Reactions of Hg(OAc)(2) with 2 equiv of TabHPF(6) [TabH = 4-(trimethylammonio)benzenethiol] in MeCN/MeOH afforded a mononuclear linear complex [Hg(Tab)(2)](PF6)(2) (1). By using 1 as a precursor, a new family of mercury(II) zwitterionic thiolate complexes, [Hg-2(Tab)(6)](PF6)(4)(.)2MeCN (2(.)2MeCN), [Hg(Tab)(2)(SCN)](PF6) (3), [Hg(Tab)(2)(SCN)(2)] (4), [Hg(Tab)l(2)] (5), {[Hg(Tab)(2)](4)[Hgl(2)][Hg(2)l(6)]}(PF6)(2)(NO3)(4) (6), [Hg(Tab)(2)][Hgl(4)] (7), [Hg(Tab)(2)][HgCl2(SCN)(2)] (8), [TabTab](2)[Hg3Cl10] (9), and [Hg-2(Tab)(6)](3)(PF6)Cl-11 (10), were prepared and characterized by elemental analysis, IR spectra, UV-vis spectra, H-1-NMR, and single-crystal X-ray crystallography. The [Hg-2(Tab)(6)](4+) tetracation of 2 or 10 contains an asymmetrical Hg2S2 rhomb with an inversion center lying on the midpoint of the (HgHg)-Hg-... line. The Hg atom of the [Hg(Tab)(2)](2+) dication of 3 is coordinated to one SCN-, forming a rare T-shaped coordination geometry, while in 4, the Hg atom of [Hg(Tab)(2)](2+) is coordinated to two SCN-, forming a seesaw-shaped coordination geometry. Through weak secondary (HgS)-S-... coordinations, each cation in 3 is further linked to afford a one-dimensional zigzag chain. The trigonal [Hg(Tab)l(2)] molecules in 5 are held together by weak secondary (HgI)-I-... and Hg...S interactions, forming a one-dimensional chain structure. In 6, the four [Hg(Tab)(2)](2+) clications, one Hgl(2) molecule, one [Hg(2)l(6)](2-) dianion, one PF6-, and four NO3- anions are interconnected by complicated secondary (HgI)-I-... and (HgO)-O-... interactions, forming a scolopendra-like chain structure. The secondary (HgI)-I-... interactions, [Hg(Tab)(2)](2+) and [Hgl(4)](2-) in 7, are combined to generate a one-dimensional chain structure, while [Hg(Tab)(2)](2+) and [HgCl2(SCN)(2)](2-) in 8 are interconnected by secondary (HgN)-N-... interactions to form a one-dimensional zigzag chain structure. Compound 9 consists of two [Tab-Tab](2+) clications and one [Hg3Cl10](4-) tetraanion. The facile approach to the construction of 2-8 and 10 from 1 may be applicable to the mimicking of a coordination sphere of the Hg sites of metallothioneins.