Template effects of lithium salts on the crystallization of diazasulfates:X-ray structures of {THF center dot Li-2[O2S((NBu)-Bu-t)(2)]}(8)center dot2LiOH center dot 2LiCl and {(THF center dot Li)(2)[O2S((NBu)-Bu-t)(2)]center dot(THF)LiCl}(2)

The addition of 2 equiv of (BuLi)-Bu-n to solutions of O2S[N(H)R](2) (R = P r-i,Bu-t) produces the dilithium diazasulfates {Li-2[O2S((NPr)-Pr-i)(2)]}(n ) (2) and {THF.Li-2[O2S((NBu)-Bu-t)(2)]}(n) (3), which were characterized b y solid-state Li-7 and C-13 NMR spectroscopy. Crystals were obtained from a THF/n-hexane solution of 3 and determined by X-ray crystallography to be { THF.Li-2[O2S((NBu)-Bu-t)(2)]}(8).2LiOH.2LiCl (4), which consists of a 64-at om (Li20S8N16O18Cl2) cluster composed of two Li4O4 cubes and a central Li4O 4 step-shaped ladder. The eight [O2S((NBu)-Bu-t)(2)](2-) dianions in 4 exhi bit three distinct modes of bonding to the Li+ cations: (a) bis-(N,O),(N', O')-chelate, (b) N,O-chelate, bis-N',O'-monodentate, and (c) bis-(N, O),(N, N')-chelate, O'-monodentate. The synthesis of 3 in the presence of 1 equiv of LiCl produces the dimer {(THF.Li)(2)[O2S((NBu)-Bu-t)(2)].(THF)LiCl}(2) ( 5). The structure of 5 incorporates an 18-atom (Li6S2N4O4Cl2) quinary clust er in which two {[THF.Li(mu-O)(mu-O)(mu-(NBu)-Bu-t)](2)S} molecules are hel d together by two (THF.LiCl) units. The mean Li-Cl distance (2.348 Angstrom ) linking the {[THF.Li(mu-O)(mu-O)(u-(NBu)-Bu-t)](2)S} molecules to the (TH F.LiCl) units is significantly shorter than the corresponding value of 2.48 3 Angstrom within these units. Crystal data: 4, monoclinic, P2(1)/n, a = 18 .557(1) Angstrom, b = 15.731(1) Angstrom, c = 28.063(2) Angstrom, beta = 10 7.381(1)degrees, V = 7817.9(9) Angstrom(3), and Z = 2; 5, monoclinic, P2(1) /n, a = 11.583(3) Angstrom, b = 17.126(5) Angstrom, c = 13.891(4) Angstrom, beta = 94.613(4)degrees, V = 2747(1) Angstrom(3), and Z = 2.