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While Δ9-tetrahydrocannabinolic acid A (THCA-A) has been reported to be difficult to crystallize and/or amorphous, we have obtained THCA-A in a pure crystalline form by extraction of marijuana and selective fractionation with liquid CO2. THCA-A (systematic name 1-hydroxy-6,6,9-trimethyl-3-pentyl-6a,7,8,10a-tetrahydro-6H-benzo[c]isochromene-2-carboxylic acid, C22H30O4) crystallizes in the orthorhombic space group P212121, with Z = 8 and Z' = 2. The two independent molecules are related by a pseudo-twofold axis centered between the two -CO2H