The crystalline conformations of fluoro-muscarine and allo-fluoro-muscarine iodides were determined by X-ray diffraction to investigate the effect of hydroxyl substitution by a fluorine atom. Comparison with muscarine analogues suggests that the 4T3 ring conformation adopted by fluoro-muscarine should be close to the minimum energy ring conformation of muscarine. allo-Fluoro-muscarine shows a different conformation, consistent with its different substitution pattern. Calculations on model compounds confirm the similarities of the conformational behavior of muscarine and its fluorinated analogue. The fluorine role is evident in the packing of the title compounds which are quasi-isomorphic even if the molecular conformations are different.