Crystal structure of valinomycin‐monohydrate cage complexes crystallized from dioxane

Valinomycin, cyclo‐[(l‐Val‐d‐Hyv‐d‐Val‐l‐Lac)₃‐], was crystallized from aqueous dioxane solvent as a mono‐hydrate complex in which water molecules were found within the ion‐binding cavity of the ionophore: monoclinic P2₁ a = 14.377 (3), b = 41.554 (14), c = 14.080 (3) Å, β= 118.27 (2)^c, Z = 4. There are two non‐equivalent valinomycin‐water complexes and three dioxane molecules in the asymmetric unit. The ionophore molecules adopt two similar but non‐identical, octahedral, bracelet, cage conformations that are a consequence of two distinct ways in which the complexed water molecules can deform the normal octahedral coordinate geometry of the metal binding site. In the first complex the water molecule forms hydrogen donor bonds to the carbonyl oxygens of two l‐valine residues on one facial side of the cavity, while in the second complex the water molecule is trigonal‐planar coordinate and binds to two l‐valine residues on one entrant face of the cavity plus a third d‐valine residue from the opposite side of the cavity.