Sodium trichloromethanesulfonate monohydrate, Na
+·CCl
3SO
3−·H
2O, crystallizes in
P2
1/
a with all the atoms located in general positions. The trichloromethanesulfonate (trichlate) anion consists of pyramidal SO
3 and CCl
3 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 SO
3 groups form a square-pyramidal arrangement around the sodium ion.
Supporting information
CCDC reference: 621262
CCl3SO3Na·H2O was obtained from a solution prepared by stirring and
heating [323 (2) K] wax-like crystals of trichloromethanesulfonyl chloride
(CCl3SO2Cl, 2.547 g, Aldrich) in an excess (36 ml) of 1 mol dm-3 sodium
hydroxide solution (Edwards & Smith, 1991). After evaporating the solvent,
first in a rotary evaporator at 355 (2) K and then at reduced pressure in a
vacuum desiccator, colourless crystals were obtained, which recrystallized
from water.
Data collection: EXPOSE in IPDS Software (Stoe & Cie, 1997); cell refinement: CELL in IPDS Software (Stoe & Cie, 1997); data reduction: INTEGRATE in IPDS Software (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
Sodium trichloromethanesulfonate monohydrate
top
Crystal data top
Na+·CCl3O3S−·H2O | F(000) = 472 |
Mr = 239.43 | Dx = 2.072 Mg m−3 |
MonoclinicP21/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yab | Cell parameters from 221 reflections |
a = 10.727 (7) Å | θ = 3.5–27.1° |
b = 5.828 (3) Å | µ = 1.47 mm−1 |
c = 12.613 (9) Å | T = 291 K |
β = 103.24 (8)° | Pentagonal prism, colourless |
V = 767.6 (9) Å3 | 0.5 × 0.3 × 0.1 mm |
Z = 4 | |
Data collection top
Stoe IPDS diffractometer | 1805 independent reflections |
Radiation source: fine-focus sealed tube | 1312 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.100 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.8°, θmin = 3.3° |
φ scans | h = −14→14 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | k = −7→7 |
Tmin = 0.579, Tmax = 0.953 | l = −16→16 |
6794 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.127 | All H-atom parameters refined |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0767P)2] where P = (Fo2 + 2Fc2)/3 |
1805 reflections | (Δ/σ)max < 0.001 |
99 parameters | Δρmax = 0.86 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
Na+·CCl3O3S−·H2O | V = 767.6 (9) Å3 |
Mr = 239.43 | Z = 4 |
MonoclinicP21/a | Mo Kα radiation |
a = 10.727 (7) Å | µ = 1.47 mm−1 |
b = 5.828 (3) Å | T = 291 K |
c = 12.613 (9) Å | 0.5 × 0.3 × 0.1 mm |
β = 103.24 (8)° | |
Data collection top
Stoe IPDS diffractometer | 1805 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | 1312 reflections with I > 2σ(I) |
Tmin = 0.579, Tmax = 0.953 | Rint = 0.100 |
6794 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.127 | All H-atom parameters refined |
S = 0.96 | Δρmax = 0.86 e Å−3 |
1805 reflections | Δρmin = −0.43 e Å−3 |
99 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S | 0.05676 (7) | 0.04739 (11) | 0.17539 (7) | 0.0266 (2) | |
