Effect of Counteranions in Self-Assembled Silver(I)-Coordination Polymers of 4-Aminobenzonitrile

Four homoleptic coordination polymers of general composition [Ag­(4ABN)4/2]­X (4ABN ≡ 4-aminobenzonitrile) were synthesized and characterized by X-ray single crystal structure analysis. For X = NO3– (P21/n, Z = 4; 1), PF6– (P21/n, Z = 4; 2), and ClO4– (P21/n, Z = 4; 3), similar topologies with undulated layers (63 nets) are found, which are separated by the anions. For X = SO3CF3– (P1̅, Z = 2; 4), a one-dimensional structural fragment with polymeric double-bridged cationic chains again separated by the anions is formed. It is rationalized that different dimensionalities of the polymeric structural fragments depend upon the size of the separating counteranions. This simple rule can also be applied for already known ∞2[Ag­(4ABN)4/2]­BF4.