THERMAL DECOMPOSITION OF MOLECULAR COMPLEXES: IV. FURTHER STUDIES OF THE β-QUINOL CLATHRATES

1966 ◽  
Vol 44 (12) ◽  
pp. 1373-1385 ◽  
Author(s):  
H. G. McAdie
Keyword(s):  
Thermal Decomposition ◽  
Guest Molecule ◽  
Molecular Complexes ◽  
X Ray Diffraction ◽  
Interpenetrating Networks ◽  
Guest Molecules ◽  
X Ray ◽  
Guest Species ◽  
Decomposition Increase ◽  
Thermal Stability Of

The endothermal decomposition of 18 β-quinol clathrates has been studied by thermo-analysis, calorimetry, and X-ray diffraction, and the decomposition process shown to be[Formula: see text]For those symmetrical guest molecules (M) which do not distort the β-quinol cavities from their normal dimensions, both temperatures and enthalpies of clathrate decomposition increase with increasing volume of the guest molecule. For those unsymmetrical guest species which require distortion of the cavities along their c-axis, temperatures and enthalpies of decomposition tend to decrease as the initial distortion required to accommodate the guest increases. Thermal stability of β-quinol clathrates is thus strongly influenced both by the size and shape of the guest molecule.The mechanism of thermal decomposition is suggested to involve a combination of the loss of stabilizing guest–wall interactions, together with increased thermal motion of the interpenetrating networks of hydrogen-bonded quinol molecules.

Inclusion compounds of plant growth regulators in cyclodextrins. V. 4-Chlorophenoxyacetic acid encapsulated in β-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin

2005 ◽  
Vol 61 (2) ◽  
pp. 207-217 ◽  
Author(s):  
Frantzeska Tsorteki ◽  
Kostas Bethanis ◽  
Nikos Pinotsis ◽  
Petros Giastas ◽  
Dimitris Mentzafos
Keyword(s):  
Guest Molecule ◽  
Crystal Packing ◽  
Host Molecule ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
Space Group ◽  
X Ray ◽  
Dimeric Complexes ◽  
The Mean ◽  
Chlorophenoxyacetic Acid

The crystal structures of 4-chlorophenoxyacetic acid (4CPA) included in β-cyclodextrin (β-CD) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TMβCD) have been studied by X-ray diffraction. The 4CPA/β-CD complex crystallizes as a head-to-head dimer in the space group C2 in the Tetrad packing mode. The packing modes of some β-CD dimeric complexes, having unique stackings, are also discussed. The 4CPA/TMβCD inclusion complex crystallizes in the space group P21 and its asymmetric unit contains two crystallographically independent complexes, complex A and complex B, exhibiting different conformations. The host molecule of complex A is significantly distorted, as a glucosidic residue rotated about the O4′—C1 and C4—O4 bonds forms an aperture where the guest molecule is accommodated. The phenyl moiety of the guest molecule of complex B is nearly perpendicular to the mean plane of the O4n atoms. The conformations of the guest molecules of the two complexes are similar. The crystal packing consists of antiparallel columns as in the majority of the TMβCD complexes published so far.

Investigation of the disorder of dibromo- and dichloromethane in their tri-ortho-thymotide clathrates using X-ray diffraction and solid-state 2H NMR spectroscopy

2011 ◽  
Vol 89 (7) ◽  
pp. 854-862
Author(s):  
Glenn A. Facey ◽  
Ilia Korobkov
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Guest Molecule ◽  
Type B ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Twofold Axis ◽  
H Nmr ◽  
Heavy Atoms

The tri-ortho-thymotide (TOT) clathrates of dibromo- and dichloromethane were characterized by single crystal X-ray diffraction at 200 K and solid-state 2H NMR spectroscopy as a function of temperature. The host structure was found to be typical of other cage-type TOT clathrates. The X-ray results showed a substantial amount of disorder among the guest molecules. In both clathrates, multiple guest molecule positions could be modeled. The heavy atoms of all the guest molecule positions lie approximately in the same plane, with some out-of-plane distortion. The guest molecules were of two different types in positions symmetric about the crystallographic twofold rotation axis: type A guests, with carbon atoms well removed from the crystallographic twofold axis, and type B guests, with carbon atoms very close to the twofold axis. The 2H NMR spectra for the guests confirmed that the disorder was dynamic. The experimental results could be accounted for by the presence of three simultaneous types of molecular motion, all fast with respect to the 2H quadrupolar interaction: (i) twofold molecular flips about the molecular C2 symmetry axis, (ii) exchange between the type A and type B sites in a single plane, and (iii) a two-site libration of the plane containing the heavy atoms of the A and B guest sites with a temperature-dependent amplitude.

