Organometallic Supramolecular Chemistry with Monosaccharides: Triethylammonium μ ‐Chloro‐bis{chloro( η 5 ‐cyclopentadienyl)(methyl 4,6‐ O ‐benzylidene‐ β ‐ D ‐glucopyranosidato‐1 κO 2 ,1:2 κO 3 )zirconate}

The reaction of [CpZrCl 3 (thf) 2 ] with methyl 4,6‐ O ‐ benzylidene‐ β ‐ D ‐glucopyranoside ( β ‐MeBG H 2 , 1 ) in the presence of Et 3 N results in the formation of the zirconate complex [Et 3 NH][(CpZrCl) 2 ( μ ‐Cl){ μ ‐( β ‐MeBG)} 2 ] ( 2 ). X‐ray structure analyses were performed from the ligand precursor β ‐MeBG H 2 1 as well as from 2 . Compound 1 crystallizes in the monoclinic chiral space group P 2 1 . The molecules show a flat arrangement including the benzylidene protecting group, and are packed in columns. The columns are held together in pairs by the formation of hydrogen bonds between the hydroxy functions in positions 2 and 3. Compound 2 crystallizes in the orthorhombic space group P 2 1 2 1 2 1 . The β ‐MeBG ligands are chelating the Zr atoms through the oxygen atoms in positions 2 and 3 of the glucopyranosidato ligand revealing a 1‐zircona‐2,5‐dioxolane moiety each; the oxygen atom in position 3 is linked to both of the Zr atoms. Additionally one chloro ligand is bridging the two Zr centers. Two terminally bound chloro ligands stick out from the two Zr atoms into a chiral U‐shaped cavity constructed by the two β ‐MeBG ligands. The cavity incorporates the tertiary ammonium cation [Et 3 NH] + , which is bound to one of the terminal chloro ligands through a hydrogen bond. The inclusion of the [Et 3 NH] + cation in the U‐shaped cavity, even in solution, is demonstrated by NMR spectroscopic data.