Silver−Thioether Crown Complexes as Templates for the Synthesis of Extended Polyiodide Networks: Synthesis and X-ray Crystal Structures of [Ag2([15]aneS5)2]I12, [Ag([18]aneS6)]I7, [Ag([18]aneS6)]I3, and [Ag([9]aneS3)2]I5

Silver(I) complexes of [9]aneS 3, [15]aneS 5, and [18]aneS 6 have been used as templates for the self-assembly of polyiodide ions. The complexes [Ag 2 ([15]aneS 5 ) 2 ]I 12, [Ag([18]aneS 6 )]I 7, [Ag([18]aneS 6 )]I 3, and [Ag([9]aneS 3 ) 2 ]I 5 have been synthesized and structurally characterized. In [Ag 2 ([15]aneS 5 ) 2 ]I 12 [C 10 H 20 AgI 6 S 5, orthorhombic, space group Pna 2 1 with a = 21.688(4) Å, b = 27.748(4) Å, c = 8.623(2) Å, Z = 8], a discrete I 12 2- polyiodide anion describable as a [2I - ·5I 2 ] charge-transfer adduct is bound to two [Ag([15]aneS 5 )] + cations by Ag−I bonds. I···S interactions contribute to build up an extended three-dimensional superstructure featuring spirals of I 12 2- and [Ag([15]aneS 5 )] + ions alternating along the c axis. In [Ag([18]aneS 6 )]I 7 [C 12 H 24 AgI 7 S 6, trigonal, space group R 3̄ m with a = b = c = 9.458(4) Å, α = β = γ = 103.79(3)°, Z = 1], the Ag(I) complex cation is embedded in a unique three-dimensional polyiodide matrix in which I - ions occupy the lattice points of a primitive rhombohedral lattice with one I 2 molecule bridging two I - ions along each cell edge to give a pseudo-perovskite structure. [Ag([18]aneS 6 )]I 3 [C 12 H 24 AgI 3 S 6, monoclinic, space group C 2/ m with a = 18.5767(11) Å, b = 11.9188(7) Å, c = 5.2714(5) Å, β = 95.634(9)°, Z = 2] features discrete [Ag([18]aneS 6 )] + cations and I 3 - in a columnar stacking arrangement. Using the [Ag([9]aneS 3 ) 2 ] + cation as template, an I 5 - salt has been obtained; this contrasts with the cubelike [I 7 - ] ∞ polyiodide array and I 3 - salt isolated with the [Ag([18]aneS 6 )] + cation. In [Ag([9]aneS 3 ) 2 ]I 5 [C 12 H 24 AgI 5 S 6, monoclinic, space group C 2/ c with a = 17.1117(12) Å, b = 12.612(2) Å, c = 14.016(2) Å, β = 118.65(4)°, Z = 4], I···S interactions contribute to an extended structure featuring polymeric successions of cations and I 5 - ions. The solid-state FT-Raman spectra of these polyiodides are discussed on the basis of their crystal structures.