Molecular strands and related properties of silver(I) triflate with 3,3′-oxybispyridine vs 3,3′-thiobispyridine

Studies on subtle spacer ligand effects of AgCF₃SO₃ with 3,3′-Py₂X (X = O vs S) have been carried out. The reaction of AgCF₃SO₃ with 3,3′-Py₂O and 3,3′-Py₂S produces [Ag(CF₃SO₃)(3,3′-Py₂O)] and [Ag(3,3′-Py₂S)] (CF₃SO₃), respectively. Crystallographic characterization of [Ag(CF₃SO₃)(3,3′-Py₂O)] (monoclinic P1, a = 8.405(2) Å, b = 10.714(2) Å, c = 18.031(2) Å, α = 77.36(2), β = 107.83(2)°, γ= 66.92(2), V = 1438.0(5) ų, Z = 2, R = 0.0486) reveals that the skeletal structure is an anion-bridged double-strand. The double-strands are packed like a plywood. The framework of [Ag(3,3′-Py₂S)](CF₃SO₃) (orthorhombic Pcab, a = 17.330(2) Å, b = 8.640(1) Å, c = 19.933(6) Å, V = 2985(1) ų, Z = 8, R = 0.0437) is a sinusoidal single-strand. The formation of each coordination polymer appears to be primarily associated with the donating ability and the conformational energy barrier of the spacer ligands. Thermal analyses indicate that [Ag(CF₃SO₃)(3,3′-Py₂O)] and [Ag(3,3′-Py₂S)](CF₃SO₃) are stable up to 250°C and 210°C, respectively. For the anion exchangeability, the nature of the spacer ligand is more significant factor than the distance of silver(I)···triflate.