Controlling the Framework Formation of Silver(I) Coordination Polymers with 1,4-Bis(phenylthio)butane by Varying the Solvents, Metal-to-Ligand Ratio, and Counteranions

The reactions of 1,4-bis(phenylthio)butane (L) with AgI salts in varied conditions (varying the solvents, metal-to-ligand ratios, and counteranions) lead to the formation of four new two-dimensional (2D) coordination polymers
with different network structures:  [Ag2L3(ClO4)2]∞ 1, [Ag2L3(ClO4)2·CH3OH]∞ 2, {[AgL2](ClO4)}∞ 3, and [AgLNO3]∞
4. All the structures were established by single-crystal X-ray diffraction analysis. Crystal data for 1:  triclinic, P-1,
a = 11.0253(9) Å, b = 11.3455(9) Å, c = 11.5231(9) Å, α = 93.931(2)°, β = 92.689(2)°, γ = 112.9810(10)°,
Z = 2. 2:  triclinic, P-1, a = 11.9147(13) Å, b = 16.1534(17) Å, c = 16.2259(17) Å, α = 74.977(2)°, β =
69.030(2)°, γ = 69.986(2)°, Z = 2. 3:  triclinic, P-1, a = 12.1617(9) Å, b = 12.5054(10) Å, c = 13.1547(10) Å,
α = 64.3370(10)°, β =85.938 (2)°, γ = 69.3010(10)°, Z = 2. 4:  monoclinic, P21/c, a = 5.4032(17) Å, b =
16.974(6) Å, c = 19.489(6) Å, β = 94.234(6)°, Z = 4. In all four complexes, each AgI center has a tetracoordination
geometry, and the 2D networks consist of fused large macrometallacyclic ring systems. The “hexagonal” 42-membered rings, Ag6L6, observed in 1 and 2 are nearly identical, which could be considered as unique examples
of self-sustaining noninterpenetrated frameworks formed with flexible ligands. The repeating rectangular 28-membered
macrometallacycle, Ag4L4, is the basis for the network of 3, in which the perchlorate anions occupy the voids to
prevent the ring from collapsing. In 4, columns of the fused rectangular 22-membered rings, Ag4L2(NO3)2, are
cross-linked through the L ligands to form a unique 2D network consisting of two types of 22-membered repeating
units.