Occupational modulation in the (3+1)-dimensional incommensurate structure of (2S,3S)-2-amino-3-hydroxy-3-methyl-4-phenoxybutanoic acid dihydrate.

Abstract

The incommensurately modulated structure of (2S,3S)-2-amino-3-hydroxy-3-methyl-4-phenoxybutanoic acid dihydrate (C₁₁H₁₅NO₄·2H₂O or I·2H₂O) is described in the (3+1)-dimensional superspace group P2₁2₁2₁(0β0)000 (β = 0.357). The loss of the three-dimensional periodicity is ascribed to the occupational modulation of one positionally disordered solvent water molecule, where the two positions are related by a small translation [ca 0.666 (9) Å] and ∼168 (5)° rotation about one of its O-H bonds, with an average 0.624 (3):0.376 (3) occupancy ratio. The occupational modulation of this molecule arises due to the competition between the different hydrogen-bonding motifs associated with each position. The structure can be very well refined in the average approximation (all satellite reflections disregarded) in the space group P2₁2₁2₁, with the water molecule refined as disordered over two positions in a 0.625 (16):0.375 (16) ratio. The refinement in the commensurate threefold supercell approximation in the space group P112₁ is also of high quality, with the six corresponding water molecules exhibiting three different occupancy ratios averaging 0.635:0.365.