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Acta Cryst. (2008). E64, m1476-m1477    [ doi:10.1107/S1600536808031814 ]

Sodium 2-mercaptoethanesulfonate monohydrate (coenzyme M sodium salt monohydrate)

S. Mayr, D. Günther, B. Jaun and W. B. Schweizer

Abstract top

The 2-thioethanesulfonate anion is the smallest known coenzyme in nature (HS-CoM) and plays a key role in methanogenesis by anaerobic archaea, as well as in the oxidation of alkenes by Gram-negative and Gram-positive eubacteria. The title compound, Na+·C2H5O3S2-·H2O, is the Na+ salt of HS-CoM crystallized as the monohydrate. Six O atoms form a distorted octahedral coordination geometry around the Na atom, at distances in the range 2.312 (4)-2.517 (3) Å. Two O atoms of the sulfonate group, one O atom of each of three other symmetry-related sulfonate groups plus the water O atom form the coordination environment of the Na+ ion. This arrangement forms Na-O-Na layers in the crystal structure, parallel to (100).

Comment top

The title compound includes 2-thioethanesulfonate ion, the smallest known coenzyme in nature, coenzyme M, which plays a key role in methanogenesis by anaerobic archaea (Thauer, 1998) and in the oxidation of alkenes by gram-negative and gram-positive eubacteria (Allen et al., 1999). Furthermore its sodium salt (mesna) is medically used as mucolytics and to prevent urotoxic side effects of certain anticancer drugs (Bruchhausen et al., 1993). Whereas the biosynthesis of coenzyme M starts by sulfitation of phosphoenolpyruvate (Graham et al., 2002), the chemical synthesis begins from sodium 2-bromoethanesulfonate and thiourea in ammoniacal solution (Bruchhausen et al., 1993). Since 2-thioethanesulfonic acid represents a highly viscous oil decomposing under release of hydrogen sulfide at room temperature, it is usually stored and sold as stable sodium or ammonium salt (Schramm et al., 1955). The title compound is the monohydrate of the sodium salt.

Six O atoms show a distorted octahedral coordination geometry around the Na atom at distances in the range of 2.312 (4)–2.517 (3) Å (Fig. 1). Two O atoms of a SO3 group and one O of three other SO3 groups plus the water O atom form the coordination sphere of the Na+ ion. This forms Na–O–Na layers parallel to (100) in the crystal (Fig. 2).

The crystal structure of the unhydrated form (Bambagiotti-Alberti et al., 2007; CSD refcode UDUVUL) shows a similar six-fold coordination of the Na atom where the water O atom is replaced by an O-atom of a SO3 group. The conformation of the S atoms is antiperiplanar in our compound and gauche in the unhydrated form.

Related literature top

For related literature about HS–CoM, see: Allen et al. (1999); Bruchhausen et al. (1993); Günther & Hattendorf (2005); Graham et al. (2002); Latkoczy & Günther (2002); Mackay et al. (1999); Schramm et al. (1955); Thauer (1998). For the structure of the unhydrated Na HS–CoM salt, see: Bambagiotti-Alberti et al. (2007).

Experimental top

When adding pure ethanol to a concentrated solution of 2-thioethanesulfonic acid in water, we noticed a precipitating white crystalline mass never described before in the literature. Micro elementary analysis based on the empirical formula (C2H8O4S2) of the hydrated acid (HS–CoM-H3O+) showed significantly low values for C and H. At the same time 1H and 13C NMR analysis of the precipitate in D2O ruled out any organic impurities. Investigations into the crystals by laser ablation inductively coupled plasma sector field mass spectrometry (LA-ICP-SF MS), however, clearly revealed the presence of sodium in hyperstoichiometric amounts: molar ratio (Na-23)/(S-32) = 1.34 (RSD: 8,5%, n = 9) (Günther & Hattendorf, 2005; Latkoczy & Günther, 2002). The white precipitate consisted of two different types of crystals, needles and thin plates. The needles were used for structure analysis by X-ray diffraction.

