Hydrogen-bonded frameworks for molecular structure determination

• Published in: Nature communications Vol. 10; no. 1; pp. 4477 - 7
• Main Authors: Li, Yuantao, Tang, Sishuang, Yusov, Anna, Rose, James, Borrfors, André Nyberg, Hu, Chunhua T., Ward, Michael D.
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 02.10.2019; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 639/638/11/879; 639/638/403/936; 639/638/541/961; Absolute configuration; Chemical bonds; Crystal growth; Crystal structure; Crystallinity; Crystallization; Crystals; Humanities and Social Sciences; Hydrogen bonding; Metal-organic frameworks; Molecular structure; multidisciplinary; Occupancy; Organosulfonates; Science; Science (multidisciplinary); Single crystals; Sulfur; X-ray diffraction
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-019-12453-6

Single crystal X-ray diffraction is arguably the most definitive method for molecular structure determination, but the inability to grow suitable single crystals can frustrate conventional X-ray diffraction analysis. We report herein an approach to molecular structure determination that relies on a versatile toolkit of guanidinium organosulfonate hydrogen-bonded host frameworks that form crystalline inclusion compounds with target molecules in a single-step crystallization, complementing the crystalline sponge method that relies on diffusion of the target into the cages of a metal-organic framework. The peculiar properties of the host frameworks enable rapid stoichiometric inclusion of a wide range of target molecules with full occupancy, typically without disorder and accompanying solvent, affording well-refined structures. Moreover, anomalous scattering by the framework sulfur atoms enables reliable assignment of absolute configuration of stereogenic centers. An ever-expanding library of organosulfonates provides a toolkit of frameworks for capturing specific target molecules for their structure determination. Single crystal X-ray diffraction is an invaluable tool for molecular structure determination, but growing single crystals is often an arduous process. Here the authors find that the structures of a wide array of molecules can be determined by SCXRD when included in hydrogen-bonded guanidinium organosulfonate host frameworks in a single-step crystallization.