In order to determine the role of carboxamido nitrogen and thiolato sulfur donors on the structure and properties of metal complexes, we have synthesized the designed ligand N,N'-napthalenebis(o-mercaptobenzamide) (NpPepSH 4 ) with an N 2 S 2 donor set. In the deprotonated form, NpPepS 4 - binds nickel(II) to afford the diamagnetic complex (Et 4 N) 2 [Ni(NpPepS)] (1) with square-planar geometry. The ligand frame of NpPepS 4 - wraps around the Ni(II) center in an unexpected butterfly fashion presumably due to steric interactions. The [Ni(NpPepS)] 2 - unit further coordinates to Ni(II) and Pd(II) to give trimeric thiolato-bridged complexes (Et 4 N) 2 [Ni(Ni{NpPepS}) 2 ] (2) and (Et 4 N) 2 [Pd(Ni{NpPepS}) 2 ] (3). The structure of the [Ni(CH 3 OH) 6 ] 2 + salt of 3 namely, [Ni(CH 3 OH) 6 ][Pd(Ni{NpPepS}) 2 ] (3') reveals a novel slant chair structure. Unlike the previously reported similar trimeric complexes, the N 2 NiS 2 PdS 2 NiN 2 moiety in 3' is planar with slant naphthalene rings attached on both ends.