Reactions of Ti(NMe2)(2)Cl-2 with a wide range of primary alkyl and arylamines RNH2 afforded the corresponding 5-coordinate imido titanium compounds Ti(NR)Cl-2(NHMe2)2 (R = Bu-i (1), Pr-i (2), CH2Ph (3), Ph (4), 2,6-C6H3Me2 (5), 2,6-(C6H3Pr2)-Pr-i (6), 2,4,6-C6H2F3 (7), 2,3,5,6-C6HF4 (8), C6F5 (9), 4-C6H4Cl (10), 2,3,5,6-C6HCl4 (11), 2-C6H4CF3 (12), 2-(C6H4Bu)-Bu-i (13)). The compounds 1-13 are monomeric in solution but in the solid state form either N-H center dot center dot center dot Cl hydrogen bonded dimers or chains or perfluorophenyl pi-stacked chains, depending on the imido R-group. The compound 13 was also prepared in a "one-pot" synthesis from RNH2 and Ti(NMe2)(4) and Me3SiCl. Reaction of certain Ti(NR)Cl-2(NHMe2)(2) compounds with an excess of pyridine afforded the corresponding bis- or tris-pyridine analogues [Ti(NR)Cl-2(py)(x)](y) (x = 3, y = 1; x = y = 2), and the structure of Ti-2(NC6F5)(2)Cl-2(U-Cl)(2)(py)(4) shows g-stacking of perfluorophenyl rings. Reaction of Ti(NMe2)(2)Cl-2 with cross-linked aminomethyl polystyrene gave quantitative conversion to the corresponding solid-supported titanium imido complex. This paper represents the first detailed study of how supramolecular structures of imido compounds may be influenced by simple variation of the imido ligand N-substituent.