Extended structures of polyiodide salts of transition metal macrocyclic complexes

Abstract

The structures of five polyiodide salts, [Co([9]aneS3)2]I11 (1), [Ni([9]aneS3)2]I6 (2), [Ni([9]aneS3)2]I10 (3), [Pd([12]aneS4)]I6 (4) and [Pd([14]aneS4)]I10·MeCN (5), containing the template cations [Co([9]aneS3)2]3+, [Ni([9]aneS3)2]2+, [Pd([12]aneS4)] 2+ and [Pd([14]aneS4)]2+ ([9]aneS3 = 1,4,7- trithiacyclononane, [12]aneS4 = 1,4,7,10-tetrathiacyclododecane, [14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane) exhibit a range of polyiodide and polyanionic framework structures. In (1) the charge on the CoIII 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. © International Union of Crystallography 2007.