The structures and dynamics of a family of crystalline ansa-metallocenes, [(C5H4)(2)-C(2)Me(4)]TiX(2) (X = F (1), Cl (2), Br (3), and I (4)), have been elucidated by the joint application of solid state NMR and single crystal X-ray diffraction techniques. X-ray crystal structures at ambient temperature indicate a single molecule with noncrystallographic 2-fold symmetry in the asymmetric unit of 1. The structure of 2 comprises two distinct layers which are each formed from only one of the two crystallographically distinct molecules found in the asymmetric unit. These two molecules have the same conformation, but do not have C-2 point symmetry. The structure of 3 has four molecules per asymmetric unit; one has axial symmetry, but the others deviate from this to a greater extent than do the molecules of 2. A layer structure with bromine atoms at the layer surfaces is discernible in 3, but in contrast to 2 each layer contains all of the crystallographically distinct molecules. The structure of 4 has a single molecule in its asymmetric unit, of similar nonaxial conformation to those of 2. The most noticeable feature is channels of iodine atoms parallel to the c-axis. The eight distinct molecules of these structures are placed into three conformational categories based on their deviation from axial symmetry.