Synthesis and Structure of Coordination Polymers of Ag(I) with Isomeric (Aminomethyl)pyridines. Formation of A Novel Circular Helicate and 2-D Networks via Ag···Ag Contacts and Coordination Shell Expansion under Anion Control

Reaction between Ag(I) salts and the three isomers of (aminomethyl)pyridines, viz., 2-amp, 3-amp, and 4-amp, lead to either discrete or polymeric (1-D and 2-D) structures influenced by anions and closed shell Ag.Ag contacts. Characterization data for Ag(2-amp)BF(4) (1) follow: monoclinic, space group C2/c, with a = 16.788(2) A, b = 11.5719(6) A, c = 11.3864(7) A, beta = 123.671(8) degrees, and Z = 8. For Ag(2)(2-amp)(3)(PF(6))(2) (2): monoclinic, space group P2(1)/a, with a = 10.029(7) A, b = 20.291(12) A, c = 13.907(6) A, beta = 95.38(5) degrees, and Z = 4. For Ag(2)(3-amp)(3)(PF(6))(2) (4): triclinic, space group P1, with a = 10.4482(7) A, b = 11.1468(9) A, c = 12.2720(11) A, alpha = 81.018(7) degrees, beta = 80.668(6) degrees, gamma = 80.977(6) degrees, and Z = 2. For Ag(4-amp)BF(4).0.75CH(3)CN (5): orthorhombic, space group C222(1), with a = 9.272(2) A, b = 16.164(12) A, c = 27.851(2) A, and Z = 8. For Ag(4-amp)PF(6) (6): monoclinic, space group P2(1)/m, with a = 5.2089(7) A, b = 14.3950(17) A, c = 7.0149(14) A, beta = 96.538(14) degrees, and Z = 2. While Ag(I) is 2-coordinate in 1, 5 and 6, it shows 3-coordination in 2 and 4. Compound 1 consists of a 1-D polymeric cation chain with interchain Ag...Ag contacts and the anions sitting on the edges of the chains. The dication in 2 is held in the form of a circular helicate by closed shell Ag...Ag interactions. Compound 4 generates a 2-D network with channels big enough to accommodate the anions. Compound 5 is a 2-D chiral network of chains connected by Ag...Ag contacts. Compound 6 shows a simple 1-D chain structure with an alternating arrangement of cationic chains and anions.