Reactions of thiosemicarbazones {R 1 R 2 C 2 dN 3 -N 2 (H)-C 1 (dS)-N 1 H 2 }, a multidonor class of ligands, with silver(I) halides in the presence of PPh 3 have yielded a variety of compounds, viz.: 6)), and (iii) monomers, [AgX(η 1 -S-Hpytsc)(PPh 3 ) 2 ] • CH 3 CN (R 1 ) pyridine, R 2 ) H, Hpytsc, X ) Br (7); Cl (8)). In contrast, silver(I) nitrate has formed only sulfur-bridged dimers, [Ag 2 (η 1 -N-µ-S-Hftsc) 2 (Ph 3 P) 2 ](NO 3 ) 2 (9) (R 1 ) furan, R 2 ) H, Hftsc), and [Ag 2 (η 1 -S-Hptsc) 2 (µ-S-Hptsc) 2 (Ph 3 P) 2 ](NO 3 ) 2 • 2CHCl 3 (10) (R 1 ) pyrrole, R 2 ) H, Hptsc) (Hpytsc ) pyridine-2-carbaldehyde thiosemicarbazone, Hptsc ) pyrrole-2-carbaldehyde thiosemicarbazone, Httsc ) thiophene-2-carbaldehyde thiosemicarbazone, Hftsc ) furan-2-carbaldehyde thiosemicarbazone, Hbtsc ) benzaldehyde thiosemicarbazone, Hactsc ) acetone thiosemicarbazone, and Haptsc ) acetophenone thiosemicarbazone). Complexes 1-10 are the first examples exhibiting new bonding modes (η 1 -S, µ-S, and µ-S-η 1 -N 3 ) in silver(I)thiosemicarbazone chemistry. The substituents at C 2 carbon appear to have significant influence on the nature of bonding in the complexes. The intermolecular interactions such as, NH • • • X (X ) S, Br, Cl, O), CH • • • π and CH • • • X (X ) S, Cl) have led to the formation of one-and two-dimensional (1D and 2D) networks. Interestingly, a novel feature is that some of the 2D networks encapsulate organic molecules in the voids.