Structural Transition of Trimethylamine Hydrate by Methane or Hydrogen Inclusion

2020 ◽  
Author(s):  
Minjun Cha
Keyword(s):  
Structural Transition ◽  
Guest Molecule ◽  
Clathrate Hydrate ◽  
Hydrogen Gas ◽  
Time Dependent ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Inclusion Process ◽  
Diffraction Patterns

<p>Recently, several alkylamine hydrates have been studied in an effort to reveal the structural transitions from semi- to ‘canonical’ clathrate hydrate in the presence of secondary guest molecules. Trimethylamine (TMA) is known to form the semi-clathrate hydrate, and it has been reported that the structural transition of the TMA semi-clathrate hydrate may not occur in the presence of hydrogen gas as a secondary guest molecule. This paper reports the structural transition of trimethylamine(TMA) hydrate induced by the type of guest molecules. Powder X-ray diffraction patterns of (TMA + H<sub>2</sub>) hydrates show the formation of hexagoanl P6/mmm hydrate, but those of (TMA + CH<sub>4</sub>) hydrates indicate the formation of cubic Fd3m hydrate. Without gaseous guest molecule, the crystal structure of pure TMA hydrate is identified as hexagonal P6/mmm. Therefore, inclusion of gaseous methane in TMA hydrate can induce the structural transition from hexagonal to cubic hydrate or the formation of metastable cubic hydrate. To clearly reveal this possibility, we also check the time-dependent structural patterns of binary (TMA + CH<sub>4</sub>) hydrates from 1 to 14 days, and the results show that the structural transition of TMA hydrate from hexagonal P6/mmm to cubic Fd3m hydrate structure can occur during the methane inclusion process.</p>

scholarly journals Construction of pillar[4]arene[1]quinone–1,10-dibromodecane pseudorotaxanes in solution and in the solid state

2020 ◽  
Vol 16 ◽  
pp. 2954-2959
Author(s):  
Xinru Sheng ◽  
Errui Li ◽  
Feihe Huang
Keyword(s):  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Guest Molecule ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Π Interactions ◽  
Host Molecules ◽  
Complexation Stoichiometry

We report novel pseudorotaxanes based on the complexation between pillar[4]arene[1]quinone and 1,10-dibromodecane. The complexation is found to have a 1:1 host–guest complexation stoichiometry in chloroform but a 2:1 host–guest complexation stoichiometry in the solid state. From single crystal X-ray diffraction, the linear guest molecules thread into cyclic pillar[4]arene[1]quinone host molecules in the solid state, stabilized by CH∙∙∙π interactions and hydrogen bonds. The bromine atoms at the periphery of the guest molecule provide convenience for the further capping of the pseudorotaxanes to construct rotaxanes.

Thermal decomposition of magnesium sesquicarbide

1983 ◽  
Vol 48 (7) ◽  
pp. 1963-1968 ◽  
Author(s):  
Bohumil Hájek ◽  
Pavel Karen ◽  
Vlastimil Brožek
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Data ◽  
Arrhenius Equation ◽  
Kinetic Equations ◽  
Decomposition Reaction ◽  
Point Of View ◽  
X Ray Diffraction ◽  
X Ray ◽  
Diffraction Patterns ◽  
Thermal Stability Of

The structure of Mg2C3 and the course of its decomposition were studied. The powder X-ray diffraction patterns were analyzed to obtain the lattice parameters for hexagonal Mg2C3, a = 743.4 ± 0.5 pm, c = 1 056.4 ± 1.6 pm. Thermal decomposition data were obtained for temperatures 670-740 °C and pressure 130 Pa; they could be fitted satisfactorily by kinetic equations for various processes, including the 1 st order decomposition reaction, and so the controlling phenomenon of the reaction cannot be deduced based on the kinetic data. The 1 st order rate constants and reaction halflives were evaluated for various temperatures and approximated by the Arrhenius equation to calculate the parameters AA = 1.97 . 1014 s-1, EA = 333 kJ mol-1. The conditions of synthesis of Mg2C3 are discussed from the point of view of the choice of a suitable hydrocarbon for the reaction with magnesium. The thermal stability of the sesquicarbide increases with increasing pressure; it could be formed from dicarbide and sustained even at a temperature of 1 450 °C by applying a pressure as high as 6 GPa.

