SOLID-STATE NMR-STUDIES OF THE MOLECULAR-MOTION OF PYRIDINE IN ITS TRI-O-THYMOTIDE CLATHRATE

被引:17
作者
FACEY, GA [1 ]
RATCLIFFE, CI [1 ]
RIPMEESTER, JA [1 ]
机构
[1] NATL RES COUNCIL CANADA,STEACIE INST MOLEC SCI,OTTAWA,ON K1A 0R6,CANADA
关键词
D O I
10.1021/j100032a030
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
When crystallized from pyridine, tri-o-thymotide forms a clathrate compound with the solvent as guest molecule. In the confined space of the cage, the pyridine molecule exhibits considerable motional freedom. At 77 K the solid state H-2 NMR spectrum is consistent with the molecules undergoing a restricted in-plane motion. The 2H NMR data also show that at temperatures above 77 K the molecules undergo an out-of-plane libration as well as 180 degrees flips about their 2-fold axis. The barrier to this activated process was evaluated from line shape simulations. The C-13 CP/MAS NMR data obtained by using the dipolar dephasing technique confirm the models for the molecular motion established by H-2 NMR. The NMR data are compared to those from single crystal X-ray diffraction, which provide little evidence regarding molecular motion.
引用
收藏
页码:12249 / 12256
页数:8
相关论文
共 37 条
[1]   CROSS POLARIZATION AND MAGIC ANGLE SAMPLE SPINNING NMR-SPECTRA OF MODEL ORGANIC-COMPOUNDS .3. EFFECT OF THE C-13-H-1 DIPOLAR INTERACTION ON CROSS POLARIZATION AND CARBON-PROTON DEPHASING [J].
ALEMANY, LB ;
GRANT, DM ;
ALGER, TD ;
PUGMIRE, RJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (22) :6697-6704
[2]  
ALLEMAND J, 1981, CRYST STRUCT COMMUN, V10, P33
[3]   STRUCTURE OF THE TRI-ORTHO-THYMOTIDE-ETHYL METHYL SULFOXIDE (2-1) CLATHRATE - CRYSTALLOGRAPHIC ESTIMATION OF THE ENANTIOSELECTIVITY [J].
ALLEMAND, J ;
GERDIL, R .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1982, 38 (AUG) :2312-2315
[4]   THE TRI-ORTHO THYMOTIDE-2-BROMOBUTANE (2-1) CLATHRATE AT 125-K [J].
ALLEMAND, J ;
GERDIL, R .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1982, 38 (MAY) :1473-1476
[5]   ABSOLUTE-CONFIGURATION OF TRI-ORTHO-THYMOTIDE AND ITS CAGE CLATHRATE INCLUSION CAVITY [J].
ARADYELLIN, R ;
GREEN, BS ;
KNOSSOW, M ;
TSOUCARIS, G .
TETRAHEDRON LETTERS, 1980, 21 (04) :387-390
[6]   ENANTIOMER RECOGNITION AND GUEST-HOST CONFIGURATIONAL CORRELATION IN CRYSTALS OF TRI-ORTHO-THYMOTIDE CLATHRATE INCLUSION-COMPOUNDS [J].
ARADYELLIN, R ;
GREEN, BS ;
KNOSSOW, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (03) :1157-1158
[7]   CHIRAL DISCRIMINATION IN CRYSTALLINE TRI-ORTHO-THYMOTIDE CLATHRATE INCLUSION COMPLEXES - CHEMICAL AND CRYSTALLOGRAPHIC STUDIES [J].
ARADYELLIN, R ;
GREEN, BS ;
KNOSSOW, M ;
TSOUCARIS, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (14) :4561-4571
[8]  
ARADYELLIN R, 1984, INCLUSION COMPOUNDS, V3, pCH9
[9]  
ARADYELLIN R, 1985, J INCLUSION PHENOM, V3, P317
[10]   8-MEMBERED AND HIGHER-MEMBERED RING COMPOUNDS .6. CIS-DI-ORTHO-THYMOTIDES AND TRI-O-THYMOTIDES [J].
BAKER, W ;
GILBERT, B ;
OLLIS, WD .
JOURNAL OF THE CHEMICAL SOCIETY, 1952, (APR) :1443-1446