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)BF4 (1) follow:  monoclinic, space group C2/c, with a = 16.788(2) Å, b =
11.5719(6) Å, c = 11.3864(7) Å, β = 123.671(8)°, and Z = 8. For Ag2(2-amp)3(PF6)2 (2):  monoclinic, space
group P21/a, with a = 10.029(7) Å, b = 20.291(12) Å, c = 13.907(6) Å, β = 95.38(5)°, and Z = 4. For Ag2(3-amp)3(PF6)2 (4):  triclinic, space group P1̄, with a = 10.4482(7) Å, b = 11.1468(9) Å, c = 12.2720(11) Å, α =
81.018(7)°, β = 80.668(6)°, γ = 80.977(6)°, and Z = 2. For Ag(4-amp)BF4·0.75CH3CN (5):  orthorhombic, space
group C2221, with a = 9.272(2) Å, b = 16.164(12) Å, c = 27.851(2) Å, and Z = 8. For Ag(4-amp)PF6 (6): 
monoclinic, space group P21/m, with a = 5.2089(7) Å, b = 14.3950(17) Å, c = 7.0149(14) Å, β = 96.538(14)°,
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.

Ag(I)盐与(氨基甲基)吡啶的三种异构体，即2-amp、3-amp和4-amp之间的反应，可形成受阴离子和闭合壳层Ag···Ag接触影响的离散或聚合物（一维和二维）结构。以下为Ag(2-amp)BF4（1）的表征数据：单斜晶系，空间群C2/c，晶胞参数为a = 16.788(2) Å，b = 11.5719(6) Å，c = 11.3864(7) Å，β = 123.671(8)°，Z = 8。对于Ag2(2-amp)3(PF6)2（2）：单斜晶系，空间群P21/a，晶胞参数为a = 10.029(7) Å，b = 20.291(12) Å，c = 13.907(6) Å，β = 95.38(5)°，Z = 4。对于Ag2(3-amp)3(PF6)2（4）：三斜晶系，空间群P1̄，晶胞参数为a = 10.4482(7) Å，b = 11.1468(9) Å，c = 12.2720(11) Å，α = 81.018(7)°，β = 80.668(6)°，γ = 80.977(6)°，Z = 2。对于Ag(4-amp)BF4·0.75CH3CN（5）：正交晶系，空间群C2221，晶胞参数为a = 9.272(2) Å，b = 16.164(12) Å，c = 27.851(2) Å，Z = 8。对于Ag(4-amp)PF6（6）：单斜晶系，空间群P21/m，晶胞参数为a = 5.2089(7) Å，b = 14.3950(17) Å，c = 7.0149(14) Å，β = 96.538(14)°，Z = 2。在化合物1、5和6中，Ag(I)为二配位，而在化合物2和4中，Ag(I)为三配位。化合物1由一维聚合物阳离子链组成，链间存在Ag···Ag接触，阴离子位于链的边缘。化合物2中的二价阳离子以闭合壳层Ag···Ag相互作用的形式保持为环形螺旋。化合物4生成二维网络，通道足够容纳阴离子。化合物5是一个由Ag···Ag接触连接的链的二维手性网络。化合物6显示了一个简单的线性链结构，阳离子链和阴离子呈交替排列。