The stacking of aryl groups once again appears to be structure-determining. The title complex, which is accessible by reaction of [Zn(CH2SiMe3)2] with two equivalents of 2,4,6-tBuC6H2SH in the presence of Et2O, has an SZnS angle of ca. 160° and ZnS distances of only 2.196 Å. In contrast, the ZnO distance is relatively large and explains the ready cleavability of the ether ligands. Zinc thiolates are of interest as model complexes for zinc-containing proteins.