New Polymorph of Dehydroepiandrosterone Obtained via Cryomodification

A new anhydrous polymorph of dehydroepiandrosterone (DHEA) is detected in cryomodified powder samples and designated as form VII. The crystal structure of form VII is determined from multiphase X-ray powder diffraction (XRPD) data. Additionally, the unknown crystal structures of anhydrous form III and the new monohydrated DHEA form designated as form S5 are also determined from multiphase XRPD data. To validate the crystal structures III, VII, and S5, energy minimization with dispersion-corrected density functional theory is performed in VASP. An extended list of the DHEA forms with the known crystal structures, which now covers anhydrous forms I, II, III, VI, and VII and solvated forms S1, S2, S4 and S5, allows quantification of DHEA solid-state transformations to be carried out.