The crystal structure of myoinositol hexaphosphate dodecasodium salt has been determined for the octatriacontahydrate form which crystallizes in space group Ce, a=23.091 (13), b--12-203 (10), c= 22"894 (14) A, fl= 108"30 (1) °, and Z=4. As the crystalline hydrated sodium salt, myoinositol hexaphosphate has the sterically unfavorable (5-axial/I-equatorial) ring conformation. This conformer is stabilized by the mutual repulsion of 1,2-vicinal ionized phosphates, sodium ion bridging of both 1,3-syn and 1,2-vicinal phosphates and hydrogen-bonded water molecules. A degree of structural stability is gained from the uncommon mode of sodium coordination to ester oxygens. Three types of polyhedral arrangements are observed for the oxygen atoms coordinated to sodium. These have triangular faces, and examples of face-, edge-, and corner-sharing are found. The phytate molecule assumes an asymmetric conformation with a pseudo-center of symmetry. An empirical stereochemical analysis of the 1,3-syn steric effects is qualitatively consistent with observed conformational features. The stereochemical properties of phytate are discussed with regard to its biological roles in enzymatic dephosphorylation and as a structural analogue of polyphosphoinositides.