Zipped-up chain-type coordination polymers: unsymmetrical amide-containing ligands inducing beta-sheet or helical structures. kazu-u@yamaguchi-u.ac.jp.

The crystal structures of thirteen AgI coordination polymers involving py-CONH-(CH2)n-py (py=pyridine; n=0, 1) derivatives were determined by means of single-crystal X-ray analyses. All of the compounds form one-dimensional chains composed of AgI atoms and bridging ligands with formulas [[Ag(py-CONH-(CH2)n-py)][X]]n (X=PF6 -, ClO4 -, BF4 -, and NO3 - with solvent molecules). The unsymmetrical coordination environments around AgI atoms induce direction in the chains, that is, -[NH-(CH2)n-py-Ag-py-CO]-, which resembles the alignment of amino acid chains in proteins. In compounds [[Ag(4-pia)][X]]n (1 supersetX; 4-pia=N-(4-pyridyl)isonicotinamide; X=PF6 -, ClO4 -, BF4 -, and NO3 -), [[Ag(4-pmia)][X]]n (2 supersetX; 4-pmia=N-(pyridin-4-ylmethyl)isonicotinamide; X=PF6 -, ClO4 -H2O, and NO3 -H2O), and [[Ag(3-pmia)][X]]n (3 supersetX; 3-pmia=N-(pyridin-3-ylmethyl)isonicotinamide; X=PF6 -, ClO4 -, BF4 -, and NO3 -H2O), each chain is aligned parallel to neighboring chains, but adjacent chains run in the opposite direction. Particularly in [[Ag(3-pmia)][PF6]]n (3 supersetPF6 -), [[Ag(3-pmia)][ClO4]]n (3 supersetClO4 -), and [[Ag(3-pmia)][BF4]]n (3 supersetBF4 -), amide moieties of 3-pmia ligands are complementarily hydrogen bonded to amide moieties in neighboring chains, as in the beta-sheet motif in proteins. On the other hand, in [[Ag(4-pmna)][PF6]MeOH]n (4-pmna=N-(pyridin-4-ylmethyl)nicotinamide), all chains in the crystal form left-handed (4 a supersetPF6 -MeOH) and right-handed (4 b supersetPF6 -MeOH) helical structures with a helical pitch of 28 A. Heterogeneous anion exchanges proceed reversibly in 2, but not in 3, which provides information about the thermal stabilities of the crystals.