The compounds [Li-3(Me(3)SiNCH(2)CH(2))(3)N(THF)(2)], 2, and {(mu(3)-Cl)Li3H4[(Me(3)SiNCH(2)CH(2))(3)N](2)}, 3, were synthesized and characterized by H-1, C-13, Si-29, and Li-7 NMR spectroscopies, and their structures were determined by single crystal X-ray crystallography. Compound 2 was shown to contain a trigonal monopyramidal lithium center while 3 utilizes a LiCl to link two amido triamine ligands together. Crystal data : 2, triclinic with a = 9.2035(8) Angstrom, b = 9.579(2) Angstrom, c = 19.881(2) Angstrom, alpha = 94.98(1)degrees, beta = 93.27(1)degrees, gamma = 103.51(1)degrees, V = 1692.4(4) Angstrom(3), Z = 2, space group P (1) over bar, R = 0.0592; 3, trigonal with a = 12.449(1) Angstrom, b = 12.449(1) Angstrom, c = 28.251(6) Angstrom, V = 3791.7(9) Angstrom(3), Z = 3, space group P3(2), 50:50 (y) over bar, (x) over bar, z twin, R = 0.0249. Variable-temperature H-1 and Li-7 NMR spectral studies reveal a dynamic behavior of 2 in solution. (HH)-H-1-H-1 DQF COSY, (HC)-H-1-C-13-heterocorrelated 2D, and VT NMR experiments confirm that the structure of 3 in solution is the same as that in the solid state.