Ja. Zerkowski et al., NEW VARIETIES OF CRYSTALLINE ARCHITECTURE PRODUCED BY SMALL CHANGES IN MOLECULAR-STRUCTURE IN TAPE-COMPLEXES OF MELAMINES AND BARBITURATES, Journal of the American Chemical Society, 116(10), 1994, pp. 4305-4315
This paper describes the crystal structures of a series of seven 1:1 c
omplexes between N,N'-bis(m-X-phenyl)-melamine and 5,5-diethylbarbitur
ic acid (X = H, F, Cl, Br, I, CH3, and CF3). This series provides smal
l perturbations on the structures of molecules (N,N'-bis(p-X-phenyl)me
lamines) used ina previous study (Zerkowski, J. A.; MacDonald, J.C.; S
eto, C.T.; Wierda, D.A.; Whitesides, G.M. J. Am. Chem. Soc. In press).
Both the meta and para complexes crystallize as hydrogen-bonded ''tap
es''. With the phenyl substituent in the meta position, however, the m
elamines can adopt a greater number of molecular conformations; this f
eature leads to a greater variety of orientations of packing. The meta
series packs in both linear and crinkled tape motifs, and four of the
seven complexes are solvates. By contrast, the para series, which use
d the same set of phenyl substituents, always yielded linear tapes and
crystals without solvent in the lattice. Inclusion of solvent increas
es the packing coefficients of members of the meta series to values ap
proximately equal to those of the para series. The multiplicity of mol
ecular conformations available to the meta series is probably largely
responsible for the clathration of solvent, which does not rely upon s
pecific non-covalent interactions except in the case of the m-iodo com
plex with acetonitrile. The wider range of crystalline architecture in
the meta series attests only to the kinetic accessibility of these pa
cking formats; polymorphic phases of greater thermodynamic stability m
ay occur. Polymorphism has not been investigated in the series of meta
-substituted compounds.