The new functionalized aryl-imido-bridged cyclopentadienyl titanium compounds [TiCl(η⁵-C₅Me₅){μ-NR}]₂, R = 4-X-C₆H₄ (X = CN (2a), X = Cl (2b), X = I (2c), X = (OMe) (2d)); 3,5-(OMe)₂C₆H₃ (2e) were prepared and their appropriateness as building blocks for constructing supramolecular structures was evaluated. The presence of a functional group in the para position within the aryl-imido ligand leads to the formation of 1D arrangement for 2a, 2c and 2d through halogen bonding or hydrogen bonding interactions. In particular, the imido titanium complex 2c forms a supramolecular chain with a [MgCl₂·(THF)₄] unit generated in the synthesis where the metallic fragments are connected by C–ICl–Mg halogen bonding interactions (XB), being the first example within group 2 metals where the XB motif M–ClI–C appears.