Acta Cryst. (2007). E63, o1796 [ doi:10.1107/S1600536807025688 ]
The crystal structure of the title compound, Na+·C2H5O3S2-, commonly known as mesna, has triple-layer sheets normal to the c axis, where the external layers of each set are formed by the anions which coordinate, through their sulfonate O atoms, the cations in the inner layer. The contacts between the outer sides of different sheets involve thiol S and methylene C atoms.
Samples of the compound, in microcrystalline form, were kindly provided by SIMS (SIMS srl, Reggello Firenze, Italy). Crystals suitable for X-ray diffraction were obtained by slow evaporation from water-methanol solutions, under a nitrogen atmosphere.
The positional parameters of hydrogen atoms were refined, with U(H) = 1.2Ueq(C) and U(H) = 1.5Ueq(S). Ranges of bond distances involving refined hydrogen atoms: C—H 0.95–1.04 Å.
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
![[Figure 1]](./lx2014fig1thm.gif)
| Fig. 1. A view of the asymmetric unit in (I). Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./lx2014fig2thm.gif)
| Fig. 2. The crystal packing of (I), viewed along the a axis. |
| Na+·C2H5O3S2– | F000 = 672 |
| Mr = 164.17 | Dx = 1.765 Mg m−3 |
| Orthorhombic, Pbca | Cu Kα radiation λ = 1.54180 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 4481 reflections |
| a = 6.1458 (3) Å | θ = 9.0–65.0º |
| b = 8.2749 (4) Å | µ = 7.88 mm−1 |
| c = 24.2995 (11) Å | T = 173 (2) K |
| V = 1235.77 (10) Å3 | Thin plate, colourless |
| Z = 8 | 0.70 × 0.20 × 0.02 mm |
| Oxford Diffraction Xcalibur PX Ultra CCD diffractometer | 1211 independent reflections |
| Radiation source: fine-focus sealed tube | 1132 reflections with I > 2σ(I) |
| Monochromator: Oxford Diffraction, Enhance ULTRA assembly | Rint = 0.050 |
| T = 173(2) K | θmax = 72.2º |
| ω scans | θmin = 3.6º |
| Absorption correction: multi-scan (ABSPACK in CrysAlis RED; Oxford Diffraction, 2006) | h = −6→7 |
| Tmin = 0.154, Tmax = 1.000 | k = −9→10 |
| 7907 measured reflections | l = −29→29 |
| Refinement on F2 | Hydrogen site location: difference Fourier map |
| Least-squares matrix: full | Only H-atom coordinates refined |
| R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0592P)2 + 0.6874P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.093 | (Δ/σ)max < 0.001 |
| S = 1.12 | Δρmax = 0.58 e Å−3 |
| 1211 reflections | Δρmin = −0.43 e Å−3 |
| 89 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0007 (2) |
| Secondary atom site location: difference Fourier map |
| Na+·C2H5O3S2– | V = 1235.77 (10) Å3 |
| Mr = 164.17 | Z = 8 |
| Orthorhombic, Pbca | Cu Kα |
| a = 6.1458 (3) Å | µ = 7.88 mm−1 |
| b = 8.2749 (4) Å | T = 173 (2) K |
| c = 24.2995 (11) Å | 0.70 × 0.20 × 0.02 mm |
| Oxford Diffraction Xcalibur PX Ultra CCD diffractometer | 1211 independent reflections |
| Absorption correction: multi-scan (ABSPACK in CrysAlis RED; Oxford Diffraction, 2006) | 1132 reflections with I > 2σ(I) |
