Thermal, spectroscopic and structural analysis of a thermosalient phase transformation in tapentadol hydrochloride

2019 ◽  
Vol 75 (2) ◽  
pp. 183-191 ◽  
Author(s):  
Pablo Gaztañaga ◽  
Ricardo Baggio ◽  
Emilia Halac ◽  
Daniel R. Vega
Keyword(s):  
Phase Transformation ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Covalent Interaction ◽  
Cell Parameters ◽  
Reversible Phase Transition ◽  
Abrupt Changes ◽  
Structural Differences ◽  
Interaction Scheme ◽  
Reversible Phase

Presented herein are detailed optical, thermal, spectroscopic and structural analyses of the phase transformation occurring in tapentadol hydrochloride (C14H24NO+·Cl−), a phenomenon already reported [Fischer et al. (2006); Patent: WO 2006000441 A2]. The thermal behaviour of the compound was studied using single-crystal X-ray diffraction, differential scanning calorimetry and Raman scattering measurements. The compound undergoes a first-order reversible phase transition at T heat = 318.0 (1) K, T cool = 300.0 (1) K, as assessed by the coexistence of both phases in the vicinity of the transition and the abrupt changes observed in the unit-cell parameters with temperature. The process is accompanied by clear thermosalient behaviour, with a conspicuous movement of the samples. On cooling, the transformation leads from a P212121 symmetry (Z′ = 1) to P21, with an abrupt change in β [90 ↔ 94.78 (1)°] and duplication of the asymmetric unit contents (Z′ = 2). The main structural differences observed across the transition are extremely small, with almost no changes in the stronger, non-covalent interaction scheme involving the `conventional' (N—H...Cl, O—H...Cl) hydrogen bonds.

Reversible phase transition of pyridinium-3-carboxylic acid perchlorate

2010 ◽  
Vol 66 (3) ◽  
pp. 387-395 ◽  
Author(s):  
Heng-Yun Ye ◽  
Li-Zhuang Chen ◽  
Ren-Gen Xiong
Keyword(s):  
Phase Transition ◽  
Carboxylic Acid ◽  
Relative Displacement ◽  
Temperature Phase ◽  
Scanning Calorimetry ◽  
Cell Parameters ◽  
Dsc Measurements ◽  
Reversible Phase Transition ◽  
Reversible Phase ◽  
Hydrogen Bonded

Pyridinium-3-carboxylic acid perchlorate was synthesized and separated as crystals. Differential scanning calorimetry (DSC) measurements show that this compound undergoes a reversible phase transition at ∼ 135 K with a wide hysteresis of 15 K. Dielectric measurements confirm the transition at ∼ 127 K. Measurement of the unit-cell parameters versus temperature shows that the values of the c axis and β angle change abruptly and remarkably at 129 (2) K, indicating that the system undergoes a first-order transition at T c = 129 K. The crystal structures determined at 103 and 298 K are all monoclinic in P21/c, showing that the phase transition is isosymmetric. The crystal contains one-dimensional hydrogen-bonded chains of the pyridinium-3-carboxylic acid cations, which are further linked to perchlorate anions by hydrogen bonds to form well separated infinite planar layers. The most distinct differences between the structures of the higher-temperature phase and the lower-temperature phase are the change of the distance between the adjacent pyridinium ring planes within the hydrogen-bonded chains and the relative displacement between the hydrogen-bonded layers. Structural analysis shows that the driving force of the transition is the reorientation of the pyridinium-3-carboxylic acid cations. The degree of order of the perchlorate anions may be a secondary order parameter.

A Reversible Non-disruptive Phase Transition Shown by the Zinc Iodide Dimethylformamide Complex ZnI2(dmf)2

1998 ◽  
Vol 54 (5) ◽  
pp. 663-670 ◽  
Author(s):  
R. A. Edwards ◽  
A. J. Easteal ◽  
O. P. Gladkikh ◽  
W. T. Robinson ◽  
M. M. Turnbull ◽  
...  
Keyword(s):  
Phase Transition ◽  
Transition Temperature ◽  
Intermolecular Forces ◽  
Scanning Calorimetry ◽  
Space Group ◽  
Cell Parameters ◽  
Reversible Phase Transition ◽  
Higher Temperature ◽  
High Temperature Form ◽  
Reversible Phase

At 228 K crystals of ZnI2(dmf)2 show a reversible phase transition which does not disrupt the lattice. Above the transition temperature the space group is C2/c and the cell contains eight symmetrically equivalent molecules. Cooling to below the transition temperature has little effect on the cell parameters or on the Zn- and I-atom positions, but the space group is now P21/n and the asymmetric unit comprises two conformationally different molecules. These arise from cooperative rotations of either ca +25 or −43° about the Zn—O bond of one of the dmf ligands in the high-temperature form. This displacive transition involves large movements of some atoms. The corresponding chloride and bromide are isomorphous with the higher temperature C2/c form, but it is only with the iodide that the weaker intermolecular forces permit the unusual phase change. The transition has been followed by differential scanning calorimetry, which gives an enthalpy change of 1.44 (5) kJ mol−1.