O1 | −0.0697 (2) | 0.1198 (4) | 0.1188 (2) | 0.0379 (6) | |
O2 | 0.1600 (2) | 0.1947 (4) | 0.1607 (2) | 0.0401 (6) | |
O3 | 0.0811 (2) | −0.1956 (4) | 0.1632 (2) | 0.0333 (5) | |
C | 0.0572 (3) | 0.0779 (5) | 0.3212 (3) | 0.0317 (7) | |
Cl1 | −0.07508 (10) | −0.07896 (17) | 0.34637 (9) | 0.0490 (3) | |
Cl2 | 0.20084 (10) | −0.02867 (19) | 0.40237 (9) | 0.0544 (3) | |
Cl3 | 0.03900 (10) | 0.37046 (15) | 0.35018 (9) | 0.0504 (3) | |
Na | −0.27893 (13) | −0.0510 (2) | 0.09992 (13) | 0.0393 (4) | |
O4 | −0.3336 (3) | 0.1051 (4) | −0.0781 (2) | 0.0391 (6) | |
H41 | −0.409 (5) | 0.124 (7) | −0.116 (4) | 0.045 (12)* | |
H42 | −0.315 (5) | 0.003 (9) | −0.107 (4) | 0.057 (16)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0232 (4) | 0.0190 (4) | 0.0403 (5) | −0.0016 (3) | 0.0132 (3) | −0.0001 (3) |
O1 | 0.0295 (12) | 0.0314 (12) | 0.0515 (15) | 0.0041 (9) | 0.0066 (10) | 0.0024 (11) |
O2 | 0.0377 (13) | 0.0285 (12) | 0.0617 (17) | −0.0095 (9) | 0.0271 (12) | −0.0012 (11) |
O3 | 0.0315 (11) | 0.0195 (10) | 0.0525 (15) | 0.0002 (8) | 0.0170 (10) | −0.0057 (10) |
C | 0.0335 (16) | 0.0222 (13) | 0.0419 (18) | 0.0024 (12) | 0.0142 (14) | −0.0014 (13) |
Cl1 | 0.0537 (6) | 0.0431 (5) | 0.0606 (6) | −0.0089 (4) | 0.0349 (5) | 0.0012 (4) |
Cl2 | 0.0479 (6) | 0.0595 (6) | 0.0507 (6) | 0.0182 (4) | 0.0007 (4) | −0.0009 (5) |
Cl3 | 0.0650 (6) | 0.0248 (4) | 0.0639 (7) | 0.0042 (4) | 0.0201 (5) | −0.0117 (4) |
Na | 0.0325 (7) | 0.0251 (6) | 0.0652 (10) | 0.0040 (5) | 0.0211 (7) | 0.0080 (6) |
O4 | 0.0313 (13) | 0.0244 (12) | 0.0607 (18) | 0.0029 (9) | 0.0087 (12) | −0.0037 (11) |
Geometric parameters (Å, º) top
S—O1 | 1.444 (3) | Na—O2iii | 2.358 (3) |
S—O2 | 1.446 (2) | Na—O4 | 2.368 (4) |
S—O3 | 1.455 (2) | Na—O3iv | 2.371 (3) |
S—C | 1.847 (4) | Na—O4v | 2.388 (3) |
O1—Na | 2.417 (3) | Na—Nav | 3.993 (3) |
O2—Nai | 2.358 (3) | Na—Navi | 3.993 (3) |
O3—Naii | 2.371 (3) | Na—H42 | 2.57 (5) |
C—Cl2 | 1.757 (4) | O4—Navi | 2.388 (3) |
C—Cl3 | 1.764 (3) | O4—H41 | 0.85 (5) |
C—Cl1 | 1.777 (3) | O4—H42 | 0.74 (5) |
| | | |
O1—S—O2 | 115.05 (15) | O2iii—Na—Nav | 160.53 (10) |
O1—S—O3 | 113.80 (14) | O4—Na—Nav | 73.89 (10) |
O2—S—O3 | 113.77 (13) | O3iv—Na—Nav | 87.72 (8) |
O1—S—C | 104.58 (17) | O4v—Na—Nav | 32.74 (8) |
O2—S—C | 104.09 (16) | O1—Na—Nav | 95.04 (9) |
O3—S—C | 103.84 (14) | O2iii—Na—Navi | 69.96 (7) |
S—O1—Na | 132.41 (15) | O4—Na—Navi | 33.05 (7) |
S—O2—Nai | 147.40 (16) | O3iv—Na—Navi | 150.34 (9) |
S—O3—Naii | 141.68 (13) | O4v—Na—Navi | 112.57 (10) |
Cl2—C—Cl3 | 110.18 (19) | O1—Na—Navi | 59.10 (8) |
Cl2—C—Cl1 | 110.11 (19) | Nav—Na—Navi | 93.72 (8) |
Cl3—C—Cl1 | 109.25 (17) | O2iii—Na—H42 | 103.5 (12) |
Cl2—C—S | 110.37 (18) | O4—Na—H42 | 16.8 (12) |
Cl3—C—S | 108.92 (18) | O3iv—Na—H42 | 117.3 (11) |
Cl1—C—S | 107.97 (19) | O4v—Na—H42 | 87.1 (12) |
O2iii—Na—O4 | 86.72 (11) | O1—Na—H42 | 88.3 (11) |
