A low-temperature modification of hexa-tert-butyldisilane and a new polymorph of 1,1,2,2-tetra-tert-butyl-1,2-diphenyldisilane

2014 ◽  
Vol 70 (7) ◽  
pp. 697-701 ◽  
Author(s):  
Stefan Scholz ◽  
Hans-Wolfram Lerner ◽  
Jan W. Bats
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Low Temperature ◽  
High Temperature Phase ◽  
Temperature Phase ◽  
Torsion Angles ◽  
Lattice Constants ◽  
Bond Lengths ◽  
Twofold Axis ◽  
Reversible Phase Transition

Crystals of hexa-tert-butyldisilane, C24H54Si2, undergo a reversible phase transition at 179 (2) K. The space group changes fromIbca(high temperature) toPbca(low temperature), but the lattice constantsa,bandcdo not change significantly during the phase transition. The crystallographic twofold axis of the molecule in the high-temperature phase is replaced by a noncrystallographic twofold axis in the low-temperature phase. The angle between the two axes is 2.36 (4)°. The centre of the molecule undergoes a translation of 0.123 (1) Å during the phase transition, but the conformation angles of the molecule remain unchanged. Between the two tri-tert-butylsilyl subunits there are six short repulsive intramolecular C—H...H—C contacts, with H...H distances between 2.02 and 2.04 Å, resulting in a significant lengthening of the Si—Si and Si—C bonds. The Si—Si bond length is 2.6863 (5) Å and the Si—C bond lengths are between 1.9860 (14) and 1.9933 (14) Å. Torsion angles about the Si—Si and Si—C bonds deviate by approximately 15° from the values expected for staggered conformations due to intramolecular steric H...H repulsions. A new polymorph is reported for the crystal structure of 1,1,2,2-tetra-tert-butyl-1,2-diphenyldisilane, C28H46Si2. It has two independent molecules with rather similar conformations. The Si—Si bond lengths are 2.4869 (8) and 2.4944 (8) Å. The C—Si—Si—C torsion angles deviate by between −3.4 (1) and −18.5 (1)° from the values expected for a staggered conformation. These deviations result from steric interactions. Four Si—C(t-Bu) bonds are almost staggered, while the other four Si—C(t-Bu) bonds are intermediate between a staggered and an eclipsed conformation. The latter Si—C(t-Bu) bonds are about 0.019 (2) Å longer than the staggered Si—C(t-Bu) bonds.

Crystal structure and phase transition of thermoelectric SnSe

2016 ◽  
Vol 72 (3) ◽  
pp. 310-316 ◽  
Author(s):  
Mattia Sist ◽  
Jiawei Zhang ◽  
Bo Brummerstedt Iversen
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Site Occupancy ◽  
Functional Materials ◽  
Atomic Displacement ◽  
High Temperature Phase ◽  
Temperature Phase ◽  
Lattice Constants ◽  
Temperature Phase Transition ◽  
Atomic Displacement Parameters

Tin selenide-based functional materials are extensively studied in the field of optoelectronic, photovoltaic and thermoelectric devices. Specifically, SnSe has been reported to have an ultrahigh thermoelectric figure of merit of 2.6 ± 0.3 in the high-temperature phase. Here we report the evolution of lattice constants, fractional coordinates, site occupancy factors and atomic displacement factors with temperature by means of high-resolution synchrotron powder X-ray diffraction measured from 100 to 855 K. The structure is shown to be cation defective with a Sn content of 0.982 (4). The anisotropy of the thermal parameters of Sn becomes more pronounced approaching the high-temperature phase transition (∼ 810 K). Anharmonic Gram–Charlier parameters have been refined, but data from single-crystal diffraction appear to be needed to firmly quantify anharmonic features. Based on modelling of the atomic displacement parameters the Debye temperature is found to be 175 (4) K. Conflicting reports concerning the different coordinate system settings in the low-temperature and high-temperature phases are discussed. It is also shown that the high-temperatureCmcmphase is not pseudo-tetragonal as commonly assumed.

