We demonstrate the combined use of NMR-enhanced crystallography and solvent-free synthesis by accelerated aging (AA), for the discovery and structural characterization of a novel cadmium-based open metal–organic framework (MOF) belonging to the class of zeolitic imidazolate frameworks (ZIFs). Although solid-state NMR spectroscopy has been used to assist in structural characterization of crystalline solids by powder X-ray diffraction (PXRD), typically through quantification of the contents of the asymmetric unit, this work highlights how it can take a more active role in guiding structure determination, by elucidating the coordination environment of the metal node in a novel MOFs. Exploration of AA reactions of cadmium oxide (CdO) and 2-methylimidazole (HMeIm) enabled the synthesis of not only the previously reported yqt1-topology framework but also a new material (1) exhibiting a Cd/MeIm ratio of 1:3, contrasting the 1:2 ratio expected for a ZIF. Structural characterization of 1 was enabled by using 111Cd solid-state nuclear magnetic resonance (SSNMR) to provide information on the coordination environment of the cadmium node. Specifically, 111Cd SSNMR experiments were conducted on a series of model compounds to correlate the cadmium coordination environment to the observed isotropic chemical shift, δiso(111Cd), followed by multinuclear SSNMR experiments on 1 to determine the nature of the metal coordination environment and the number of distinct chemical sites. This information was used in refinement of the molecular level structure from the available PXRD data, a technique termed NMR-enhanced crystallography, revealing that 1 is an open diamondoid (dia) topology Cd(MeIm)2 framework based on Cd2+ ions tetrahedrally coordinated with MeIm– ligands and additional HMeIm guest molecules within the framework pores. Although AA was initially devised as a clean, mild route for making MOFs, these results provide a proof-of-principle of how, by combining it with SSNMR spectroscopy as a means to overcome limitations of PXRD structure determination, it can be used to screen for new solid phases in the absence of solvents, high temperatures, or mechanical impact that are inherent to other thermally-, solution-, or mechanochemically-based techniques.