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]anCS(4))]I-6 (4) and [Pd([14]aneS(4))](I10MeCN)-Me-. (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-3(-) anions, which along with a neutral di-iodine molecule form I-11(3-) 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 (SI)-I-... interactions into well separated sheets of cations and anions, while in (3), I-5(-) anions are linked by (II)-I-... interactions into helices which are crosslinked by (SI)-I-... contacts to form sheets. Rather longer (II)-I-... contacts in (4) assemble I-3(-) ions into 2 x 2 rods, which are linked into a three-dimensional network by (SI)-I-... contacts. In (5) the N atom of the acetonitrile solvent molecule forms an array of four weak C-(HN)-N-... hydrogen bonds to the macrocycle. The extended structure comprises corrugated zigzag chains of polyiodide rings formed by linked I-5(-) units; the complex cations are attached to the polyiodide network by (SI)-I-... contacts, which link the chains to form layers.