Refinement top

H-positions for the methylene CH2 groups have been calculated with fixed distance of 1.08 Å. H atoms for the water molecule and the thiol group have been taken from a difference map and were included in the refinement in their as-found positions.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek 2003); software used to prepare material for publication: maXus (Mackay et al., 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of sodium 2-thioethanesulfonate hydrate with 50% probability displacement ellipsoids. H atoms are omitted for clarity. The complete coordination of the Na atom is shown. Symmetry codes: (a) x, -1+y, z; (b) x, 1+y, z; (c) 1/2-x, -1/2+y, -1/2+z; (d) 1/2-x, -1/2+y, 1/2+z; (e) 1/2-x, 1/2+y, -1/2+z; (f) 1/2-x, 1/2+y, 1/2+z.
[Figure 2] Fig. 2. Crystal structure viewed down the diagonal of the a–b axis, showing the layer structure of Na—O clusters.
sodium 2-mercaptoethanesulfonate monohydrate top
Crystal data top
Na+·C2H5O3S2−·H2ODx = 1.676 Mg m−3
Mr = 182.19Melting point: 473 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 5975 reflections
a = 23.4301 (8) Åθ = 2.3–27.5°
b = 5.0324 (2) ŵ = 0.74 mm−1
c = 6.1254 (2) ÅT = 223 K
V = 722.24 (4) Å3Plate, colourless
Z = 40.26 × 0.20 × 0.01 mm
F(000) = 376.0
Data collection top
Nonius KappaCCD
diffractometer		Rint = 0.065
Radiation source: fine-focus sealed tubeθmax = 27.5°, θmin = 3.4°
CCD scansh = −29→30
1647 measured reflectionsk = −6→6
1534 independent reflectionsl = −7→7
1263 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max < 0.001
1534 reflectionsΔρmax = 0.25 e Å−3
88 parametersΔρmin = −0.37 e Å−3
1 restraintAbsolute structure: Flack (1983), 627 Friedel pairs
0 constraintsFlack parameter: 0.13 (18)
Crystal data top
Na+·C2H5O3S2−·H2OV = 722.24 (4) Å3
Mr = 182.19Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 23.4301 (8) ŵ = 0.74 mm−1
b = 5.0324 (2) ÅT = 223 K
c = 6.1254 (2) Å0.26 × 0.20 × 0.01 mm
Data collection top
Nonius KappaCCD
diffractometer		1263 reflections with I > 2σ(I)
1647 measured reflectionsRint = 0.065
1534 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.131Δρmax = 0.25 e Å−3
S = 0.95Δρmin = −0.37 e Å−3
