Reaction of [(PPh2=NSiMe3)(PPh2=S)CSn:](2) (1) with elemental sulfur in toluene afforded [{(mu-S) (SnC)-C-IV(PPh2=NSiMe3)(PPh2=S)}(3)Sn-II(mu(3)-S)] (2) and [CH2(PPh2=NSiMe3)(PPh2=S)] (3). Compound 2 comprises a (SnS)-S-II moiety coordinated with the Sn-IV and S atoms of a trimeric 2-stannathiomethendiide {(PPh2=NSiMe3)(PPh2=S)CSn(mu-S)}(3). Compound 2 has been characterized by NMR spectroscopy, Sn-119 Mossbauer studies, X-ray crystallography, and theoretical studies. Sn-119 NMR spectroscopy and Mossbauer studies show the presence of Sn-IV and Sn-II atoms in 2. X-ray crystallography suggests that the (SnS)-S-II moiety does not have multiple bond character. Theoretical studies illustrate that the C-methanediide-Sn bonds comprise a lone pair orbital on each C-methanediide atom and an C-Sn occupied sigma orbital.