| Tmin = 0.154, Tmax = 1.000 | Rint = 0.050 |
| 7907 measured reflections |
| R[F2 > 2σ(F2)] = 0.032 | 89 parameters |
| wR(F2) = 0.093 | Only H-atom coordinates refined |
| S = 1.12 | Δρmax = 0.58 e Å−3 |
| 1211 reflections | Δρmin = −0.43 e Å−3 |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | −0.11102 (11) | 0.24713 (8) | 0.69546 (2) | 0.0427 (2) | |
| H1S | −0.182 (6) | 0.253 (4) | 0.6475 (12) | 0.064* | |
| C1 | 0.0621 (4) | 0.0714 (3) | 0.68613 (8) | 0.0327 (5) | |
| H11 | 0.142 (4) | 0.057 (3) | 0.7234 (11) | 0.039* | |
| H12 | −0.029 (5) | −0.023 (4) | 0.6839 (11) | 0.039* | |
| C2 | 0.2284 (3) | 0.0829 (2) | 0.63964 (7) | 0.0231 (4) | |
| H21 | 0.293 (4) | 0.187 (3) | 0.6382 (9) | 0.028* | |
| H22 | 0.340 (4) | 0.001 (3) | 0.6436 (9) | 0.028* | |
| S2 | 0.11652 (7) | 0.04671 (5) | 0.573398 (17) | 0.01618 (19) | |
| O1 | −0.0356 (2) | 0.17785 (15) | 0.56133 (5) | 0.0215 (3) | |
| O2 | 0.3006 (2) | 0.05000 (15) | 0.53498 (5) | 0.0238 (3) | |
| O3 | 0.0128 (2) | −0.11106 (16) | 0.57597 (5) | 0.0253 (3) | |
| Na | −0.37169 (11) | 0.18754 (9) | 0.51844 (3) | 0.0202 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0508 (4) | 0.0445 (4) | 0.0328 (4) | −0.0012 (3) | 0.0161 (2) | −0.0068 (2) |
| C1 | 0.0492 (13) | 0.0256 (10) | 0.0234 (10) | −0.0089 (10) | 0.0006 (9) | 0.0017 (8) |
| C2 | 0.0275 (10) | 0.0185 (9) | 0.0234 (8) | −0.0007 (8) | −0.0069 (7) | 0.0003 (7) |
| S2 | 0.0168 (3) | 0.0124 (3) | 0.0193 (3) | 0.00017 (14) | −0.00088 (14) | −0.00126 (14) |
| O1 | 0.0214 (7) | 0.0186 (7) | 0.0244 (6) | 0.0060 (5) | −0.0020 (5) | 0.0005 (5) |
| O2 | 0.0196 (7) | 0.0233 (7) | 0.0285 (7) | −0.0013 (5) | 0.0044 (5) | −0.0059 (5) |
| O3 | 0.0318 (8) | 0.0156 (7) | 0.0285 (7) | −0.0066 (6) | −0.0043 (5) | −0.0003 (5) |
| Na | 0.0177 (4) | 0.0170 (4) | 0.0259 (4) | 0.0018 (3) | −0.0004 (2) | −0.0019 (3) |
| S1—C1 | 1.816 (3) | O2—Naiii | 2.3482 (15) |
| S1—H1S | 1.25 (3) | O2—Naii | 2.3958 (14) |
| C1—C2 | 1.526 (3) | O2—Nai | 2.7428 (15) |
| C1—H11 | 1.04 (3) | O3—Naiv | 2.3418 (14) |
| C1—H12 | 0.96 (3) | Na—O3v | 2.3418 (14) |
| C2—S2 | 1.7759 (18) | Na—O2vi | 2.3482 (15) |
| C2—H21 | 0.95 (3) | Na—O2ii | 2.3958 (14) |
| C2—H22 | 0.97 (3) | Na—O1vii | 2.4522 (15) |
| S2—O3 | 1.4542 (14) | Na—O2vii | 2.7428 (15) |
| S2—O1 | 1.4620 (13) | Na—S2vii | 3.1339 (8) |
| S2—O2 | 1.4669 (13) | Na—S2ii | 3.3462 (8) |
| S2—Nai | 3.1339 (8) | Na—Nai | 3.3637 (6) |
| S2—Naii | 3.3462 (8) | Na—Navii | 3.3637 (6) |
| O1—Na | 2.3150 (15) | Na—Naviii | 3.5949 (14) |
| O1—Nai | 2.4522 (15) | ||
| C1—S1—H1S | 97.0 (16) | O2ii—Na—O1vii | 91.11 (5) |
| C2—C1—S1 | 115.73 (15) | O1—Na—O2vii | 84.04 (5) |
| C2—C1—H11 | 109.7 (15) | O3v—Na—O2vii | 82.06 (5) |
| S1—C1—H11 | 104.9 (15) | O2vi—Na—O2vii | 142.74 (5) |
| C2—C1—H12 | 113.5 (17) | O2ii—Na—O2vii | 108.83 (5) |
| S1—C1—H12 | 108.5 (17) | O1vii—Na—O2vii | 54.88 (4) |
| H11—C1—H12 | 103 (2) | O1—Na—S2vii | 111.44 (4) |
