Determination of the structure of cellulose II.

The structure of regenerated cellulose is shown by x-ray diffraction to be comprised of an array of antiparallel chain molecules. The determination was based on the intensity data from rayon fibers and utilized rigid-body least-squares refinement techniques. The unit cell is monoclinic with space group P2(1) and dimensions a = 8.01 A, b = 9.04 A, c = 10.36 A (fiber axis), and gamma = 117.1 degrees. Models containing chains with the same sense (parallel) or alternating sense (antiparallel) were refined against the intensity data. The only acceptable model contains antiparallel chains. The -CH2OH groups of the corner chain are oriented near to the gt position while those of the center chain are near to the tg position. Both chains possess an O3-H-O5' intramolecular hydrogen bond, and the center chain also has an O2'-H-O6 intramolecular bond. Intermolecular hydrogen bonding occurs along the 020 planes (o6-h-o2 bonds for the corner chains and O6-H-O3 bonds for the center chains) and also along the 110 planes with a hydrogen bond between the O2-H of the corner chain and the O2' of the center chain. This center-corner chain hydrogen bonding is a major difference between the native and regenerated structures and may account for the stability of the latter form.