1534 reflectionsAbsolute structure: Flack (1983), 627 Friedel pairs
88 parametersFlack parameter: 0.13 (18)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S3−0.00830 (4)0.7465 (2)0.8298 (4)0.0483 (4)
H3−0.01540.85420.68130.058*
S40.17410 (3)0.75424 (11)0.66676 (19)0.0185 (2)
Na90.26442 (4)0.3309 (2)0.6658 (4)0.0238 (3)
O50.19813 (10)0.6264 (6)0.4720 (5)0.0239 (7)
O60.18238 (8)1.0402 (4)0.6710 (8)0.0286 (5)
O70.33586 (10)0.6737 (5)0.6717 (8)0.0338 (5)
H10.32590.80980.75950.023 (11)*
H20.33740.74650.53320.047 (16)*
O80.19475 (10)0.6245 (6)0.8649 (5)0.0257 (7)
C10.06798 (17)0.8051 (9)0.8424 (9)0.0464 (11)
H1A0.07561.01660.85090.056*
H1B0.08460.71690.99000.056*
C20.09943 (14)0.6946 (6)0.6517 (10)0.0279 (8)
H2A0.08290.78270.50390.033*
H2B0.09200.48300.64310.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S30.0235 (5)0.0688 (8)0.0526 (8)−0.0031 (4)0.0074 (6)0.0024 (6)
S40.0182 (4)0.0178 (4)0.0194 (4)−0.00146 (19)0.0008 (4)0.0002 (7)
Na90.0267 (6)0.0228 (6)0.0219 (6)0.0034 (4)−0.0009 (9)−0.0004 (10)
O50.0302 (16)0.0223 (15)0.0191 (18)−0.0013 (11)0.0050 (14)−0.0031 (12)
O60.0325 (10)0.0188 (10)0.0344 (12)−0.0029 (8)0.0011 (17)−0.003 (2)
O70.0398 (13)0.0345 (11)0.0271 (13)0.0012 (10)0.004 (2)−0.005 (2)
O80.0301 (16)0.0271 (17)0.0197 (18)0.0020 (12)−0.0011 (13)−0.0027 (14)
C10.0228 (17)0.063 (3)0.053 (3)−0.0050 (17)0.010 (2)−0.013 (3)
C20.0182 (14)0.0364 (16)0.029 (2)−0.0033 (12)−0.001 (2)−0.008 (2)
Geometric parameters (Å, °) top
S3—C11.813 (4)Na9—Na9i4.0207 (5)
S3—H31.0714Na9—Na9ii4.0207 (5)
S4—O61.4522 (19)Na9—Na9v4.0207 (5)
S4—O81.460 (4)O5—Na9v2.312 (4)
S4—O51.468 (3)O6—Na9vi2.416 (2)
S4—C21.778 (3)O7—H10.9012
S4—Na93.0028 (13)O7—H20.9247
Na9—O5i2.312 (4)O8—Na9iv2.322 (4)
Na9—O8ii2.322 (4)C1—C21.489 (6)
Na9—O72.404 (3)C1—H1A1.0800
Na9—O6iii2.416 (2)C1—H1B1.0800
Na9—O52.456 (3)C2—H2A1.0800
Na9—O82.517 (3)C2—H2B1.0800
Na9—Na9iv4.0207 (5)
C1—S3—H396.1O8—Na9—Na9i83.64 (8)
O6—S4—O8112.6 (2)S4—Na9—Na9i108.91 (6)
O6—S4—O5113.4 (2)Na9iv—Na9—Na9i77.477 (11)
O8—S4—O5110.64 (11)O5i—Na9—Na9ii113.78 (8)
O6—S4—C2107.43 (13)O8ii—Na9—Na9ii35.38 (7)
O8—S4—C2107.1 (2)O7—Na9—Na9ii125.28 (13)
O5—S4—C2105.2 (2)O6iii—Na9—Na9ii59.83 (11)
O6—S4—Na9127.52 (9)O5—Na9—Na9ii84.52 (8)