O(2) spin model and the Kosterlitz–Thouless’s phase transition

2021 ◽  
pp. 747-759
Author(s):  
Jean Zinn-Justin
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Low Temperature ◽  
Correlation Length ◽  
Lattice Model ◽  
Coulomb Gas ◽  
High Temperature Phase ◽  
Spin Model ◽  
Temperature Phase ◽  
Distance Properties

At low temperature, the large distance properties of the O(2) spin lattice model can be described by the O(2) non-linear σ-model. The latter model is free and massless in two dimensions. The origin of this peculiarity can be found in the local structure of the field manifold: for N = 2, the O(N) sphere reduces to a circle, which cannot be distinguished locally from a straight line. Because the physical fields are sin θ or cos θ, or equivalently e± iθ, instead of θ, a field renormalization is necessary, and temperature-dependent anomalous dimensions are generated. However, the free θ action cannot describe the long-distance properties of the lattice model for all temperatures, since a high temperature analysis of the corresponding spin model shows that the correlation length is finite at high temperature, and thus a phase transition is required. In fact, it is necessary to take into account the property that θ is a cyclic variable. This condition is irrelevant at low temperature, but when the temperature increases, classical configurations with singularities at isolated points, around which θ varies by a multiple of 2π become important. The action of these configurations (vortices) can be identified with the energy of a neutral Coulomb gas, which exhibits a transition between a low temperature of bound neutral molecules and a high temperature phase of a plasma of free charges. The Coulomb gas can be mapped onto the sine-Gordon (sG) model, mapping in which the low- and high-temperature regions of the models are exchanged. This correspondence helps to understand some properties of the famous Kosterlitz-Thouless (KT) phase transition, which separates an infinite correlation length phase without order, the low-temperature phase of the O(2) spin model, from a finite correlation length phase, the high-temperature phase of the O(2) spin model.

A low temperature reversible phase transition for 1,1'-bis-(ferrocenyldimethylsilyl)ferrocenylene, (η5-FcSiMe2C5H4)2Fe, an oligomeric model for silyleneferrocenylene polymers

2000 ◽  
Vol 78 (11) ◽  
pp. 1511-1518 ◽  
Author(s):  
Mikhail Yu Antipin ◽  
Ivan I Vorontsov ◽  
Irene I Dubovik ◽  
Vladimir Papkov ◽  
Francisco Cervantes-Lee ◽  
...  
Keyword(s):  
Phase Transition ◽  
Solid State ◽  
Phase Space ◽  
Low Temperature ◽  
High Temperature Phase ◽  
Temperature Phase ◽  
X Ray Diffraction ◽  
Space Group ◽  
Reversible Phase Transition ◽  
Reversible Phase

We have reinvestigated the solid state structure of 1,1'-bis-(ferrocenyldimethylsilyl)ferrocenylene, (η5-FcSiMe2C5H4)2Fe, Fc = (η5-C5H5)Fe(η5-C5H4). Using a DSC technique we observed a reversible phase transition for this compound at 169(3)K with ΔH = 1.1 kJ/mol, and ΔS = 6.54 J/mol K. A single crystal X-ray diffraction study has demonstrated that this phase change involves a transformation from a high temperature phase, space group P21/c, Z = 2, to a triclinic low temperature phase, space group P[Formula: see text], Z = 4. The phase transition involves the loss of the molecular crystallographic center of symmetry and rotations about the terminal and central cyclopentadienyl ring pairs. The results are compared to those reported for ferrocene.Key words: solid state, phase transition, silyleneferrocenylene.

Single-crystal structure refinement of NaTiSi2O6 clinopyroxene at low temperatures (298 < T < 100 K)

2003 ◽  
Vol 59 (6) ◽  
pp. 730-746 ◽  
Author(s):  
Günther J. Redhammer ◽  
Haruo Ohashi ◽  
Georg Roth
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Low Temperature ◽  
Bond Length ◽  
Octahedral Site ◽  
Tetrahedral Site ◽  
Temperature Phase ◽  
Bond Lengths ◽  
Distortion Parameters ◽  
Low Temperature Phase