Phase Transition and Thermochromism of the Hybrid (C12H25NH3)2FeCl4

2006 ◽  
Vol 111 ◽  
pp. 55-58
Author(s):  
L.L. Guo ◽  
Y.D. Dai ◽  
H.X. Liu ◽  
Shi Xi Ouyang
Keyword(s):  
Phase Transition ◽  
Structural Changes ◽  
Energy Transition ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Thermal Gravimetry ◽  
Reversible Phase Transition ◽  
Rotational Motions ◽  
Xrd Patterns ◽  
Reversible Phase

This paper focuses on the structural change and the thermochromism of the phase transition of the hybrid (C12H25NH3)2FeCl4. The temperature and the structures of the phase transition is investigated by a thermal gravimetry (TG) and differential scanning calorimetry (DSC), an infrared spectra (IR) and X-ray diffraction (XRD) patterns. The UV adsorption spectra account for the thermochromism. The results suggest that the reversible phase transition arises from the structural changes of the organic chains. The thermochromism is presumably due to the electrons redistribution on the levels and to the energy transition to translational and rotational motions of the organic chains.

scholarly journals Tris(ethylenediamine) Cobalt(II) and Manganese(II) Nitrates

Crystals ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 472
Author(s):  
Miguel Cortijo ◽  
Ángela Valentín-Pérez ◽  
Mathieu Rouzières ◽  
Rodolphe Clérac ◽  
Patrick Rosa ◽  
...  
Keyword(s):  
Phase Transition ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
Scanning Calorimetry ◽  
Orbital Contribution ◽  
X Ray ◽  
Reversible Phase Transition ◽  
Heat Capacity Measurements ◽  
Reversible Phase

Octahedral tris(ethylenediamine) coordination complexes demonstrate helicoidal chirality, due to the arrangement of the ligands around the metal core. The enantiomers of the nitrate salts [Ni(en)3](NO3)2 and [Zn(en)3](NO3)2 spontaneously resolve to form a mixture of conglomerate crystals, which present a reversible phase transition from space group P6322 to enantiomorphic P6522 or P6122, with the latter depending on the handedness of the enantiomer. We report here the synthesis and characterization of [Mn(en)3](NO3)2 and [Co(en)3](NO3)2, which are isostructural to the Zn(II) and Ni(II) derivatives. The Mn(II) analogue undergoes the same phase transition centered at 150(2) K, as determined by single-crystal X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. The Co(II) derivative does not demonstrate a phase transition down to 2 K, as evidenced by powder X-ray diffraction and heat capacity measurements. The phase transition does not impact the magnetic properties of the Ni(II) and Mn(II) analogues; these high spin compounds display Curie behavior that is consistent with S = 1 and 5/2, respectively, down to 20 K, while the temperature-dependent magnetic moment for the Co(II) compound reveals a significant orbital contribution.

Morphological Transitions in Fluorinated and Non-Fluorinated Parylenes

1999 ◽  
Vol 565 ◽  
Author(s):  
Michael Morgen ◽  
Jie-Hua Zhao ◽  
Seung-Hyun Rhee ◽  
E. Todd Ryant ◽  
Huei-Min Ho ◽  
...  
Keyword(s):  
Significant Shift ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Two Phase ◽  
X Ray ◽  
Reversible Phase Transition ◽  
Morphological Transitions ◽  
Crystallinity Changes ◽  
Chain Contraction ◽  
Reversible Phase

AbstractA study of temperature-induced crystallinity changes in fluorinated and nonfluorinated parylene thin films using differential scanning calorimetry, thermal stress and wide angle x-ray diffraction measurements is presented. The nonfluorinated parylene (ppx-N) is shown to undergo two phase transitions between 200°C and 300°C. Both transitions show at least some degree of reversibility. The high temperature (β1 -β2) transition is accompanied by a sudden shift in stress, which is attributed to a contraction of the polymers chains. A single, reversible phase transition, occurring between 360°C and 400°C, is observed for fluorinated parylene (ppx-F). This transition is likewise marked by a significant shift in stress, and is apparently due to a similar chain contraction.

scholarly journals Nanocrystal, phase transformation and microstructure of Ni50Ti50 shape memory alloy

2018 ◽  
Vol 24 (02) ◽  
pp. 22-25
Author(s):  
Dovchinvanchig M ◽  
Chunwang Zhao
Keyword(s):  
Differential Scanning Calorimetry ◽  
Phase Transformation ◽  
Shape Memory Alloy ◽  
Shape Memory ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
One Step ◽  
Niti Matrix ◽  
Electronic Microscope

