Sodium trichloromethanesulfonate monohydrate

Abstract

Sodium trichloromethanesulfonate monohydrate, Na+.CCl3SO3-.H2O, crystallizes in P2(1)/a with all the atoms located in general positions. The trichloromethanesulfonate (trichlate) anion consists of pyramidal SO3 and CCl3 groups connected via an S-C bond in a staggered conformation with approximate C3v symmetry. The water molecule is hydrogen bonded to the sulfonate O atoms, with one water H atom forming weak bifurcated O-H...O hydrogen bonds to two different trichlate ions. Two water O atoms and three O atoms from different SO3 groups form a square-pyramidal arrangement around the sodium ion.

Sulfur X-ray Absorption and Vibrational Spectroscopic Study of Sulfur Dioxide, Sulfite, and Sulfonate Solutions and of the Substituted Sulfonate Ions X3CSO3- (X = H, Cl, F)

“…For trichloromethanesulfonate, Cl 3 C−SO 3 - , the much lower value, 2.57 N cm -1 , must largely be an effect of the steric repulsion between the CCl 3 and SO 3 groups. Examination of the intramolecular distances in the trichloromethanesulfonate ion shows that the six closest Cl···O distances in the staggered conformation range from 3.11 to 3.25 Å, mean value 3.18 Å, which is slightly less than the sum of the nonbonded van der Waals radii, 1.81 Å (Cl) + 1.40 Å (O)…”

“…As could be expected, the S−O stretching force constants generally decrease with increasing mean S−O bond distance except for one clear exception, the trichloromethanesulfonate (Cl 3 CSO 3 - ) ion. The mean O−S−O bond angle (within parentheses) in the pyramidal SO 3 group decreases in the order Cl 3 C−SO 3 - (114.2°), F 3 C−SO 3 - (113.8°), H 3 C−SO 3 - (113.6°), H−SO 3 - (113.1°), O−SO 3 2- (109.47°), and SO 3 2- (105.7°) …”

“…Theoretical spectra were obtained in a similar way as above (Table ) for the X 3 CSO 3 - (X = H, Cl, F) anions in staggered C 3 v conformation, ,, with the hydration simulated by assuming one water molecule hydrogen bonded to each oxygen atom, and compared with the corresponding solution and solid-state experimental spectra in Figures −14, respectively. For the hydrated CH 3 SO 3 - anion, the corrections to the calculated transition energies were obtained by applying the separately calculated relaxation effects for the first 9 A 1 and 7 E states and shifting the remaining states with the mean value (−4.04 eV).…”

“…Crystals of NaCCl 3 SO 3 ·H 2 O and CsHSO 3 were prepared as described elsewhere, , and CsDSO 3 was synthesized using D 2 O instead of H 2 O. Oxygen-free sulfite aqueous solutions for the sulfur XANES absorption and Raman measurements were prepared by dissolving Na 2 SO 3 in degassed water to approximately 0.05 and 1 M, respectively, under nitrogen atmosphere. The pH was measured with an IQ150 pH meter equipped with a glass electrode calibrated with standard buffers and adjusted with 1 M HCl or NaOH to pH = 0.0, 3.9 and 10.7 (XANES) and 0.0, 4.1, and 10.8 (Raman), respectively.…”

“…In nucleophilic substitution reactions the trifluoromethanesulfonate ion is a good leaving entity, a property ascribed to the electronegative CF 3 group. − However, a recent 35 Cl nuclear quadrupole resonance study indicated the smallest coordinating ability for the trichloromethanesulfonate (CCl 3 SO 3 - ) ion . Several analyses of the vibrational spectra of the anions above have been performed by normal coordinate analysis or quantum chemical calculations, despite the lack of structural data for trichloromethanesulfonate. − Numerous crystallographic studies have been carried out to structurally characterize methanesulfonate and trifluoromethanesulfonate compounds − but only one recently for the trichloromethanesulfonate ion …”