Five versatile non-chelating heterocyclic ligands, benzimidazo[1,2- b]benzo[ e]-1-thia-3-azacyclicheptane (bbch), 1,2-bis[(4-pyridinyl)-sulfanylmethyl]benzene (psb), 2,3-bis[(4-pyridinyl)-sulfanylmethyl]quinoxaline (psmq), 2-[( p-pyridinyl)-sulfanylmethyl]-pyrimidine (ppsp), and 2-[( m-pyridinyl)-sulfanylmethyl]pyrimidine (mpsp) were designed and prepared. Self-assembly between silver nitrate and bbch resulted in a coordination polymer [Ag 2(bbch) 2(NO 3) 2] n ( 1) with a double silver atom chain, while treatment of silver perchlorate and bbch under the same conditions generated a discrete mononuclear complex [Ag(bbch) 2](ClO 4) ( 2). A 30-membered macrocyclic complex [Ag 2(psb) 2](ClO 4) 2 ( 3) was obtained by the stoichiometric reaction of silver perchlorate and psb. A coordination polymer [Ag(psmq)ClO 4] n ( 4) with a zigzag chain was obtained by the reaction of silver perchlorate and psmq. Reaction of silver nitrate with ppsp and mpsp gave rise to polymers [Ag 2(ppsp) 2(NO 3) 2] n ( 5) and [Ag 2(mpsp) 2(NO 3) 2] n ( 6) with single stranded helical chain structures.