O8—S4—Na956.70 (12)O8—Na9—Na9ii128.86 (8)
O5—S4—Na954.35 (12)S4—Na9—Na9ii109.09 (5)
C2—S4—Na9125.01 (11)Na9iv—Na9—Na9ii160.65 (6)
O5i—Na9—O8ii106.77 (8)Na9i—Na9—Na9ii99.226 (14)
O5i—Na9—O792.45 (14)O5i—Na9—Na9v163.76 (8)
O8ii—Na9—O792.65 (14)O8ii—Na9—Na9v75.20 (9)
O5i—Na9—O6iii91.25 (13)O7—Na9—Na9v71.31 (12)
O8ii—Na9—O6iii93.87 (12)O6iii—Na9—Na9v104.78 (10)
O7—Na9—O6iii171.25 (9)O5—Na9—Na9v31.43 (7)
O5i—Na9—O5154.34 (14)O8—Na9—Na9v83.84 (8)
O8ii—Na9—O598.49 (14)S4—Na9—Na9v55.88 (5)
O7—Na9—O590.75 (11)Na9iv—Na9—Na9v99.226 (14)
O6iii—Na9—O582.52 (10)Na9i—Na9—Na9v160.65 (6)
O5i—Na9—O896.56 (14)Na9ii—Na9—Na9v77.476 (11)
O8ii—Na9—O8156.12 (14)S4—O5—Na9v127.60 (18)
O7—Na9—O891.32 (12)S4—O5—Na996.60 (16)
O6iii—Na9—O880.38 (10)Na9v—O5—Na9114.93 (10)
O5—Na9—O857.90 (7)S4—O6—Na9vi134.91 (12)
O5i—Na9—S4125.55 (10)Na9—O7—H1112.0
O8ii—Na9—S4127.54 (10)Na9—O7—H2107.3
O7—Na9—S488.94 (7)H1—O7—H2104.9
O6iii—Na9—S482.46 (6)S4—O8—Na9iv126.59 (19)
O5—Na9—S429.05 (8)S4—O8—Na994.29 (16)
O8—Na9—S429.01 (8)Na9iv—O8—Na9112.33 (10)
O5i—Na9—Na9iv74.00 (8)C2—C1—S3113.2 (3)
O8ii—Na9—Na9iv162.52 (8)C2—C1—H1A108.9
O7—Na9—Na9iv69.91 (11)S3—C1—H1A108.9
O6iii—Na9—Na9iv103.59 (10)C2—C1—H1B108.9
O5—Na9—Na9iv83.28 (8)S3—C1—H1B108.9
O8—Na9—Na9iv32.29 (7)H1A—C1—H1B107.8
S4—Na9—Na9iv55.67 (5)C1—C2—S4112.5 (3)
O5i—Na9—Na9i33.64 (7)C1—C2—H2A109.1
O8ii—Na9—Na9i113.20 (9)S4—C2—H2A109.1
O7—Na9—Na9i123.68 (13)C1—C2—H2B109.1
O6iii—Na9—Na9i58.49 (11)S4—C2—H2B109.1
O5—Na9—Na9i129.85 (9)H2A—C2—H2B107.8
O6—S4—Na9—O5i91.9 (3)O8—Na9—O5—S44.61 (8)
O8—S4—Na9—O5i−2.37 (19)Na9iv—Na9—O5—S4−16.81 (12)
O5—S4—Na9—O5i−174.30 (19)Na9i—Na9—O5—S450.69 (17)
C2—S4—Na9—O5i−90.6 (3)Na9ii—Na9—O5—S4148.14 (13)
O6—S4—Na9—O8ii−92.9 (3)Na9v—Na9—O5—S4−137.0 (2)
O8—S4—Na9—O8ii172.8 (2)O5i—Na9—O5—Na9v147.7 (2)
O5—S4—Na9—O8ii0.92 (18)O8ii—Na9—O5—Na9v−42.28 (14)
C2—S4—Na9—O8ii84.6 (3)O7—Na9—O5—Na9v50.50 (18)
O6—S4—Na9—O7−0.3 (3)O6iii—Na9—O5—Na9v−135.11 (15)
O8—S4—Na9—O7−94.6 (2)O8—Na9—O5—Na9v141.6 (2)
O5—S4—Na9—O793.4 (2)S4—Na9—O5—Na9v137.0 (2)
C2—S4—Na9—O7177.2 (2)Na9iv—Na9—O5—Na9v120.17 (13)
O6—S4—Na9—O6iii178.0 (4)Na9i—Na9—O5—Na9v−172.34 (6)
O8—S4—Na9—O6iii83.75 (18)Na9ii—Na9—O5—Na9v−74.88 (13)
O5—S4—Na9—O6iii−88.17 (17)O8—S4—O6—Na9vi67.2 (4)
