In molecular and materials sciences a central question is how can we determine the structure of organic materials or inorganic complexes at natural isotopic abundance without the need for monocrystals? This would provide an alternative to diffraction methods, and set the field for the development of NMR Crystallography. Our group has developed an approach that allows either structure validation by NMR or that yields access to full structure determination in powder. Both approaches use a combination of high resolution proton and carbon-13 NMR and advanced calculation methods such as molecular modelling, periodic DFT calculations, or advanced crystal structure prediction methods. In 2013 we published the first de novo structure determination in a molecular powder by solid-state NMR spectroscopy.