scholarly journals THERMAL DECOMPOSITION OF MOLECULAR COMPLEXES: III. UREA INCLUSION COMPOUNDS OF MONOSUBSTITUTED ALIPHATIC SERIES

1963 ◽  
Vol 41 (9) ◽  
pp. 2144-2153 ◽  
Author(s):  
H. G. McAdie
Keyword(s):  
Thermal Decomposition ◽  
Inclusion Compounds ◽  
Guest Molecule ◽  
Molecular Complexes ◽  
Decomposition Temperature ◽  
Urea Inclusion Compounds ◽  
Guest Species ◽  
Alkyl Bromides ◽  
Sufficient Energy ◽  
Urea Inclusion

Examination of the thermal decomposition of urea inclusion compounds has been extended to complexes of the even-numbered members of the following aliphatic series: n-alcohols, n-alkylamines, n-alkyl bromides, and n-carboxylic acids. The decomposition has been studied primarily by differential thermal analysis and an attempt made to correlate the observed decomposition temperatures and heats of decomposition with the particular guest species. The decomposition mechanism appears to involve acquisition of sufficient energy by the guest molecule to permit its diffusion from the canal, the decomposition temperature being related to the activation energy required for this diffusion process.

scholarly journals Niclosamide methanol solvate and niclosamide hydrate: structure, solvent inclusion mode and implications for properties

2014 ◽  
Vol 70 (8) ◽  
pp. 758-763 ◽  
Author(s):  
Bethany I. Harriss ◽  
Claire Wilson ◽  
Ivana Radosavljevic Evans
Keyword(s):  
Guest Molecule ◽  
Crystal Packing ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Consistent Picture ◽  
First Time ◽  
Facile Transformation

Structural studies have been carried out of two solid forms of niclosamide [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide, NCL], a widely used anthelmintic drug, namely niclosamide methanol monosolvate, C13H8Cl2N2O4·CH3OH or NCL·MeOH, and niclosamide monohydrate, denoted HA. The structure of the methanol solvate obtained from single-crystal X-ray diffraction is reported for the first time, elucidating the key host–guest hydrogen-bonding interactions which lead to solvate formation. The essentially planar NCL host molecules interactviaπ-stacking and pack in a herringbone-type arrangement, giving rise to channels along the crystallographicaaxis in which the methanol guest molecules are located. The methanol and NCL molecules interactviashort O—H...O hydrogen bonds. Laboratory powder X-ray diffraction (PXRD) measurements reveal that the initially phase-pure NCL·MeOH solvate readily transforms into NCL monohydrate within hours under ambient conditions. PXRD further suggests that the NCL monohydrate, HA, is isostructural with the NCL·MeOH solvate. This is consistent with the facile transformation of the methanol solvate into the hydrate when stored in air. The crystal packing and the topology of guest-molecule inclusion are compared with those of other NCL solvates for which the crystal structures are known, giving a consistent picture which correlates well with known experimentally observed desolvation properties.

Synthesis and Structure of a Clathrated Two-Dimensional Metal-Organic Framework: [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2·H2O (L = Bis(1-pyrazinylethylidene)hydrazine)

2008 ◽  
Vol 73 (1) ◽  
pp. 24-31
Author(s):  
Dayu Wu ◽  
Genhua Wu ◽  
Wei Huang ◽  
Zhuqing Wang
Keyword(s):  
Metal Organic Framework ◽  
Channel Structure ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Square Planar ◽  
Metal Organic ◽  
Aqueous Meoh ◽  
Organic Framework

The compound [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2 was obtained by the reaction of Cd(ClO4)2, bis(1-pyrazinylethylidene)hydrazine (L) and 4,4'-bipyridine in aqueous MeOH. Single-crystal X-ray diffraction has revealed its two-dimensional metal-organic framework. The 2-D layers superpose on each other, giving a channel structure. The square planar grids consist of two pairs of shared edges with Cd(II) ion and a 4,4'-bipyridine molecule each vertex and side, respectively. The square cavity has a dimension of 11.817 × 11.781 Å. Two guest molecules of bis(1-pyrazinylethylidene)hydrazine are clathrated in every hydrophobic host cavity, being further stabilized by π-π stacking and hydrogen bonding. The results suggest that the hydrazine molecules present in the network serve as structure-directing templates in the formation of crystal structures.

