For the high-throughput (HT) crystallization screen, we initially screened the solubility of TMA and ADTA in 44 commercially available aliphatic and aromatic solvents (SI, Table ), by attempting to dissolve TMA (15 mg) or ADTA (3 mg) in 1 mL of each solvent at room temperature. The solvents which dissolved ≥ 15 mg/mL of TMA, or ≥ 3 mg/mL of ADTA, at room temperature, and had boiling points < 120 °C, were used as 'good solvents' for the crystallization screens (SI, Table ). In total, we used 8 'good' solvents for TMA (methanol, THF, ethanol, 2-propanol, tetrahydropyran, 1-propanol, 1,4-dioxane, and 1-buanol) and 6 'good' solvents for ADTA (methanol, THF, ethanol, 2-propanol, 1-propanol, and 1-butanol) to prepare stock solutions of these molecules (15 mg/mL TMA and 3 mg/mL ADTA, respectively). The remaining organic solvents that dissolved < 15 mg/mL TMA, or < 3 mg/mL ADTA at room temperature were used as anti-solvents for the crystallization screen. In total, we used 28 and 30 anti-solvents to direct the crystallization of TMA and ADTA, respectively. Isooctane and tetradecane were not used for the TMA crystallization screen because TMA solvates have been reported in the literature. The crystallization screens were carried out on a Chemspeed Technologies SWING POWDERDOSE robot using the experimental design shown in the SI (section 2.1.1 for full experimental details). Using this robot, we could add the anti-solvents at different rates to create different crystallization conditions. For the TMA crystallizations reported here, 1 ml of 'good solvent' and 1 mL of anti-solvent was added into each crystallization vial. For the ADTA crystallizations, 2 ml of 'good solvent' and 2 mL of anti-solvent was added into each vial. After evaporation of the crystallization solvent at room temperature over several days, the crystalline materials were transferred into HT 96-well PXRD plate with a mylar film base. PXRD patterns were recorded over the 2 range 2-40, on a PANalytical Empyrean diffractometer (Cu-Kα), operating in transmission geometry mode, and equipped with a HT screening XYZ sample stage and PIXcel detector. The PXRD patterns for the screened crystallization conditions were compared with the simulated PXRD patterns for the predicted crystal structures and previously reported TMA and ADTA crystal structures from the literature (SI, Table -4) using PANalytical X'Pert HighScore software package (PW3212). X-ray crystal structures were determine using Rigaku MicroMax-007 HF rotating anode diffractometer (Mo-Kα radiation,  = 0.71073 Å, kappa 4-circle goniometer, Rigaku Saturn724+ detector); or at beamline I19, Diamond Light Source, Didcot, UK using silicon double crystal monochromated synchrotron radiation (λ = 0.6889 Å, Pilatus 2M detector).