Investigations of the phase transitions in thiourea inclusion compounds with cycloheptane, cyclooctane, and cyclooctanone

被引:25
|
作者
Maris, T
Henson, MJ
Heyes, SJ
Prout, K [1 ]
机构
[1] Chem Crystallog Lab, 9 Parks Rd, Oxford OX1 3PD, England
[2] Inorgan Chem Lab, Oxford OX1 3QR, England
关键词
D O I
10.1021/cm991173u
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Variable temperature single-crystal X-ray diffraction and solid-state NMR experiments have been performed on the thiourea cycloheptane (TC7), cyclooctane (TC8), and cyclooctanone (TCO8) inclusion compounds. Three different phases have been evidenced for TC7 and four for TC8, while only one phase change at high temperature has been found for TCO8. At room temperature, the cyclooctane and cycloheptane adducts exhibit the classical rhombohedral lattice (space group R (3) over barc). In these structures, the well-resolved host thiourea structure is composed of one-dimensional nonintersecting channels running along the c axis. The guest molecules, located in the center of the channels, are highly disordered as confirmed by the solid-state C-13 NMR spectra. Lowering temperature leads to a monoclinic phase resulting from the distortion of the room-temperature lattice where the guest molecules still have some degrees of disorder. Refinement has been performed with a model involving two cycloalkane rings. For TC8, a supplementary phase with a doubling of the b axis is observed below 200 K, having two apparently ordered cyclooctane rings with the same conformation. The cyclooctanone adduct, TCO8, is already monoclinic at room temperature with an ordered guest molecule stabilized within the thiourea channels by a hydrogen bond. Upon heating, a phase change can be detected by solid-sate NMR and X-ray powder diffraction just before decomposition.
引用
收藏
页码:2483 / 2492
页数:10
相关论文
共 50 条
  • [1] PHASE TRANSITIONS IN THE THIOUREA CYCLOOCTANE INCLUSION COMPOUND.
    Maris, T.
    Henson, M. J.
    Prout, C. K.
    Heyes, S. J.
    ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES, 1999, 55 : 406 - 406
  • [2] ON CONFORMATIONS OF CYCLOHEPTANE AND CYCLOOCTANE IN THE GAS-PHASE
    DOROFEEVA, OV
    GURVICH, LV
    MASTRYUKOV, VS
    JOURNAL OF MOLECULAR STRUCTURE, 1985, 129 (1-2) : 165 - 168
  • [3] Phase transitions and molecular dynamics in the cyclohexane/thiourea inclusion compound
    Desmedt, A
    Kitchin, SJ
    Guillaume, F
    Couzi, M
    Harris, KDM
    Bocanegra, EH
    PHYSICAL REVIEW B, 2001, 64 (05):
  • [4] Structural properties of low-temperature phase transitions in the prototypical thiourea inclusion compound: Cyclohexane/thiourea
    Pan, Zhigang
    Desmedt, Arnaud
    MacLean, Elizabeth J.
    Guillaume, Francois
    Harris, Kenneth D. M.
    JOURNAL OF PHYSICAL CHEMISTRY C, 2008, 112 (03): : 839 - 847
  • [5] Diffuse scattering and phase transitions in aperiodic inclusion compounds
    Rabiller, P.
    Toudic, B.
    Guerin, L.
    Mariette, C.
    Hollingsworth, M.
    ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES, 2014, 70 : C621 - C621
  • [6] CALORIMETRIC STUDY OF PHASE-TRANSITIONS IN THE THIOUREA CARBON-TETRACHLORIDE INCLUSION COMPOUND
    SEKII, M
    MATSUO, T
    SUGA, H
    JOURNAL OF INCLUSION PHENOMENA AND MOLECULAR RECOGNITION IN CHEMISTRY, 1990, 9 (03): : 243 - 251
  • [7] SOLID-PHASES AND PHASE-TRANSITIONS OF CYCLOHEPTANE
    SNYDERMAN, DM
    ADAMS, JM
    MCDOWELL, AF
    CONRADI, MS
    BUNNELLE, WH
    JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (24): : 6234 - 6236
  • [8] C-13 MAGIC ANGLE SPINNING NMR INVESTIGATIONS OF THIOUREA INCLUSION-COMPOUNDS
    MULLER, K
    MAGNETIC RESONANCE IN CHEMISTRY, 1992, 30 (03) : 228 - 234
  • [9] INCLUSION COMPOUNDS OF UREA AND THIOUREA WITH CATIONIC SURFACTANTS
    CADWALLADER, DE
    RICHARDS, JB
    JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY, 1965, 42 (04) : 337 - +
  • [10] INFRARED SPECTRA OF SOME THIOUREA INCLUSION COMPOUNDS
    NISHIKAWA, M
    CHEMISTRY & INDUSTRY, 1963, (06) : 256 - 257