For the HT crystallization screen with TMA, we screened 224 'good/bad' solvent combinations and 56 'good-good' solvent combinations. Hence, we screened a total of 280 crystallization conditions using a Chemspeed robot platform. After evaporation of the 'good solvents' at room temperature, as well as all or part of the anti-solvents, we collected the crystalline products and recorded PXRD data for the samples after drying in air. Using a library of simulated PXRD patterns for previously reported TMA crystal structures obtained from the Cambridge Structure Database (CSD) and the literature (SI, Table ), we identified six potential 'hits' (SI, Figure ), which produced structures that appeared to be unknown. We determined all six structures using single crystal X-ray diffraction (Table , see SI, Tables S5-6 for full refinement details); as a result of the hexagonal layered packing of the TMA molecules in these six solvates, we observed a close similarity between the simulated PXRD pattern of the a priori predicted low-density polymorph, 1, (Figure ) and the experimental PXRD patterns (SI, Figure ). This shows that CSP, coupled with HT crystallization screening, can identify new forms of 'old', well-studied molecules in a targeted way.