Crystal structure and twisted aggregates of oxcarbazepine form III

Polyzois, Hector and Guo, Rui and Srirambhatla, Vijay K. and Warzecha, Monika and Prasad, Elke and Turner, Alice and Halbert, Gavin W. and Keating, Patricia and Price, Sarah L. and Florence, Alastair J. (2022) Crystal structure and twisted aggregates of oxcarbazepine form III. Crystal Growth and Design, 22 (7). pp. 4146-4156. ISSN 1528-7483 (

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Polymorphism and crystal habit play vital roles in dictating the properties of crystalline materials. Here, the structure and properties of oxcarbazepine (OXCBZ) form III are reported along with the occurrence of twisted crystalline aggregates of this metastable polymorph. OXCBZ III can be produced by crystallization from the vapor phase and by recrystallization from solution. The crystallization process used to obtain OXCBZ III is found to affect the pitch, with the most prominent effect observed from the sublimation-grown OXCBZ III material where the pitch increases as the length of aggregates increases. Sublimation-grown OXCBZ III follows an unconventional mechanism of formation with condensed droplet formation and coalescence preceding nucleation and growth of aggregates. A crystal structure determination of OXCBZ III from powder X-ray diffraction methods, assisted by crystal structure prediction (CSP), reveals that OXCBZ III, similar to carbamazepine form II, contains void channels in its structure with the channels, aligned along the c crystallographic axis, oriented parallel to the twist axis of the aggregates. The likely role of structural misalignment at the lattice or nanoscale is explored by considering the role of molecular and closely related structural impurities informed by crystal structure prediction.