AbstractStructural elements of the arylglycerol b-syringyl ether type are very frequent in hardwood lignins. A variety of crystalline dimeric lignin models representing different diastereomeric forms of structural elements in lignin of this type have been studied using X-ray crystallography. Bond distances and bond angles in the model compounds are in all probability nearly identical with those of the corresponding structural elements in lignins. Special attention was paid to the geometry of the b-O-syringyl linkage, since the reactivity of this linkage is of particular interest in connection with pulping reactions. The crystal structures of the model compounds suggest that two types of conformations are predominating; in both of them the aromatic rings are separated by ca. 4.5 Å (maximal distance 4.9-5 Å). Based on X-ray crystallographic data from four compounds a sequence of units (5 aromatic rings, 8 chiral C-atoms) attached to each other by b-syringyl ether linkages was constructed. The appearance of the resulting oligomer illustrates that stereoisomerism can be expected to influence the shape of the lignin molecules to a great extent.