Multi-Crystal X-Ray Diffraction (MCXRD) Bridges the Crystallographic Characterisation Gap in Chemistry and Materials...

Structure determination by X-ray diffraction is limited by crystal size and can be compromised by radiation damage when using very intense X-ray radiation. X-ray structure determination from partial diffraction data sets combined from multiple crystals is a potential solution, but its exploitation in chemistry and materials science is largely unrealized. Here we report the use of synchrotron radiation for multi-crystal X-ray diffraction (MCXRD) adapted for structure determination of metal-organic framework (MOF) materials with crystal dimensions too small for conventional single-crystal diffraction studies. We further show that radiation-induced chemical changes and degradation of diffraction quality can be alleviated. Our approach encompasses both rotation- and stationary-MCXRD measurements for 10 to 1000s of crystals with software-optimized combination of the multiple data sets. We report the crystal structures of six MOFs: MOF-919(Sc/Cu), MET-2, MIL-88B(Cr)-1,4-NDC, PCN-260(Sc), UiO-66, and UiO-66-MoO₄ with unit cell dimensions ranging from 18-114 Å and crystal sizes from 0.5-480 µm³. This approach can address the challenges of structure determination in a regime of particle size and sample radiation sensitivity that lies between existing single-crystal X-ray diffraction and the emerging field of electron diffraction. MCXRD can provide accurate atomic-resolution structure determination for some of the most challenging cases in chemistry and materials science.