[Ag 2 L 2 (NO 3 ) 2 ] n (1), [HgL0.52OAc2]n (2), [HgL 2 I 2 ] n (3), [Ag3L23(NO3)3]n (4) and [HgL 3 I 2 ] n (5) were assembled by the reactions of L 2 and L 3 (L 2 =1,2-bis[4-(3-pyridyl)pyrimidinylthiomethyl]benzene, L 3 =1,3-bis[4-(3-pyridyl)pyrimidinylthiomethyl]benzene) with AgNO 3 , Hg(OAc) 2 and HgI 2 . The structural motifs of these complexes are multiform, from 3D interpenetrating networks and corrugated 2D networks to a 1D single stranded helix. It is found that conformation changes of the ligands after interaction with the metal salts occur due to positional isomerism of the xylyl groups and the effect of the metal ions.