We obtained a single crystal structure of the 4-fold interpenetrated form from the THF crystallization (ADTA_2-2, SI, Table ). In ADTAˑ0.25(THF), there are THF molecules located in extrinsic voids between ADTA molecules, rationalizing the formation of the 4fold structure from this crystallization solvent. The arrangement of ADTA molecules in this structure agrees very well with the lowest energy 4-fold interpenetrated structure from the CSP calculations (Figure , Table ). We found that the THF molecules were trapped in the extrinsic cavities, and both TGA and differential scanning calorimetry (DSC) showed that the THF molecules remained in the crystal lattice until ~ 215 °C (SI, Figure -32). Hence, to activate the 4-fold THF solvated structure, a sample of ADTA_2-2, was heated at 210 °C for 2.5 h. After activation at this temperature, PXRD data revealed that there was no notable structural change (SI, Figure ) and no THF was found in the NMR of this sample upon dissolution (SI, Figure ), but this activated 4-fold ADTA structure was non-porous to N 2 at 77.3 K. However, a CO 2 sorption isotherm, recorded at 0 °C, showed that the activated 4-fold structure does adsorb 2 mmol/g of CO 2 at 10 bar (SI, Figure ). The 3-fold structure was only clearly observed in the crystallization screen when tetradecane was used as the anti-solvent (Figure ). We characterized the 3-fold structure using the ethanol/tetradecane (ADTA_3-38) and dioxane/tetradecane (ADTA_7-38) crystallizations. Disordered tetradecane solvent occupies 1-D pores in both of the 3-fold structures, rationalizing their formation with this anti-solvent, but we observed slight differences in crystallographic symmetry for these structures; Fddd for ADTA_3-38 vs. I4 1 /amd for