Crystal and Molecular Structures of Ionophore−Siderophore Host−Guest Supramolecular Assemblies Relevant to Molecular Recognition

Ionophore-siderophore host−guest assemblies composed of 18-crown-6 and ferrioxamine B,
benzo-18-crown-6 and ferrioxamine B, and cis-syn-cis-dicyclohexano-18-crown-6 and ferrioxamine B were
successfully crystallized, and their structures were determined by single-crystal X-ray diffraction. All three
crystal lattices also include solvated Mg(II) and perchlorate ions. The ionophore−siderophore host−guest
assembly is noncovalently held together by a hydrogen bonding interaction between the pendant protonated
amine in the second coordination sphere of ferrioxamine B and the hydrogen bond acceptor oxygen atoms
in the crown ether. The crystals of 18-crown-6:ferrioxamine B host−guest assembly are monoclinic, with
space group P21/c, and four molecules per unit cell with dimensions a = 19.8327(11) Å, b = 20.4111(11)
Å, c = 15.1698(8) Å, and β = 96.435(1)°. The crystals of benzo-18-crown-6:ferrioxamine B host−guest
assembly are triclinic, with space group P1̄, and two molecules per unit cell with dimensions a = 11.1747(10)
Å, b = 16.0580(15) Å, c = 18.4175(17) Å, α = 80.469(3) °, β = 81.481(3)° and γ = 70.212(2)°. The
crystals of cis-syn-cis-dicyclohexano-18-crown-6:ferrioxamine B host−guest assembly are monoclinic, with
space group P21/c, and four molecules per unit cell with dimensions a = 20.1473(13) Å, b = 21.5778(15)
Å, c = 14.8013(10) Å, and β = 94.586(2)°. The crystal structures of all three host−guest assemblies contain
a racemic mixture of Λ-N-cis, cis and Δ-N-cis, cis coordination isomers of ferrioxamine B. The crystal
structures indicate that the steric rigidity of the benzo-18-crown-6 and cis-syn-cis-dicyclohexano-18-crown-6
cavity has a pronounced effect on the conformation of the crown ring and ultimately on the hydrogen bonding
interactions between the crown ethers and ferrioxamine B. The structural parameters and the conformational
features of the ferrioxamine B guests compare very well with each other and with those of the ferrioxamine
B structure obtained in the absence of a host. Structural features relevant to siderophore molecular
recognition are discussed.