Extended structures of polyiodide salts of transition metal macrocyclic complexes

The structures of five polyiodide salts, [Co([9]aneS 3 ) 2 ]I 11 (1), [Ni([9]aneS 3 ) 2 ]I 6 (2), [Ni([9]aneS 3 ) 2 ]I 10 (3), [Pd([12]aneS 4 )]I 6 (4) and [Pd([14]aneS 4 )]I 10 ·MeCN (5), containing the template cations [Co([9]aneS 3 ) 2 ] 3+ , [Ni([9]aneS 3 ) 2 ] 2+ , [Pd([12]aneS 4 )] 2+ and [Pd([14]aneS 4 )] 2+ ([9]aneS 3 = 1,4,7‐trithiacyclononane, [12]aneS 4 = 1,4,7,10‐tetrathiacyclododecane, [14]aneS 4 = 1,4,8,11‐tetrathiacyclotetradecane) exhibit a range of polyiodide and polyanionic framework structures. In (1) the charge on the Co III cation is balanced by three I anions, which along with a neutral di‐iodine molecule form I rings in an extended structure comprising undulating chains of alternating I rings and complex cations. In (2) the complex cation is linked to two tri‐iodide anions by S⋯I interactions into well separated sheets of cations and anions, while in (3), I anions are linked by I⋯I interactions into helices which are cross‐linked by S⋯I contacts to form sheets. Rather longer I⋯I contacts in (4) assemble I ions into 2 × 2 rods, which are linked into a three‐dimensional network by S⋯I contacts. In (5) the N atom of the acetonitrile solvent molecule forms an array of four weak C—H⋯N hydrogen bonds to the macrocycle. The extended structure comprises corrugated zigzag chains of polyiodide rings formed by linked I units; the complex cations are attached to the polyiodide network by S⋯I contacts, which link the chains to form layers.