The crystal structure of the alimemazine (trimeprazine) cation radical, a phenothiazine drug molecule, has been determined from three-dimensional X-ray diffraction data and refined by least-squares methods. Cell constants were a 10.674 9(4), b 12.741 9(5), c 9.509 9(4) A, a 110.863(3), p 103.433(3), y 66.671 (4)", Z = 2. The molecule is planar, the angle between the best planes for the two benzene rings being 1.9(3)", The C-S-C angle is 102.6(4)" and S-C bonds are 1.709(11) and 1.71 O(7) A in length. The side-chain is protonated at the nitrogen atom and asymmetrically placed in relation to the tricyclic system.The pharmacological properties of phenothiazine drugs has stimulated research on their structural features in the solid state by X-ray in an attempt to provide information on the structure-activity relationships in this class of However, in spite of the biological activity of the cation radical and of the interesting solidstate properties of their ion radical salts9*10 the number of X-ray diffraction studies on this type of species is few. 11-'In previous works we have studied the alimemazine cationphenothiazine], a phenothiazine drug with a side-chain branched due to the presence of a methyl group at the level of the second carbon,14*15 by means of e.s.r. The results showed conformational changes in solution in relation to unbranched radicals. To determine how this difference in the side-chain affects the structural characteristics of ALMZ' in the solid state, we have carried out an X-ray diffraction study of this radical. The results are compared with those previously reported for other phenothiazine cation radicals, mainly chlorpromazine (CPZ'), because the single crystals contained the same type of counterion.