Reaction of Thiamine Diphosphate Hydrochloride (H3TDPCl) With Methylphenyltin(IV) Dichloride in Water. Molecular and Crystal Structures of the Oxygen−Capped Cluster [{SnMe(HTDP)(OH)}3O](OH)·21H2O, in Which Thiamine Diphosphate Coordinates via Its Terminal Phosphate Group

Abstract

Reaction between thiamine diphosphate hydrochloride (H3TDPCl) and methylphenyltin dichloride in water at pH ca. 5.6 afforded the title complex, which was studied by X-ray diffraction and IR and Raman spectroscopy in the solid state and by multinuclear NMR spectroscopy (1H, 13C, 31P, and 119Sn) in aqueous solution. The crystals of this compound are formed by the oxygen-capped cluster cation [{SnMe(HTDP)(OH)}3O]+, an OH- counterion, and water of crystallization. The cation has 3-fold symmetry, and the tin atom has coordination number 6 and a distorted octahedral coordination polyhedron. The HTDP- anion is bis-monodentate bridging between two Sn atoms via two of the oxygens belonging to the terminal phosphate of the ethyl diphosphate side chain [Sn-O = 2.074(3), 2.100(5) A]. The thiamine moiety has F conformation, with torsion angles C(2)-N(3)-C(3,5′)-C(5′) = -5.8(11)° and N(3)-C(3,5′)-C(5′)-C(4′) = -83.0(10)°, and the ethyl diphosphate side chain is folded back, directing the pyrimidine and thiazolium rings of the three HTDP- anions away from the missing corner of the Sn3O4 core so that they form the walls of a with the core as its floor. Although the diffraction data do not allow direct location of most of the hydrogen atoms, indirect structural evidence suggests (i) that the OH- counterion lies inside the nest on the 3-fold symmetry axis, (ii) that the remaining dissociable proton of the HTDP- anion forms a strong hydrogen bond between the pyrimidine N(1′) atom and the uncoordinated oxygen of the terminal phosphate of another HTDP- belonging to the same cluster, and (iii) that one of the oxygens of the nonterminal phosphate is hydrogen-bonded to one of the -OH groups that bridge between the Sn atoms. Features ii and iii are probably responsible for the folding of the ethyl diphosphate side chain. Hydrogen bonds involving the N(4′α)H2 group on the pyrimidine ring and the water molecules of crystallization are also present. The multinuclear NMR results indicate that most of the structural features exhibited by the cluster in the solid state remain in D20 solution. IR and Raman spectra are also discussed.