Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number of different coordination modes are found within the complexes including η(2)-allyl, aryl, and OR groups binding to Ag(I). AgSbF(6) gives two types of three-dimensional (3-D) coordination polymer with unusual topologies, along with a discrete Ag(2)L(2) capsule dependent on reaction stoichiometry and reaction conditions. Isostructural coordination chain structures are found with AgBF(4) and AgClO(4), while use of Ag(CF(3)SO(3)) gives two-dimensional (2-D) and 3-D coordination polymers through bridging triflate anions.