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 1

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 3 h m with a ) b ) c ) 9.458(4) Å, R) ‚ ) Á ) 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, ‚ ) 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, ‚ ) 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.