C2—S4—Na9—O6iii−4.5 (3)O5—S4—O6—Na9vi−59.3 (4)
O6—S4—Na9—O5−93.8 (3)C2—S4—O6—Na9vi−175.1 (4)
O8—S4—Na9—O5171.92 (14)Na9—S4—O6—Na9vi2.7 (5)
C2—S4—Na9—O583.7 (3)O6—S4—O8—Na9iv1.0 (3)
O6—S4—Na9—O894.3 (3)O5—S4—O8—Na9iv129.03 (19)
O5—S4—Na9—O8−171.92 (14)C2—S4—O8—Na9iv−116.9 (2)
C2—S4—Na9—O8−88.2 (3)Na9—S4—O8—Na9iv122.0 (2)
O6—S4—Na9—Na9iv65.9 (3)O6—S4—O8—Na9−121.06 (16)
O8—S4—Na9—Na9iv−28.43 (14)O5—S4—O8—Na97.01 (12)
O5—S4—Na9—Na9iv159.65 (14)C2—S4—O8—Na9121.08 (15)
C2—S4—Na9—Na9iv−116.6 (2)O5i—Na9—O8—S4178.06 (16)
O6—S4—Na9—Na9i125.1 (3)O8ii—Na9—O8—S4−14.1 (4)
O8—S4—Na9—Na9i30.82 (14)O7—Na9—O8—S485.44 (17)
O5—S4—Na9—Na9i−141.11 (14)O6iii—Na9—O8—S4−91.78 (16)
C2—S4—Na9—Na9i−57.4 (2)O5—Na9—O8—S4−4.62 (8)
O6—S4—Na9—Na9ii−127.6 (3)Na9iv—Na9—O8—S4132.6 (2)
O8—S4—Na9—Na9ii138.14 (14)Na9i—Na9—O8—S4−150.81 (13)
O5—S4—Na9—Na9ii−33.78 (14)Na9ii—Na9—O8—S4−54.07 (17)
C2—S4—Na9—Na9ii49.9 (2)Na9v—Na9—O8—S414.40 (12)
O6—S4—Na9—Na9v−68.3 (3)O5i—Na9—O8—Na9iv45.45 (13)
O8—S4—Na9—Na9v−162.63 (14)O8ii—Na9—O8—Na9iv−146.7 (2)
O5—S4—Na9—Na9v25.45 (14)O7—Na9—O8—Na9iv−47.17 (17)
C2—S4—Na9—Na9v109.2 (2)O6iii—Na9—O8—Na9iv135.61 (15)
O6—S4—O5—Na9v−8.3 (3)O5—Na9—O8—Na9iv−137.2 (2)
O8—S4—O5—Na9v−135.9 (2)S4—Na9—O8—Na9iv−132.6 (2)
C2—S4—O5—Na9v108.8 (2)Na9i—Na9—O8—Na9iv76.58 (13)
Na9—S4—O5—Na9v−128.7 (2)Na9ii—Na9—O8—Na9iv173.32 (6)
O6—S4—O5—Na9120.40 (17)Na9v—Na9—O8—Na9iv−118.21 (13)
O8—S4—O5—Na9−7.21 (12)S3—C1—C2—S4179.9 (2)
C2—S4—O5—Na9−122.50 (16)O6—S4—C2—C1−60.6 (4)
O5i—Na9—O5—S410.8 (4)O8—S4—C2—C160.6 (4)
O8ii—Na9—O5—S4−179.26 (15)O5—S4—C2—C1178.3 (3)
O7—Na9—O5—S4−86.47 (18)Na9—S4—C2—C1121.5 (3)
O6iii—Na9—O5—S487.92 (15)
Symmetry codes: (i) −x+1/2, y−1/2, z+1/2; (ii) −x+1/2, y−1/2, z−1/2; (iii) x, y−1, z; (iv) −x+1/2, y+1/2, z+1/2; (v) −x+1/2, y+1/2, z−1/2; (vi) x, y+1, z.
Table 1
Selected geometric parameters (Å) top
Na9—O5i2.312 (4)Na9—O6iii2.416 (2)
Na9—O8ii2.322 (4)Na9—O52.456 (3)
Na9—O72.404 (3)Na9—O82.517 (3)
Symmetry codes: (i) −x+1/2, y−1/2, z+1/2; (ii) −x+1/2, y−1/2, z−1/2; (iii) x, y−1, z.
Acknowledgements top

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references
References top

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