| C1—C2—S2 | 113.64 (15) | O3v—Na—S2vii | 85.25 (4) |
| C1—C2—H21 | 111.5 (15) | O2vi—Na—S2vii | 116.24 (4) |
| S2—C2—H21 | 106.4 (14) | O2ii—Na—S2vii | 101.19 (4) |
| C1—C2—H22 | 110.8 (14) | O1vii—Na—S2vii | 26.98 (3) |
| S2—C2—H22 | 104.1 (14) | O2vii—Na—S2vii | 27.90 (3) |
| H21—C2—H22 | 110 (2) | O1—Na—S2ii | 82.07 (4) |
| O3—S2—O1 | 113.24 (8) | O3v—Na—S2ii | 169.72 (4) |
| O3—S2—O2 | 112.46 (8) | O2vi—Na—S2ii | 103.61 (4) |
| O1—S2—O2 | 110.59 (8) | O2ii—Na—S2ii | 22.76 (3) |
| O3—S2—C2 | 106.39 (9) | O1vii—Na—S2ii | 85.90 (4) |
| O1—S2—C2 | 107.70 (9) | O2vii—Na—S2ii | 87.83 (3) |
| O2—S2—C2 | 105.98 (9) | S2vii—Na—S2ii | 86.70 (2) |
| O3—S2—Nai | 132.13 (6) | O1—Na—Nai | 46.80 (3) |
| O1—S2—Nai | 49.55 (5) | O3v—Na—Nai | 106.18 (5) |
| O2—S2—Nai | 61.05 (5) | O2vi—Na—Nai | 168.01 (5) |
| C2—S2—Nai | 121.20 (7) | O2ii—Na—Nai | 86.62 (4) |
| O3—S2—Naii | 73.39 (6) | O1vii—Na—Nai | 91.44 (5) |
| O1—S2—Naii | 126.58 (6) | O2vii—Na—Nai | 43.77 (3) |
| O2—S2—Naii | 39.19 (5) | S2vii—Na—Nai | 67.40 (3) |
| C2—S2—Naii | 121.40 (7) | S2ii—Na—Nai | 64.67 (2) |
| Nai—S2—Naii | 85.45 (2) | O1—Na—Navii | 161.03 (5) |
| S2—O1—Na | 133.36 (8) | O3v—Na—Navii | 66.55 (4) |
| S2—O1—Nai | 103.47 (7) | O2vi—Na—Navii | 53.91 (3) |
| Na—O1—Nai | 89.71 (4) | O2ii—Na—Navii | 105.93 (5) |
| S2—O2—Naiii | 141.20 (8) | O1vii—Na—Navii | 43.49 (4) |
| S2—O2—Naii | 118.05 (7) | O2vii—Na—Navii | 89.03 (4) |
| Naiii—O2—Naii | 98.53 (5) | S2vii—Na—Navii | 64.75 (3) |
| S2—O2—Nai | 91.05 (6) | S2ii—Na—Navii | 115.37 (3) |
| Naiii—O2—Nai | 82.32 (4) | Nai—Na—Navii | 132.00 (5) |
| Naii—O2—Nai | 117.62 (6) | O1—Na—Naviii | 118.28 (5) |
| S2—O3—Naiv | 140.85 (8) | O3v—Na—Naviii | 126.93 (5) |
| O1—Na—O3v | 94.95 (5) | O2vi—Na—Naviii | 41.23 (3) |
| O1—Na—O2vi | 132.19 (6) | O2ii—Na—Naviii | 40.24 (4) |
| O3v—Na—O2vi | 85.71 (5) | O1vii—Na—Naviii | 90.85 (4) |
| O1—Na—O2ii | 93.02 (5) | O2vii—Na—Naviii | 137.31 (4) |
| O3v—Na—O2ii | 167.14 (6) | S2vii—Na—Naviii | 114.72 (3) |
| O2vi—Na—O2ii | 81.47 (5) | S2ii—Na—Naviii | 62.56 (2) |
| O1—Na—O1vii | 137.58 (5) | Nai—Na—Naviii | 126.85 (4) |
| O3v—Na—O1vii | 89.80 (5) | Navii—Na—Naviii | 78.35 (2) |
| O2vi—Na—O1vii | 90.17 (5) | ||
| S1—C1—C2—S2 | −79.35 (18) | C2—S2—O2—Nai | −117.22 (7) |
| C1—C2—S2—O3 | −55.72 (17) | Naii—S2—O2—Nai | 122.36 (9) |
| C1—C2—S2—O1 | 66.00 (16) | O1—S2—O3—Naiv | 76.61 (15) |
| C1—C2—S2—O2 | −175.62 (14) | O2—S2—O3—Naiv | −49.67 (16) |
| C1—C2—S2—Nai | 118.91 (14) | C2—S2—O3—Naiv | −165.28 (13) |
| C1—C2—S2—Naii | −135.95 (13) | Nai—S2—O3—Naiv | 20.92 (19) |
| O3—S2—O1—Na | −23.73 (13) | Naii—S2—O3—Naiv | −46.67 (12) |
| O2—S2—O1—Na | 103.54 (11) | S2—O1—Na—O3v | 144.00 (11) |
| C2—S2—O1—Na | −141.08 (11) | Nai—O1—Na—O3v | −107.60 (5) |
| Nai—S2—O1—Na | 102.65 (11) | S2—O1—Na—O2vi | 55.32 (14) |
| Naii—S2—O1—Na | 62.33 (13) | Nai—O1—Na—O2vi | 163.72 (7) |
| O3—S2—O1—Nai | −126.38 (7) | S2—O1—Na—O2ii | −25.90 (11) |
