Plausible molecular and crystal structures of chitosan/HI type II salt Original Research Article

Chitosan/HI type II salt prepared from crab tendon was investigated by X-ray fiber diffraction. Two polymer chains and 16 iodide ions (I−) crystallized in a tetragonal unit cell with lattice parameters of a=b=10.68(3), c (fiber axis)=40.77(13) Å, and a space group P41. Chitosan forms a fourfold helix with a 40.77 Å fiber period having a disaccharide as the helical asymmetric unit. One of the O-3⋯O-5 intramolecular hydrogen bonds at the glycosidic linkage is weakened by interacting with iodide ions, which seems to cause the polymer to take the 4/1-helical symmetry rather than the extended 2/1-helix. The plausible orientations of two O-6 atoms in the helical asymmetric unit were found to be gt and gg. Two chains are running through at the corner and the center of the unit cell along the c-axis. They are linked by hydrogen bonds between N-21 and O-61 atoms. Two out of four independent iodide ions are packed between the corner chains while the other two are packed between the corner and center chains when viewing through the ab-plane. The crystal structure of the salt is stabilized by hydrogen bonds between these iodide ions and N-21, N-22, O-32, O-61, O-62 of the polymer chains.