Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025688/lx2014sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025688/lx2014Isup2.hkl |
CCDC reference: 655734
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.032
- wR factor = 0.093
- Data-to-parameter ratio = 13.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.85 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.70 mm PLAT220_ALERT_2_C Large Non-Solvent S Ueq(max)/Ueq(min) ... 2.64 Ratio PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 2.00 Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 39.19 Deg. O2 -S2 -NA 1.555 1.555 5.556
Author Response: The apparently abnormal O2---S2---Na 39.19 angle listed among CIF entries is actually irrelevant, since the S2---Na distance is not a bond distance. The same applies to other entries involving the distance between the S2 atom and the Na ion, as well as to entries involving distances between two Na ions. |
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.854 Tmax scaled 0.854 Tmin scaled 0.132
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL023_ALERT_1_A There is a mismatched ^ on line 125 The structure of the title compound, Na^+^.C~2~H~5~O~3~S~2~^-, commonly If you require a ^ then it should be escaped with a \, i.e. \^ Otherwise there must be a matching closing ~, e.g. ^12^C
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
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.
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.
For related literature, see: Bradley et al. (2007); Goren et al. (1998); Shaw & Graham (1987).
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.
Fig. 1. A view of the asymmetric unit in (I). Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. The crystal packing of (I), viewed along the a axis. |
Na+·C2H5O3S2− | F(000) = 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 = 9.0–65.0° |
b = 8.2749 (4) Å | µ = 7.88 mm−1 |
c = 24.2995 (11) Å | T = 173 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) |
Oxford Diffraction, Enhance ULTRA assembly monochromator | Rint = 0.050 |
ω scans | θmax = 72.2°, θmin = 3.6° |
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 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Only H-atom coordinates refined |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0592P)2 + 0.6874P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
1211 reflections | Δρmax = 0.58 e Å−3 |
89 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | 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) |
Na+·C2H5O3S2− | V = 1235.77 (10) Å3 |
Mr = 164.17 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 6.1458 (3) Å | µ = 7.88 mm−1 |
b = 8.2749 (4) Å | T = 173 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 | 0 restraints |
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 |
89 parameters |
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. |
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) |
Experimental details
Crystal data | |
Chemical formula | Na+·C2H5O3S2− |
Mr | 164.17 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 6.1458 (3), 8.2749 (4), 24.2995 (11) |
V (Å3) | 1235.77 (10) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 7.88 |
Crystal size (mm) | 0.70 × 0.20 × 0.02 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur PX Ultra CCD |
Absorption correction | Multi-scan (ABSPACK in CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.154, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7907, 1211, 1132 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.093, 1.12 |
No. of reflections | 1211 |
No. of parameters | 89 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.58, −0.43 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97.
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 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.