The alkali-metal clinopyroxene NaTi3+Si2O6, one of the rare compounds with trivalent titanium, was synthesized at high temperature/high pressure and subsequently investigated by single-crystal X-ray diffraction methods between 298 and 100 K. One main difference between the high- and the low-temperature form is the sudden appearance of two different Ti3+—Ti3+ interatomic distances within the infinite chain of the TiO6 octahedra just below 197 K. This change can be seen as direct evidence for the formation of Ti—Ti singlet pairs in the low-temperature phase. Mean Ti—O bond lengths smoothly decrease with decreasing temperature and the phase transition is associated with a slight jump in the Ti—O bond length. The break in symmetry, however, causes distinct variations, especially with respect to the two Ti—Oapex bond lengths, but also with respect to the four Ti—O bonds in the equatorial plane of the octahedron. The TiO6 octahedron appears to be stretched in the chain direction with a slightly larger elongation in the P\bar 1 low-temperature phase compared with the C2/c high-temperature phase. Polyhedral distortion parameters such as bond-length distortion and octahedral angle variance suggest the TiO6 octahedron in P\bar 1 to be closer to the geometry of an ideal octahedron than in C2/c. Mean Na—O bond lengths decrease with decreasing temperature and the variations in individual Na—O bond lengths are the result of variations in the geometry of the octahedral site. The tetrahedral site acts as a rigid unit, which does not show pronounced changes upon cooling and through the phase transitions. There are neither large changes in bond lengths and angles nor in polyhedral distortion parameters, for the tetrahedral site, when they are plotted. In contrast with the C2/c → P21/c phase transition, found especially in LiMSi2O6 clinopyroxenes, no very large variations are found for the tetrahedral bridging angle. Thus, it is concluded that the main factor inducing the phase transition and controlling the structural variations is the M1 octahedral site.

Topological polymorphism and temperature-driven topotactic transitions of metal–organic coordination polymers

CrystEngComm ◽  
2020 ◽  
Vol 22 (38) ◽  
pp. 6295-6301
Author(s):  
Vadim A. Dubskikh ◽  
Anna A. Lysova ◽  
Denis G. Samsonenko ◽  
Danil N. Dybtsev ◽  
Vladimir P. Fedin
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Solid State ◽  
Low Temperature ◽  
High Temperature Phase ◽  
Phase Changes ◽  
Organic Ligands ◽  
Temperature Phase ◽  
Metal Organic ◽  
Low Temperature Phase

A facile crystal-to-crystal solid-state phase transition between a low-temperature phase and a high temperature phase changes the MOF topology and involves a significant rearrangement of bulky organic ligands.

Reversible high-temperature phase transition of a manganese(II) formate framework with imidazolium cations

2013 ◽  
Vol 69 (6) ◽  
pp. 616-619 ◽  
Author(s):  
Bi-Qin Wang ◽  
Hai-Biao Yan ◽  
Zheng-Qing Huang ◽  
Zhi Zhang
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Low Temperature ◽  
Variable Temperature ◽  
Structural Phase ◽  
High Temperature Phase ◽  
Mirror Plane ◽  
Temperature Phase ◽  
Temperature Structure ◽  
Imidazolium Cations

A new metal–formate framework, poly[1H-imidazol-3-ium [tri-μ2-formato-manganese(II)]], {(C3H5N2)[Mn(HCOO)3]}n, was synthesized and its structural phase transition was studied by thermal analysis and variable-temperature X-ray diffraction analysis. The transition temperature is around 435 K. The high-temperature phase is tetragonal and the low-temperature phase is monoclinic, with a β angle close to 90°. The relationship of the unit cells between the two phases can be described as:aHT= 0.5aLT+ 0.5bLT;bHT= −0.5aLT+ 0.5bLT;cHT = 0.5cLT. In the high-temperature phase, both the framework and the guest 1H-imidazol-3-ium (HIm) cations are disordered; the HIm cations are located about 2mmsites and were modelled as fourfold disordered. The Mn and a formate C atom are located on fourfold rotary inversion axes, while another formate C atom is on a mirror plane. The low-temperature structure is ordered and consists of two crystallographically independent HIm cations and two crystallographically independent Mn2+ions. The phase transition is attributable to the order–disorder transition of the HIm cations.