O2iii—Na—O3iv | 101.21 (10) | Nav—Na—H42 | 57.2 (12) |
O4—Na—O3iv | 121.34 (12) | Navi—Na—H42 | 43.8 (11) |
O2iii—Na—O4v | 164.20 (12) | Na—O4—Navi | 114.21 (13) |
O4—Na—O4v | 103.58 (9) | Na—O4—H41 | 125 (3) |
O3iv—Na—O4v | 83.81 (10) | Navi—O4—H41 | 106 (3) |
O2iii—Na—O1 | 85.76 (10) | Na—O4—H42 | 97 (4) |
O4—Na—O1 | 87.58 (12) | Navi—O4—H42 | 115 (4) |
O3iv—Na—O1 | 150.33 (11) | H41—O4—H42 | 99 (5) |
O4v—Na—O1 | 82.80 (10) | | |
Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y−1/2, z; (iii) x−1/2, −y+1/2, z; (iv) x−1/2, −y−1/2, z; (v) −x−1/2, y−1/2, −z; (vi) −x−1/2, y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H41···O3vi | 0.85 (5) | 2.09 (5) | 2.871 (4) | 153 (4) |
O4—H42···O1v | 0.75 (5) | 2.54 (5) | 3.016 (4) | 123 (5) |
O4—H42···O2vii | 0.75 (5) | 2.25 (5) | 2.915 (4) | 148 (5) |
Symmetry codes: (v) −x−1/2, y−1/2, −z; (vi) −x−1/2, y+1/2, −z; (vii) −x, −y, −z. |
Experimental details
Crystal data |
Chemical formula | Na+·CCl3O3S−·H2O |
Mr | 239.43 |
Crystal system, space group | MonoclinicP21/a |
Temperature (K) | 291 |
a, b, c (Å) | 10.727 (7), 5.828 (3), 12.613 (9) |
β (°) | 103.24 (8) |
V (Å3) | 767.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.5 × 0.3 × 0.1 |
|
Data collection |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1997) |
Tmin, Tmax | 0.579, 0.953 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6794, 1805, 1312 |
Rint | 0.100 |
(sin θ/λ)max (Å−1) | 0.657 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.127, 0.96 |
No. of reflections | 1805 |
No. of parameters | 99 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.86, −0.43 |
Selected geometric parameters (Å, º) topS—O1 | 1.444 (3) | C—Cl2 | 1.757 (4) |
S—O2 | 1.446 (2) | C—Cl3 | 1.764 (3) |
S—O3 | 1.455 (2) | C—Cl1 | 1.777 (3) |
S—C | 1.847 (4) | | |
| | | |
O1—S—O2 | 115.05 (15) | O3—S—C | 103.84 (14) |
O1—S—O3 | 113.80 (14) | Cl2—C—Cl3 | 110.18 (19) |
O2—S—O3 | 113.77 (13) | Cl2—C—Cl1 | 110.11 (19) |
O1—S—C | 104.58 (17) | Cl3—C—Cl1 | 109.25 (17) |
O2—S—C | 104.09 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H41···O3i | 0.85 (5) | 2.09 (5) | 2.871 (4) | 153 (4) |
O4—H42···O1ii | 0.75 (5) | 2.54 (5) | 3.016 (4) | 123 (5) |
O4—H42···O2iii | 0.75 (5) | 2.25 (5) | 2.915 (4) | 148 (5) |
Symmetry codes: (i) −x−1/2, y+1/2, −z; (ii) −x−1/2, y−1/2, −z; (iii) −x, −y, −z. |
S—C and mean S—O and C—X bond distances (Å), and
O—S—O, C—S—O and X—C—X angles (°), for several related
compounds (X = F or Cl) topCompound | S-C | S-O | C-X | O-S-O | C-S-O | X-C-X |
1 | 1.754 (2) | 1.45 | - | 111.9 | 106.9 | - |
2 | 1.746 (5) | 1.45 | - | 112.8 | 105.9 | - |
3 | 1.747 (6) | 1.44 | - | 112.5 | 106.2 | - |
4 | 1.811 (4) | 1.43 | 1.31 | 114.3 | 104.1 | 108.5 |
5 | 1.809 (4) | 1.43 | 1.31 | 113.8 | 104.3 | 108.7 |
6 | 1.833 (6) | 1.44 | 1.31 | 114.4 | 103.9 | 109.3 |
7 | 1.878 | 1.438 | 1.777 | - | 102.3 | - |
8 | 1.907 | 1.476 | 1.778 | - | 101.7 | - |
