The N-alkylated azatitanatranes N(CH2CH2NR)3TiCl [R = Me (1), Et (2), i-Pr (3)] have been prepared and 1 and 3 structurally characterized by X-ray crystallography : 1, orthorhombic, Pmna, a = 11.293(3) angstrom, b = 11.977(3) angstrom, c = 9.722(3) angstrom, V = 1314.96 angstrom3, Z = 4, R = 0.0629; 3, cubic, Pa3, a = 15.928(4) angstrom, V = 4040.95 angstrom3, Z = 8, R = 0.0792. The halide ligand in 2 and 3 could be replaced by more labile ligands by chloride abstraction using the appropriate silver salts. A single-crystal X-ray structure analysis of N(CH2CH2NEt)3TiOSO2CF3 (4), the first azatrane-triflate to be reported, was carried out. Crystal data for 4 : triclinic, P1BAR (No. 2), a = 16.039(4) angstrom, b = 16.473(4) angstrom, c = 8.954(3) angstrom, alpha = 105.75-degrees, beta = 106.17(2)-degrees, gamma = 107.54(2)-degrees, V = 1996.33 angstrom3, Z = 4, R = 0.0842. The titanium amido complexes reported here may find use as building blocks in more complex structural arrays.