ISSN:
1572-8854
Keywords:
Diels-Alder adduct
;
molecular mechanics
;
MOPAC
;
bond asymmetry
;
ring conformations
;
absorption errors
Source:
Springer Online Journal Archives 1860-2000
Topics:
Geosciences
,
Physics
Notes:
Abstract In the solid state the 2∶1 Diels-Alder adduct between spiro[4.2]hepta-1,3-diene and p-benzoquinone has a planar cyclohexadione ring with a center of symmetry. Both planar and boat conformations have been observed in similar systems, and the relative stability of the two conformers is of interest. The adduct in the gas phase should contain a mirror plane perpendicular to the cyclohexadione ring; however, a data set collected on a crystal in a capillary resulted in a structure where some bond lengths related by this mirror plane differed by more than 4σ in the solid state. Molecular mechanics, MOPAC, and the Cambridge Structural Data Base were used to investigate the factors influencing the conformation of the cyclohexadione ring and the asymmetry across the noncrystallographic mirror plane. The energy differences between the planar and nonplanar ring system is small, and the conformation is determined by crystal packing. No reason for the bond length asymmetry could be found, and a recollection of data on a crystal exposed to the environment led to a structure with statistically equivalent bond lengths.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01667038
Permalink