Structural properties of the guest species in diacyl peroxide/urea inclusion compounds: an X-ray diffraction investigation

1990 ◽  
Vol 431 (1882) ◽  
pp. 245-269 ◽  
Keyword(s):  
Single Crystal ◽  
Structural Properties ◽  
Inclusion Compounds ◽  
X Ray Diffraction ◽  
Channel Axis ◽  
Guest Molecules ◽  
X Ray ◽  
Urea Inclusion Compounds ◽  
Diacyl Peroxide ◽  
Urea Inclusion

In this paper we report single crystal X-ray diffraction studies of urea inclusion compounds containing diacyl peroxides (dioctanoyl peroxide (OP), diundecanoyl peroxide (UP), lauroyl peroxide (LP)) as the guest component. In these inclusion compounds, the host (urea) molecules crystallize in a hexagonal structure that contains linear, parallel, non-intersecting channels (tunnels). The guest (diacyl peroxide) molecules are closely packed inside these channels with a periodic repeat distance that is incommensurate with the period of the host structure along the channel axis. Furthermore, there is pronounced inhomogeneity within the guest structure: within each single crystal, there are regions in which the guest molecules are three-dimensionally ordered, and other regions in which they are only one-dimensionally ordered (along the channel axis). Although it has not proven possible to ‘determine’ the guest structures in the conventional sense, substantial information concerning their average periodicities and their orientational relationships with respect to the host has been deduced from single crystal X-ray diffraction photographs recorded at room temperature. For OP/urea, UP/urea and LP/urea, the guest structure in the three-dimensionally ordered regions is monoclinic, and six types of domain of this monoclinic structure can be identified within each single crystal. The relative packing of diacyl peroxide molecules is the same in each domain, and the different domains are related by 60° rotation about the channel axis. For each of these inclusion compounds, the offset between the ‘heights’ of the guest molecules in adjacent channels is the same ( ca . 4.6 Å (4.6 x 10 -10 m)) within experimental error, suggesting that the relative interchannel packing of the guest molecules is controlled by a property of the diacyl peroxide group. In addition to revealing these novel structural properties, the work discussed in this paper has more general relevance concerning the measurement and interpretation of single crystal X-ray diffraction patterns that are based on more than one three-dimensionally periodic reciprocal lattice. Seven separate reciprocal lattices are required to rationalize the complete X-ray diffraction pattern from each diacyl peroxide/urea crystal studied here.

Formation and Thermal Stability of Nd0.32Y0.68Si1.7 Layers Formed by Channeled Ion Beam Synthesis

1998 ◽  
Vol 514 ◽  
Author(s):  
M. F. Wu ◽  
A. Vantomne ◽  
S. Hogg ◽  
H. Pattyn ◽  
G. Langouche ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Ion Beam ◽  
Hexagonal Structure ◽  
Orthorhombic Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Good Crystalline Quality ◽  
Ion Beam Synthesis ◽  
Thermal Stability Of

ABSTRACTThe Nd-disilicide, which exists only in a tetragonal or an orthorhombic structure, cannot be grown epitaxially on a Si(111) substrate. However, by adding Y and using channeled ion beam synthesis, hexagonal Nd0.32Y0.68Si1.7 epilayers with lattice constant of aepi = 0.3915 nm and cepi = 0.4152 nm and with good crystalline quality (χmin of Nd and Y is 3.5% and 4.3 % respectively) are formed in a Si(111) substrate. This shows that the addition of Y to the Nd-Si system forces the latter into a hexagonal structure. The epilayer is stable up to 950 °C; annealing at 1000 °C results in partial transformation into other phases. The formation, the structure and the thermal stability of this ternary silicide have been studied using Rutherford backscattering/channeling, x-ray diffraction and transmission electron microscopy.

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