research communications
The crystal structures of two novel polymorphs of bis(oxonium) ethane-1,2-disulfonate
aArdena, Solid State Research Services, Meibergdreef 31, 1105 AZ Amsterdam, The Netherlands
*Correspondence e-mail: jaroslaw.mazurek@ardena.com
Two novel crystal forms of bis(oxonium) ethane-1,2-disulfonate, 2H3O−·C2H4O6S22−, are reported. Polymorph II has monoclinic (P21/n) symmetry, while the symmetry of form III is triclinic (P). Both structures display extensive networks of O—H⋯O hydrogen bonds. While this network in Form II is similar to that observed for the previously reported Form I [Mootz & Wunderlich (1970). Acta Cryst. B26, 1820–1825; Sartori et al. (1994). Z. Naturforsch. 49, 1467–1472] and extends in all directions, in Form III it differs significantly, forming layers parallel to the ab plane. The sulfonate molecule in all three forms adopts a nearly identical geometry. The other observed differences between the forms, apart from the hydrogen-bonding network, are observed in the crystal density and packing index.
Keywords: crystal structure; polymorphism; oxonium cation; sulfonate anions.
1. Chemical context
). Salts of ethane-1,2-disulfonic acid account for 0.38% of all the FDA-approved commercially marketed salts (Steele & Talbir, 2016) and therefore its toxicology, dosage (Saal & Becker, 2013) and various physico-chemical properties are widely studied (Black et al., 2007; Elder et al., 2010). In our laboratory, ethane-1,2-disulfonic acid is commonly used in the salt screening for increasing solubility as well as improving the crystallinity of various researched active pharmaceutical ingredients (APIs).
are commonly used in salt formation in the pharmaceutical industry, especially for poorly or non soluble in water drugs (Neau & Loka, 20182. Structural commentary
The sulfonate anion in all polymorphs, including the previously determined form (Mootz & Wunderlich, 1970, refcode HOEDSO; Sartori et al., 1994, refcode HOEDSO01) has a nearly identical geometry. In all cases, the center of the C—C bond is located on an inversion center, and the C—S and C—O distances in all cases are within 3σ. The sulfonate group adopts the geometry of an open umbrella with the C—S—O bond angles of 106.51 (6), 105.82 (6), 107.23 (6)° for Form II (Fig. 1) and 106.16 (11), 106.21 (10), 107.20 (12)° for Form III (Fig. 2). The values of all O—S—O angles are above 110° [112.91 (7), 111.48 (7), 112.37 (7)° for Form II and 111.31 (11), 113.45 (11), 112.00 (12)° for Form III]. In this way, the molecular symmetry of the sulfonate group becomes slightly distorted C3V. In all crystals, the oxonium cations have a pyramidal geometry with slightly elongated O—H distances for one H atom. This is most likely an effect of the fast exchange of a proton (H atom) between the sulfonate group and the water molecules.
The biggest differences between forms are observed in the density of the crystal, as well as in the packing coefficient (Kitajgorodskij, 1973). The lowest values of both parameters are attributed to Form III (1.60 g cm−3 and 0.67, respectively), which suggests that this polymorph is the least stable. Form II presented here has a slightly better packing index than previously reported for Form I (Mootz & Wunderlich, 1970; Sartori et al., 1994) 0.75 versus 0.73. On the other hand, the density is lower: 1.78 versus 1.82 g cm−3, respectively.
3. Supramolecular features
The hydrogen bonds between the oxonium cations and sulfonate anions in the crystal of Form II (Table 1, Fig. 3) extend in all directions forming a three-dimensional network similar to that observed for Form I (Mootz & Wunderlich, 1970; Sartori et al., 1994). However, contrary to the previously reported form, where the hydrogen-bond network is built from alternate anion–cations layers, in Form II such layers could not be distinguished. The supramolecular behaviour of Form III is significantly different. In this case (Table 2 and Fig. 4), the anion–cation hydrogen-bond network forms separate layers parallel to the ab plane built from sulfonate anions surrounded by oxonium cations with no interactions between the planes.
4. Database survey
As mentioned above, the , refcode HOEDSO; Sartori et al., 1994, refcode HOEDSO01). Apart from these structures, there are 12 hits for ethane-1,2-disulfonate salts in the Cambridge Structural Database (CSD, Version 5.40; ConQuest 2.02; Groom et al., 2016), one of which is disordered. The geometry of the sulfonate group in all of the anions is nearly the same, with slightly distorted C3v molecular symmetry for the open-umbrella geometry. The average values of the C—S—O and O—S—O bond angles are very close to those reported in this paper: 105.9±0.8 and 112.8±0.9°, respectively.
of a different polymorphic form of oxonium ethane-1,2-disulfonate has been previously reported (Mootz, & Wunderlich, 19705. Synthesis and crystallization
Both crystals were obtained from an aqueous solution during unsuccessful salt formation with an unnamed free base (API) in water. Firstly, columnar crystals of Form III that appeared to be unstable were grown from the thick oil and within time transformed into prismatic crystals of Form II.
