Molecular and crystal structure of konjac glucomannan in the mannan II polymorphic form

A probable crystal structure of konjac glucomannan (mannose:glucoe ratio = 1.6) is proposed based on X-ray data and constrained linked-atom least squares model refinement. The structure crystallizes in the mannan II polymorphic form, in an orthorhombic unit-cell with a = 9.01 Å, b = 16.73 Å, c (fiber axis) = 10.40 Å, and a probable space group I222. The backbone conformation of the chain is a two-fold helix stabilized by intramolecular O-3O-5′ hydrogen bonds, with the O-6 rotational position gt. The unit cell contains four chains with antiparallel packing polarity and eight water molecules which reside in crystallographic positions. Intermolecular hydrogen bonds occur exclusively between chains and water molecules, establishing a three-dimensional hydrogen-bond network in the crystal structure. The glucose residues replace mannoses in the structure in isomorphous fashion, although some disorder appears possible. A structure having alternating gg - gt O-6 rotational positions and conforming to space group P222 appears to describe the disorder regions of the crystal. The reliability of the structure analysis is indicated by the X-ray residuals R = 0.276 and R″ = 0.223.