A reaction of Cp(2)Ti(SH)(2) with n-BuSnCl(OH)(2) gave two unusual ionic compounds; the cation in both is a hexatitanium cluster, [Cp(6)Ti(6)O(8)](2+), while the anion is a six membered cyclic (chair form) [n-Bu(3)Sn(3)Cl(SH)(3)(S)(3)](-) in one and acyclic [n-Bu(3)Sn(3)Cl(3)(SH)(3)(S)(2)](-) in the other. Besides X-ray crystallography, theoretical studies have also been completed to understand the structures of these complexes.