The conformations and conformational equilibria of RA-VII and related natural products in THF-d(8) were found to be similar to that observed in conventional solvents (CDCl3, 15% CD3OD-CDCl3). The addition of 1 equiv of LiCl resulted in the adoption of a single dominant solution conformation (94%) that corresponds to the major conformation detected in conventional solvents (CDCl3, CD3OD, DMSO-d(6), THF-d(8)), and the further addition of LiCl (2-12 equiv) had no additional effect on the structure or conformational equilibria of the agent. The LiCl complexed solution conformation in THF-d(8) closely resembles the X-ray structure conformation. This conformation contains a characteristic and diagnostic cis C-30-N-29 N-methyl amide central to a type VI beta-turn and the rigid cycloisodityrosine subunit, a trans C-8-N-9 N-methyl amide central to a typical type II beta-turn capped with a tight transannular Ala(1)-C=O-HN-Ala(4) hydrogen bond, a trans C-14-N-15 N-methyl amide, and a fully accessible Ala(2)-NH. Unlike the conformation observed in THF-d(8) but similar to the X-ray structure conformation, the LiCl complexed conformation of RA-VII lacks the weak transannular Ala(1)-NH-O=C-Ala(4) hydrogen bond which results in a small perturbation in the relative orientations of the two aromatic rings of the characteristic biaryl ether ring system. This may be attributed to preferential complexation or a preferential effect of the LiCl complexation to the Ala(1)-Tyr(6) amide. Interestingly, and not fortuitous, this is the exact location occupied by an ordered water molecule in the X-ray crystal structure of a derivative of RA-VII.