Optical and X-ray diffraction characterizations of crystals I and II of (2Z)-2-(4-bromophenyl)-3-[4-(dimethylamino)phenyl]prop-2-enenitrile (Z-4-BrPhDMAPhACN) are reported. I and II belong to the same monoclinic space group and have nearly identical unit-cell dimensions [I: a = 11.0169(2); b = 6.02041(11); c = 21.8541(4); (β) 98.4082(18). II: a = 11.0475(6); b = 6.0273(3); c = 21.8533(11); (β) 98.315(5)]. Crystals I and II were formed under different conditions and have different crystal habits and colors: crystals I are yellow blocks, whereas crystals II are small, orange needles. I and II show absorption maxima (λabs) in solution at 404 nm and emission (λem) maxima at 501 nm (I) and at 502 nm (II). However, their emission maxima are different in the solid state: I shows an emission at 512 nm and a shoulder at 534 nm, whereas II exhibits a λem maximum at 582 nm. The differences in solid-state photoluminescence were attributed to variations in the crystal morphology and to the crystal habit and size. Both...