Five-coordinate and six-coordinate 2-methyl-2-propanethiolato complexes of zirconium, [Li(DME)(3)][Zr(SCMe(3))(5)] (1) and [(THF)Li]Zr-2(SCMe(3))(6) (2), were obtained from the ZrCl4/LiSCMe(3) reaction system. The control of the Zr coordination number, by the ether ligands, THF or DME, bound to Li, is demonstrated by the conversion of 2 into 1 upon dissolution in DME. 1 and 2 were crystallographically characterized. The structures are extensively disordered. Crystal data follow : 1, hexagonal P6(3)/m, a = b = 12.496(3) Angstrom, c = 17.561(9) Angstrom, Z = 2, V = 2375(1) Angstrom(3), R = 5.0%, R(w) = 6.8%; 2, trigonal R32, a = b = 11.813(3) Angstrom c = 28.37(1) Angstrom, Z = 3, V = 3428(1) Angstrom(3), R = 5.2%, R(w) = 6.4%.