A nonlinear optical chromophore, 4,5-bis(4-dimethylaminophenyl)-2-(4-nitrophenyl)imidazole, was investigated by X-ray crystallography. The study focused on coplanarity among several aromatic rings, including phenyls and imidazole. Two phenyl rings with NMe2 groups are twisted by 46.39(3) degrees from each other. However, they are twisted by 23.05(5) degrees and 46.84(3) degrees from the imidazole, respectively. These unequal twists were elucidated by different conjugation pathways from the donors to the acceptor. The phenyl ring with the NO2 group is twisted by only 6.76(6) degrees from the imidazole.