Crystal structure and solution studies of the product of the reaction of β-mercaptoethanol with vanadate

Reaction of beta-mercaptoethanol with vanadate under slightly alkaline conditions provided a crystalline complex that was characterized by X-ray diffraction and FTIR spectroscopy. The complex was dimeric in structure with a central [VO](2) core and a pentacoordinate, crudely trigonal bipyramidal arrangement about each vanadium atom with a sulphur occupying a pseudo-axial position. A single V-51 NMR signal was observed for this complex when dissolved in water, chloroform or acetonitrile. A large influence of acetonitrile on the vanadium chemical shift suggested the possibility of reaction with acetonitrile. FTIR showed the presence of two complexes in acetonitrile solution but only one in chloroform or water. Mixed solvent studies were carried out in an effort to further characterize the solution complexes. Crystal structure of [{VO2(OC2H4S)}(2)][NEt4](2): monoclinic, space group P2(1)/n,. a = 8.3451(17), b = 16.954(4), c = 10. 2064(25) Angstrom; beta = 101. 271(18)degrees; V = 1416.2 Angstrom(3); Z = 2; R-F = 0.048 for 1355 data (I-o greater than or equal to 2.5 sigma (I-o)) and 147 variables.