6. Refinement
Crystal data, data collection and structure . All H atoms were found in difference-Fourier maps and refined with isotropic displacement parameters. The DFIX 0.98 0.03 O6 H61, O6 H62 and O6 H63 instruction in SHELXL2014/7 (Sheldrick, 2015b) was used to restrain the oxonium O—H distance in Form II. All of the oxonium H atoms in Form III were refined independently without any restraints.
details are summarized in Table 3
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Supporting information
https://doi.org/10.1107/S2056989019013367/lh5920sup1.cif
contains datablocks I, II. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019013367/lh5920Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019013367/lh5920IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019013367/lh5920Isup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989019013367/lh5920IIsup5.cml
For both structures, data collection: COLLECT (Hooft, 1998); cell
HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).2H3O+·C2H4O6S22− | F(000) = 236 |
Mr = 226.22 | Dx = 1.778 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.8050 (3) Å | Cell parameters from 11538 reflections |
b = 8.3566 (6) Å | θ = 1.0–35.0° |
c = 8.7433 (6) Å | µ = 0.64 mm−1 |
β = 95.148 (4)° | T = 296 K |
V = 422.43 (5) Å3 | Prism, pale yellow |
Z = 2 | 0.45 × 0.32 × 0.23 mm |
Bruker KappaCCD diffractometer | 1848 independent reflections |
Radiation source: fine-focus sealed tube | 1768 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.075 |
Detector resolution: 9 pixels mm-1 | θmax = 34.9°, θmin = 3.4° |
CCD scans | h = −9→9 |
Absorption correction: integration Gaussian integration (Coppens, 1970) | k = −13→13 |
Tmin = 0.748, Tmax = 0.907 | l = −14→14 |
17906 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0797P)2 + 0.1864P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.026 |
1848 reflections | Δρmax = 0.62 e Å−3 |
76 parameters | Δρmin = −0.93 e Å−3 |
3 restraints | Extinction correction: SHELXL-2014/7 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: difference Fourier map | Extinction coefficient: 0.20 (2) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.03777 (17) | 0.61584 (15) | 0.29236 (14) | 0.0319 (2) | |
O2 | 0.4298 (2) | 0.65073 (13) | 0.21941 (13) | 0.0302 (2) | |
O3 | 0.30307 (19) | 0.79554 (12) | 0.43552 (13) | 0.0308 (2) | |
S4 | 0.27802 (4) | 0.64978 (3) | 0.34467 (3) | 0.01890 (13) | |
C5 | 0.3753 (2) | 0.48838 (15) | 0.46678 (14) | 0.0231 (2) | |
H5A | 0.270 (5) | 0.476 (3) | 0.541 (3) | 0.043 (6)* | |
H5B | 0.360 (4) | 0.393 (3) | 0.404 (2) | 0.025 (5)* | |
O6 | 0.7708 (2) | 0.90258 (15) | 0.39286 (16) | 0.0363 (3) | |
H61 | 0.822 (6) | 1.009 (3) | 0.357 (4) | 0.066 (9)* | |
H62 | 0.588 (4) | 0.889 (4) | 0.383 (4) | 0.067 (9)* | |
H63 | 0.797 (4) | 0.795 (3) | 0.350 (3) | 0.041 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0219 (4) | 0.0345 (5) | 0.0373 (5) | −0.0002 (3) | −0.0079 (4) | 0.0012 (4) |
O2 | 0.0341 (5) | 0.0339 (5) | 0.0238 (4) | 0.0083 (4) | 0.0096 (4) | 0.0055 (3) |
O3 | 0.0333 (5) | 0.0227 (4) | 0.0362 (5) | 0.0020 (3) | 0.0025 (4) | −0.0081 (4) |
S4 | 0.01863 (17) | 0.01917 (17) | 0.01865 (17) | 0.00184 (7) | 0.00025 (10) | 0.00054 (7) |