9 | 1.847 (4) | 1.45 | 1.77 | 114.2 | 104.2 | 109.8 |
10 | - | - | 1.76 | - | - | 110.9 |
Notes:
(1) CH3SO3Na (Wei & Hingerty, 1981);
(2) C20H23ClN3OS+.CH3SO3- (Wei, 1981);
(3) C21H26NO+.CH3SO3-.H2O (Jones et al., 1978);
(4) CF3SO3H.2H2O at 225K (Delaplane et al., 1975);
(5) CF3SO3Na (Sofina et al., 2003);
(6) Tb(H2O)9(CF3SO3)3 (Abbasi et al., 2005);
(7) CCl3SO3- at HF 6-31G* (Gejji et al., 1994);
(8) CCl3SO3- at MP2 6-31G* (Gejji et al., 1994);
(9) CCl3SO3Na.H2O (this work);
(10) CHCl3 (Sutton, 1965). |
Trichloromethanesulfonate (CCl3SO3-) salts were first prepared more than 150 years ago (Kolbe, 1845). The trichlate and the related trifluoromethanesulfonate (CF3SO3-) and mesylate (CH3SO3-) anions have been studied by means of vibrational spectroscopy complemented by normal coordinate analysis (Miles et al., 1969; Bürger et al., 1970). Gejji et al. (1994) performed quantum chemical calculations of the structure and vibrational frequencies of trichloromethanesulfonic acid, CCl3SO3H, and its anion. Edwards & Smith (1991) reported vibrational assignments of the acid and determined its dissociation constant in 2 mol dm-3 aqueous solution by Raman measurements. A recent 35Cl nuclear quadrupole resonance study concluded that the trichlate anion has weaker coordination ability than several chloroacetate anions (Wulfsberg et al., 2004). The present study of sodium trichloromethanesulfonate monohydrate (CCl3SO3Na·H2O) seems to be the first crystal structure reported containing a trichlate anion.
The crystal structure is described in the space group P21/a with all atoms located in general sites (4e). The pyramidal SO3 and CCl3 groups of the triclate anion are in a staggered conformation (Fig. 1 and Table 1). One water H atom (H42) is involved in a weak, bifurcated hydrogen bond to two O atoms, O1 and O2, of different trichlate ions, while the other H atom (H41) forms a shorter hydrogen bond (Fig. 1 and Table 2). The Na+ ion has an almost square-pyramidal environment of O atoms from two water molecules and three different SO3 groups, with a mean Na+···O distance of 2.38 Å.
As shown in Table 3, the mean S—O bond distance is not significantly influenced by hydrogen bonding or by replacing the –CCl3 group with –CH3 or –CF3. The C—S bond increases considerably from the mesylate (H3C—SO3-) to the trifluoromethanesulfonate (F3C—SO3-) ion, with an even longer C—S bond for the trichlate (Cl3C—SO3-), as predicted by theoretical studies. The electron-withdrawing effect of the electronegative Cl and F atoms evidently weakens the C—S bond and makes the O—S—O angles about two degrees larger than in the mesylate ion. The mean C—Cl bond length and Cl—C—Cl angle determined in this work agree well with the values found for trichloromethane (Sutton, 1965). Please check all of the values in Table 2 carefully; O4—H42 distance in _geom_bond loop in CIF is 0.74 (5).