title: Raman, infrared and force field studies of K2(12)C2O4 x H2O and K2(13)C2O4 x H2O in the solid state and in aqueous solution, and of (NH4)2(12)C2O4 x H2O and (NH4)2(13)C2O4 x H2O in the solid state.
abstract: The Raman and infrared spectra of solid K2(12)C2O4 x H2O are reported together with, for the first time, the corresponding Raman and infrared spectra of solid K2(13)C2O4 x H2O. Raman spectra of aqueous solutions of both isotopomers are also reported. In the solid state the oxalate anion is planar with D2h symmetry in this salt, whereas in aqueous solution the Raman spectra of the anion are best interpreted on the basis of D2d symmetry. The Raman spectra of solid (NH4)2(12)C2O4 x H2O and (NH4)2(13)C2O4 x H2O, in which the oxalate anion is twisted from planarity by 28 degrees about the CC bond, have also been recorded. Several reassignments have been made. The harmonic force field for the oxalate anion in the D2h, D2 and D2d geometries has been determined in part, and approximate values of key valence force constants determined. All the observed band wavenumbers and 12C/13C isotopic shifts are well reproduced by the force fields. The potential energy distribution of the totally symmetric normal modes of planar oxalate indicates that each mode consists of extensively mixed symmetry corrdinates and that the labels previously used for the bands seen here at 475 and 879 cm(-1) would better be described as v(CC) and deltaS(CO2), respectively, putting them in the same wavenumber order as v(NN) and deltaS(NO2) for the isoelectronic and isostructural molecule N2O4. The stretching force constants of N2O4 and planar C2O4(2-) are established to be in the order f(NN) < f(CC) and f(NO) > f(CO), consistent with the known relative bond lengths.
authors.affiliation: Department of Chemistry, University College London, UK. r.j.h.clark@ucl.ac.uk
authors.forename: Robin J H
authors.initials: RJ
authors.lastname: Clark
authors.forename: Steven
authors.initials: S
authors.lastname: Firth
mesh_terms: D018360:Crystallography, X-Ray; D015394:Molecular Structure; D010070:Oxalates / Q000737:chemistry*; D012996:Solutions; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D014867:Water
chemical_list: D010070:Oxalates; D012996:Solutions; D014867:Water