Monoclinic-to-orthorhombic phase transition of the hexamethylenetetramine–2-methylbenzoic acid (1/2) cocrystal with temperature-dependent dynamic molecular disorder

2016 ◽  
Vol 72 (12) ◽  
pp. 971-980 ◽  
Author(s):  
Tze Shyang Chia ◽  
Ching Kheng Quah
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Low Temperature ◽  
Structural Phase ◽  
Point Group ◽  
High Temperature Phase ◽  
Temperature Phase ◽  
Temperature Dependent ◽  
Space Group ◽  
Low Temperature Phase

As a function of temperature, the hexamethylenetetramine–2-methylbenzoic acid (1/2) cocrystal, C6H12N4·2C8H8O2, undergoes a reversible structural phase transition. The orthorhombic high-temperature phase in the space groupPccnhas been studied in the temperature range between 165 and 300 K. At 164 K, at2phase transition to the monoclinic subgroupP21/cspace group occurs; the resulting twinned low-temperature phase was investigated in the temperature range between 164 and 100 K. The domains in the pseudomerohedral twin are related by a twofold rotation corresponding to the matrix (100/0-10/00-1. Systematic absence violations represent a sensitive criterium for the decision about the correct space-group assignment at each temperature. The fractional volume contributions of the minor twin domain in the low-temperature phase increases in the order 0.259 (2) → 0.318 (2) → 0.336 (2) → 0.341 (3) as the temperature increases in the order 150 → 160 → 163 → 164 K. The transformation occurs between the nonpolar point groupmmmand the nonpolar point group 2/m, and corresponds to a ferroelastic transition or to at2structural phase transition. The asymmetric unit of the low-temperature phase consists of two hexamethylenetetramine molecules and four molecules of 2-methylbenzoic acid; it is smaller by a factor of 2 in the high-temperature phase and contains two half molecules of hexamethylenetetramine, which sit across twofold axes, and two molecules of the organic acid. In both phases, the hexamethylenetetramine residue and two benzoic acid molecules form a three-molecule aggregate; the low-temperature phase contains two of these aggregates in general positions, whereas they are situated on a crystallographic twofold axis in the high-temperature phase. In both phases, one of these three-molecule aggregates is disordered. For this disordered unit, the ratio between the major and minor conformer increases upon cooling from 0.567 (7):0.433 (7) at 170 Kvia0.674 (6):0.326 (6) and 0.808 (5):0.192 (5) at 160 K to 0.803 (6):0.197 (6) and 0.900 (4):0.100 (4) at 150 K, indicating temperature-dependent dynamic molecular disorder. Even upon further cooling to 100 K, the disorder is retained in principle, albeit with very low site occupancies for the minor conformer.

scholarly journals The order/disorder phase transition of hypophosphorous acid H3PO2

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Martin Nastran ◽  
Berthold Stöger
Keyword(s):  
Phase Transition ◽  
Hydrogen Bonding ◽  
High Temperature ◽  
Low Temperature ◽  
Hydrogen Bonds ◽  
Rotation Axis ◽  
High Temperature Phase ◽  
Temperature Phase ◽  
Hypophosphorous Acid ◽  
Disorder Phase Transition

Abstract Hypophosphorous acid, H3PO2 is dimorphic with a phase transition in the 200–225 K range. The H3PO2 molecules are connected by hydrogen bonding to infinite chains extending in the [100] direction. In the high-temperature phase (P21212, Z ′ = 1 2 ${Z}^{\prime }=\frac{1}{2}$ ), the hydrogen bonds are disordered about a two-fold rotation axis. On cooling below the phase transition temperature, the hydrogen bonds become ordered, resulting in a symmetry reduction of the klassengleiche type of index 2. In the low-temperature phase (P212121, Z ′ = 1 ${Z}^{\prime }=1$ ), the c parameter is doubled with respect to the high-temperature phase. The hydrogen-bonding topology of the high- and low-temperature phases are double-infinite directed and undirected linear graphs, respectively.

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