The structures of model compounds for the polyaromatic quinone diimine polymers were determined. These polymers were obtained by polycondensation of tricyclic quinones with aromatic diamines in the presence of TiCl 4 and DABCO. The N-phenyldiimine and monoimine derivatives of the following quinones were synthesized: naphthoquinone, 2-methyl- and 2-tert-butyloxazolonaphthoquinone, 2,2'-dimethylbis(oxazolo)benzoquinone, and bisthiophenobenzoquinone. X-ray single-crystal structure determinations are reported for the following derivatives: N,N'-bis(p-fluorophenyl)naphthoquinone 1,4-diimine, N-phenyl-2-tert-butylnaphtho[2,3-d]oxazole-4,9-dione 4-imine and 9-imine, N-(p-fluorophenyl)-2-tert-butylnaphtho[2,3-d]oxazole-9-one 4-imine, N-phenyl-2-isobutylnaphtho[2,3-d]oxazole-9-one diimine, and N,N'-diphenylbenzo[1,2-b:4,5-b']dithiophene-4,8-dione diimine. The following common features are observed for these structures: the central ring systems are planar in contrast to the anthraquinone diimine derivatives in which the central ring system is buckled, the N-phenyl ring is twisted out of the plane of the central ring system, and the N-phenyl rings are twisted toward the ring with the heteroatom and away from the C-H group on the adjacent ring. Molecular modeling calculations are found to be in agreement with the X-ray structures. The implications of the crystal structures of the model compounds for the polymeric structures are discussed