| O2—S2—O1—Nai | 0.89 (9) | Nai—O1—Na—O2ii | 82.50 (5) |
| C2—S2—O1—Nai | 116.27 (8) | S2—O1—Na—O1vii | −120.86 (11) |
| Naii—S2—O1—Nai | −40.32 (9) | Nai—O1—Na—O1vii | −12.46 (4) |
| O3—S2—O2—Naiii | −154.07 (12) | S2—O1—Na—O2vii | −134.53 (11) |
| O1—S2—O2—Naiii | 78.23 (14) | Nai—O1—Na—O2vii | −26.13 (4) |
| C2—S2—O2—Naiii | −38.21 (15) | S2—O1—Na—S2vii | −129.17 (10) |
| Nai—S2—O2—Naiii | 79.01 (12) | Nai—O1—Na—S2vii | −20.77 (4) |
| Naii—S2—O2—Naiii | −158.63 (18) | S2—O1—Na—S2ii | −45.90 (10) |
| O3—S2—O2—Naii | 4.56 (11) | Nai—O1—Na—S2ii | 62.50 (3) |
| O1—S2—O2—Naii | −123.14 (8) | S2—O1—Na—Nai | −108.40 (12) |
| C2—S2—O2—Naii | 120.42 (9) | S2—O1—Na—Navii | 156.33 (12) |
| Nai—S2—O2—Naii | −122.36 (9) | Nai—O1—Na—Navii | −95.27 (16) |
| O3—S2—O2—Nai | 126.92 (7) | S2—O1—Na—Naviii | 7.00 (13) |
| O1—S2—O2—Nai | −0.78 (8) | Nai—O1—Na—Naviii | 115.40 (5) |
| Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x, −y, −z+1; (iii) x+1, y, z; (iv) −x−1/2, y−1/2, z; (v) −x−1/2, y+1/2, z; (vi) x−1, y, z; (vii) x−1/2, −y+1/2, −z+1; (viii) −x−1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| S1—H1S···O1 | 1.25 (3) | 2.36 (3) | 3.342 (1) | 133 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| S1—H1S···O1 | 1.25 (3) | 2.36 (3) | 3.342 (1) | 133 (2) |
The authors acknowledge financial support from the Italian Ministero dell'Istruzione, dell'Universitá e della Ricerca.
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.
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The title compound Mesna, (I), is a drug used therapeutically to reduce the incidence of haemorrhagic cystitis and haematuria in patients receiving cancer chemotherapy (Shaw & Graham, 1987; Goren et al., 1998; Bradley et al., 2007). It is rapidly oxidized to its major metabolite, mesna disulfide (dimesna).
In the anion (Fig. 1) the S1—H1S bond almost eclipses the S2—O1 bond, forming a sort of six-membered ring with a long O1···H1S 2.36 (3) Å contact distance. The structure presents alternating layers of anions and cations parallel to the ab face, grouped in sets of three. The two outer layers of each set are formed by anions, oriented with their sulfonate sides toward the inner layer, formed by the cations (Fig. 2). The outer sides of each three-layer sheet are occupied by methylene carbons and thiol sulfur atoms. The shortest contacts between thiol sulfur atoms are 4.476 (1) Å (intralayer) and 4.058 (1) Å (interlayer). The shortest contacts between thiol sulfurs and carbon atoms of vicinal sheets are 3.799 (2) Å. The Na+ ion is in an irregular environment of six oxygen atoms from five different anions. Five Na—O distances are in the range 2.315 (2)–2.452 (2) Å; the sixth one, formed by an oxygen of the unique chelating sulfonate group in the Na+ coordination sphere, is longer: 2.743 (2) Å. The oxygen atoms differ in their coordination modes: O1 bridges between two cations, O2 is bound to three, whereas O3 only to one.