Abstract
A H-bond capable chiral tetradentate ligand, Fe3+, and acetate ion assembles into a hydroxo-bridged binuclear complex with the formula [FeIII2(mu-OH)(mu-OAc)(S-L)2] x 4H2O (1) where H2S-L = S-2-(2-hydroxy-benzylamino)-3-(1H-imidazol-4-yl)-propionic acid. The crystal of 1 contains right-handed one-dimensional (1D) helical channels with 7.3-9.8 A diameter. A similar reaction with a ligand having opposite chirality forms the complex with left-handed helical channels (1a). Heating the crystals of 1 at 95 degrees C under reduced pressure selectively removes three waters from the channel forming an enantiopure porous crystal with empty channels (solvent accessible voids 18% v/v). Intermolecular hydrogen bonding between the imidazole N-H and phenolate oxygen in 1-2 forms a C6 symmetric helix with bridging hydroxo groups pointing inside the channels. All the H-bond capable atoms in the ligand along with one water molecule form an extended H-bonded network throughout the crystal. Exposing the empty channels of 2 to iodine vapor indicates partial filling of the channels with iodine. Crystal data for 1 x 4H2O include the following: hexagonal, P61, a = b = 13.164(3) A, c = 36.305 (11) A, alpha = beta = 90 degrees , gamma = 120 degrees , Z = 6, R1 = 0.0387, wR2 = 0.0842. Crystal data for 1a x 2H2O include the following: hexagonal, P6(5), a = b = 13.151(4) A, c = 36.558(2) A, alpha = beta = 90 degrees , gamma = 120 degrees , Z = 6, R1 = 0.0416, wR2 = 0.1190. Crystal data for 2 x H2O include the following: hexagonal, P61, a = b = 13.160(7) A, c = 36.559 (4) A, alpha = beta = 90 degrees , gamma = 120 degrees , Z = 6, R1 = 0.0574, wR2 = 0.1423.
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