The nanocrystal, phase transformation and microstructure behavior of Ni50Ti50 shape memory alloy was investigated by scanning electronic microscope, X-ray diffraction and differential scanning calorimetry. The results showed that the microstructure of Ni-Ti binary alloy consists of the NiTi2 phase and the NiTi matrix phase. One-step phase transformation was observed alloy.

scholarly journals Crystallization and preliminary crystallographic analysis of manganese lipoxygenase

2014 ◽  
Vol 70 (4) ◽  
pp. 522-525 ◽  
Author(s):  
Anneli Wennman ◽  
Ernst H. Oliw ◽  
Saeid Karkehabadi
Keyword(s):  
Expression System ◽  
Crystallographic Analysis ◽  
Gaeumannomyces Graminis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cell Parameters ◽  
Apparent Homogeneity ◽  
Structural Differences ◽  
Position Specificity ◽  
Take All

Lipoxygenases constitute a family of nonhaem metal enzymes with catalytic iron or, occasionally, catalytic manganese. Lipoxygenases oxidize polyunsaturated fatty acids with position specificity and stereospecificity to hydroperoxides, which contribute to inflammation and the development of cancer. Little is known about the structural differences between lipoxygenases with Fe or Mn and the metal-selection mechanism. APichia pastorisexpression system was used for the production of the manganese lipoxygenase of the take-all fungus of wheat,Gaeumannomyces graminis. The active enzyme was treated with α-mannosidase, purified to apparent homogeneity and subjected to crystal screening and X-ray diffraction. The crystals diffracted to 2.6 Å resolution and belonged to space groupC2, with unit-cell parametersa= 226.6,b= 50.6,c= 177.92 Å, β = 91.70°.

scholarly journals Synthesis and Crystal Structure of the Bioinorganic Complex [Sb(Hedta)]·2H2O

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
Di Li ◽  
Guo-Qing Zhong
Keyword(s):  
Crystal Structure ◽  
Ethylenediaminetetraacetic Acid ◽  
Raw Materials ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Cell Parameters ◽  
Composition And Structure ◽  
Decomposition Processes ◽  
Distorted Trigonal Bipyramid

The antimony(III) complex [Sb(Hedta)]·2H2O was synthesized with ethylenediaminetetraacetic acid (H4edta) and antimonous oxide as main raw materials in aqueous solution. The composition and structure of the complex were characterized by elemental analysis, infrared spectra, single crystal X-ray diffraction, X-ray powder diffraction, thermogravimetry, and differential scanning calorimetry. The crystal structure of the antimony(III) complex belongs to orthorhombic system, space group Pna2(1), with cell parameters ofa=18.4823(18) Å,b=10.9408(12) Å,c=7.3671(5) Å,V=1489.7(2) Å3,Z=4, andDc=1.993 g cm−3. The Sb(III) ion is five-coordinated by two amido N atoms and three carboxyl O atoms from a single Hedta3−ligand, forming a distorted trigonal bipyramid geometry. The thermal decomposition processes of the complex include dehydration, oxidation, and pyrolysis of the ligand, and the last residue is Sb2O3at the temperature of 570°C.

scholarly journals Structure, Optical, and Thermal Properties of 9, 10-diphenylanthracene Crystals

Crystals ◽  
2019 ◽  
Vol 9 (10) ◽  
pp. 512 ◽  
Author(s):  
Liu ◽  
Zhu ◽  
Hu ◽  
Dong ◽  
Tan
Keyword(s):  
Single Crystal ◽  
Emission Wavelength ◽  
Molecular Formula ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Cell Parameters ◽  
Lattice Constants ◽  
Solution Methods ◽  
Fast Neutron Detection ◽  
Better Than

9,10-diphenylanthracene (DPA) single crystal is a promising scintillator material for fast-neutron detection. Two centimetre-sized polymorph crystals of DPA were grown by melting and solution methods (DPA-Melt and DPA-Solution, respectively), and characterised by single-crystal X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, fluorescence spectroscopy, UV-Vis absorbance spectroscopy, and thermogravimetric/differential scanning calorimetry. The DPA-Melt crystal possessed a P21/n structure, with excitation bands at approximately 331, 348, 367, and 387 nm, and the strongest emission wavelength at approximately 454 nm. On the other hand, the DPA-Solution crystal possessed a C2/c structure, with excitation bands at approximately 335, 353, 372, and 396 nm, and the strongest emission wavelength at approximately 468 nm. The two kinds of DPA crystals have the same molecular formula but different crystal structures, crystal lattice constants, and cell parameters. The theoretical density of the DPA-Solution crystal was 1.239 g/cm3, while that of the DPA-Melt crystal was 1.211 g/cm3. The two types of crystals exhibited the same melting point, but the thermal stability of the DPA-Solution crystal is better than that of the DPA-Melt crystal.

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