Crystal-to-crystal photodimerization of trans-cinnamamides

In the crystals of trans-4-methylcinnamamide, C10HT11NO (I), trans-4-chlorocinnamamide, C9H8ClNO (II), trans-3-(2-thienyl)acrylamide, C7H7NOS (III), and trans-cinnamamide, C9H9NO (IV), the shortest intermolecular C...C distances between the C=C double bonds are 3.670 (2), 3.632 (2), 3.762 (3) and 4.120 (2) A, respectively, for the pair of molecules related by a center of symmetry. The structure analysis was also carried out for trans-2-(p-chlorophenyl)-cis4-(p-chlorophenyl)-1-trans-3-diamidocyclobutane, C18H16Cl2N2O2 (V), which is the alpha-type photodimer of (II). The NH...O hydrogen-bond networks in (I)-(III) are composed of two-dimensional pleated sheets, and those in (IV) and (V) of one-dimensional flat ribbons. The single crystals of (I), (II) and (IV) were photoirradiated with a 250 W ultra-high-pressure mercury lamp through a band-pass filter or a long-pass filter for 2-5 h. The photodimer was produced in each crystal with retention of the single-crystal form. The populations of the dimers were converged to 86.2 (4), 48.4 (6) and 4.5 (2)% in the refinement of the crystals after photoirradiation, (I'), (II') and (IV'), respectively. Although the intermolecular N-H...O hydrogen-bond network remained in (I') and (II'), the network was partly broken in (IV') in the process of photoreaction.