Variability in the Structures of [4-(Aminomethyl)pyridine]silver(I) Complexes through Effects of Ligand Ratio, Anion, Hydrogen Bonding, and π-Stacking

The reaction of the asymmetric 4-(aminomethyl)pyridine (4-amp) ligand with silver(I) salts of trifluoromethanesulfonate
(triflate, OTf-), trifluoroacetate (tfa-), or tetrafluoroborate (BF4-) have produced a variety of one- and two-dimensional
structural motifs depending upon the ratio in which the components are mixed. When the proportion of ligand to
metal is 1:1, linear coordination polymers are formed with silver(I) OTf- (1) and tfa- (2). Altering the ratio to 2:1,
a linear polymer of corner-shared boxes (3) is formed with tfa-, a linear box-in-box “chain link” polymer (4) is
formed with OTf-, and a two-dimensional sheet (5) is constructed with BF4-. Addition of 5,5‘-dimethyl-2,2‘-bipyridine
to a solution of 4-ampAgBF4 disrupts the polymerization of the previous structure and results in the construction
of the infinite metal−metal bound strings of 6a regardless of ratio of amp to silver present. H-bonding, π-stacking,
and closed-shell Ag−Ag interactions are all involved in the overall conformations of the final structures.