The influence of solvent and anion on the formation of coordination polymers between silver(I) and 3,6-bis(pyridin-3-yl)-1,2,4,5-tetrazine (3,3Ј-pytz), a bridging ligand that can adopt both cisoid and transoidconformations, is reported. Reaction of AgPF 6 in MeCN with 3,3Ј-pytz in CH 2 Cl 2 gives ([{Ag(NCMe) 2 }(-3,3Ј-pytz)][PF 6 ]⅐MeCN) ϱ , 1, of AgPF 6 in MeNO 2 and 3,3Ј-pytz in CH 2 Cl 2 gives ([{Ag 2 (-3,3Ј-pytz) 2 }(-3,3Ј-pytz)][PF 6 ] 2 ⅐ 4MeNO 2 ) ϱ , 2, and of AgCF 3 SO 3 in MeCN and 3,3Ј-pytz in CH 2 Cl 2 gives {[Ag(-3,3Ј-pytz)]CF 3 SO 3 } ϱ , 3. These cationic coordination polymers exclusively form chain structural motifs. That in 1, ([{Ag(NCMe) 2 }(-3,3Јpytz)] ϩ ) ϱ , has a castellated construction with each tetrahedral silver(I) center coordinated by two solvent molecules as well as two linking transoid-oriented 3,3Ј-pytz bridges (Ag . . . Ag 13.210 Å) in a 1:1 polymeric chain. That in 2, ([{Ag 2 (-3,3Ј-pytz) 2 }(-3,3Ј-pytz)] 2ϩ ) ϱ , is novel. It is the first coordination polymer to exhibit both cisoid and transoid conformations of a bridging ligand coordinated to the same metal center. Pairs of silver(I) centers are linked by pairs of cisoid-oriented 3,3Ј-pytz molecules (Ag . . . Ag ϭ 11.695 Å) to form [Ag 2 (-3,3Ј-pytz) 2 ] motifs, which are bridged, in turn, by transoid-oriented 3,3Ј-pytz molecules (Ag . . . Ag ϭ 13.318 Å) to form a 3:2 ligand:metal infinite polymeric zigzag chain. That in 3, {[Ag(-3,3Ј-pytz)] ϩ } ϱ , has a zigzag architecture despite being based on linear silver(I) centers. Transoid-oriented 3,3Ј-pytz molecules link silver(I) centers (Ag . . . Ag 13.225 Å) to give a 1:1 ligand:metal infinite polymeric zigzag chain. The chains aggregate in parallel