-1-{3-[(2-cyanophenyl)methyl]-1-methyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-yl}piperidin-3-aminium benzoate), C18H22N5O2(+)·C7H5O2(-), the NH3(+) group of the cation is engaged in three intermolecular N-H···O hydrogen bonds to yield a hydrogen-bonded layer structure. The benzoate salt and the free base differ fundamentally in the conformations of their alogliptin moieties.

Dipotassium hydrogencarbonate fluoride monohydrate.

Single crystals of the title compound, K2(HCO3)F·H2O, were obtained as a secondary product after performing flux synthesis experiments aimed at the preparation of potassium rare earth silicates. The basic building unit of the structure is an [(HCO3)(H2O)F](2-) zigzag chain running parallel to [001]. Both types of anions as well as the water mol-ecules reside on mirror planes perpendicular to [010] at y = 0.25 and y = 0.75, respectively. Linkage between the different constituents of the chains is provided by O-H⋯O and O-H⋯F hydrogen bonding. The K(+) cations are located between the chains and are coordinated by two F and five O atoms in form of a distorted monocapped trigonal prism.

A murine model of phosphate nephropathy.

We established a murine model of phosphate nephropathy with secondary hyperparathyroidism. db/db mice, which develop obesity and type 2 diabetes mellitus, were uninephrectomized at the age of 6 weeks and were fed either standard chow or a phosphorus-rich diet during the next 8 weeks. Thereafter, renal cryosections showed abundant tubular casts with a strong histochemical von Kossa reaction in all db/db mice on the phosphorus-rich diet but none in the controls. X-ray diffraction and Raman spectroscopy proved that these tubular casts consist mostly of hydroxyapatite Ca5(PO4)3(OH). These intraluminal precipitations were located in distal tubuli and collecting ducts and were associated with degenerative tubular changes and peritubular infiltration of T cells and macrophages. In line, kidneys of db/db mice on the phosphorus-rich diet displayed significantly increased mRNA expression of the T(H)1 cytokines interferon γ, IL-6, and tumor necrosis factor α. In addition, mice developed signs of secondary hyperparathyroidism as shown by elevated serum phosphate, decreased serum calcium, and increased parathyroid hormone, osteopontin, and fibroblast growth factor 23 levels. db/db mice on the phosphorus-rich diet also presented with significantly lower body weight, lower homeostasis model assessment of insulin resistance index, and hypertrophic cardiomyopathy. Thus, we provide a murine model of phosphate nephropathy and secondary hyperparathyroidism, which can be used for future pharmacologic and pathophysiologic studies to analyze the effect of hyperphosphatemia on renal, metabolic, and cardiovascular phenotypes.

Form II of adipic acid-nicotinohydrazide (1/2).

The crystal structure of the title co-crystal, 2C(6)H(7)N(3)O·C(6)H(10)O(4), is a second polymorph, designated form II, of the co-crystal formed between the two mol-ecules [Lemmerer et al. (2011 ▶). CrystEngComm, 13, 55-59]. The asymmetric unit comprises one mol-ecule of nicotinic acid hydrazide, and one half-mol-ecule of adipic acid (the entire mol-ecule is completed by the application of a centre of inversion). In the crystal, mol-ecules assemble into a three-dimensional network of hydrogen bonds, formed by three N-H⋯O hydrogen bonds and one O-H⋯N hydrogen bond. The O-H⋯N hydrogen bond formed between the carboxyl group and the pyridine ring is supported by a C-H⋯O hydrogen bond.

N'-Cyclo-pentyl-idene-pyridine-4-carbo-hydrazide.

The title compound, C(11)H(13)N(3)O, is a derivative of the anti-tuberculosis drug isoniazid [systematic name: pyridine-4-carbohydrazide]. The crystal structure consists of repeating hydrogen-bonded chains parallel to the b axis. Adjacent mol-ecules in the chains are linked by bifurcated N-H⋯(O,N) hydrogen bonds, which form an R(1) (2)(5) ring motif.