C5 | 0.0218 (4) | 0.0231 (5) | 0.0234 (5) | −0.0027 (3) | −0.0032 (3) | 0.0061 (4) |
O6 | 0.0307 (5) | 0.0320 (5) | 0.0452 (6) | −0.0022 (4) | −0.0012 (4) | 0.0000 (5) |
O1—S4 | 1.4561 (10) | C5—H5A | 0.94 (3) |
O2—S4 | 1.4658 (11) | C5—H5B | 0.97 (2) |
O3—S4 | 1.4544 (10) | O6—H61 | 1.00 (2) |
S4—C5 | 1.7804 (11) | O6—H62 | 1.06 (2) |
C5—C5i | 1.523 (2) | O6—H63 | 0.99 (2) |
O3—S4—O1 | 112.37 (7) | S4—C5—H5A | 108.0 (16) |
O3—S4—O2 | 111.48 (7) | C5i—C5—H5B | 110.7 (12) |
O1—S4—O2 | 112.91 (7) | S4—C5—H5B | 106.3 (12) |
O3—S4—C5 | 107.23 (6) | H5A—C5—H5B | 105 (2) |
O1—S4—C5 | 106.51 (6) | H61—O6—H62 | 113 (3) |
O2—S4—C5 | 105.82 (6) | H61—O6—H63 | 129 (2) |
C5i—C5—S4 | 111.82 (11) | H62—O6—H63 | 93 (2) |
C5i—C5—H5A | 114.1 (17) | ||
O3—S4—C5—C5i | −57.98 (14) | O2—S4—C5—C5i | 61.12 (14) |
O1—S4—C5—C5i | −178.48 (12) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H63···O2 | 0.99 (2) | 2.62 (2) | 3.1795 (17) | 116 (2) |
O6—H61···O2ii | 1.00 (2) | 2.02 (3) | 2.9312 (16) | 150 (3) |
O6—H62···O3 | 1.06 (2) | 1.92 (3) | 2.9141 (16) | 154 (3) |
O6—H61···O3iii | 1.00 (2) | 2.60 (3) | 2.9857 (16) | 103 (2) |
O6—H63···O1iv | 0.99 (2) | 2.14 (2) | 3.0266 (18) | 148 (2) |
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z+1; (iv) x+1, y, z. |
2H3O+·C2H4O6S22− | Z = 1 |
Mr = 226.22 | F(000) = 118 |
Triclinic, P1 | Dx = 1.597 Mg m−3 |
a = 5.0371 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 5.5424 (2) Å | Cell parameters from 4728 reflections |
c = 8.8188 (4) Å | θ = 1.0–32.6° |
α = 98.426 (5)° | µ = 0.57 mm−1 |
β = 104.511 (3)° | T = 296 K |
γ = 91.663 (4)° | Columnar, colorless |
V = 235.22 (2) Å3 | 0.30 × 0.12 × 0.11 mm |
Bruker KappaCCD diffractometer | 1708 independent reflections |
Radiation source: fine-focus sealed tube | 1192 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.131 |
Detector resolution: 9 pixels mm-1 | θmax = 32.6°, θmin = 2.4° |
CCD scans | h = −7→6 |
Absorption correction: integration Gaussian integration (Coppens, 1970) | k = −8→8 |
Tmin = 0.813, Tmax = 0.947 | l = −11→13 |
7504 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | All H-atom parameters refined |
wR(F2) = 0.163 | w = 1/[σ2(Fo2) + (0.0869P)2 + 0.0186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.016 |
1708 reflections | Δρmax = 0.66 e Å−3 |
76 parameters | Δρmin = −0.67 e Å−3 |
0 restraints | Extinction correction: SHELXL-2014/7 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: difference Fourier map | Extinction coefficient: 0.19 (3) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.6030 (4) | 0.9888 (3) | 0.7642 (2) | 0.0387 (4) | |
O2 | 0.6622 (4) | 0.5760 (3) | 0.8252 (2) | 0.0378 (4) | |
O3 | 0.2119 (4) | 0.6995 (4) | 0.7086 (3) | 0.0417 (5) | |
S4 | 0.50463 (11) | 0.73087 (9) | 0.72171 (6) | 0.0267 (2) | |
C5 | 0.5533 (5) | 0.6324 (4) | 0.5302 (3) | 0.0290 (5) | |
H5A | 0.473 (7) | 0.750 (6) | 0.459 (4) | 0.043 (8)* | |
H5B | 0.737 (7) | 0.654 (6) | 0.526 (4) | 0.054 (9)* | |
O6 | 0.1360 (5) | 0.2554 (4) | 0.8443 (3) | 0.0477 (5) | |
H61 | 0.318 (10) | 0.173 (8) | 0.827 (5) | 0.083 (13)* | |
H62 | 0.113 (7) | 0.415 (6) | 0.798 (5) | 0.049 (9)* | |
H63 | −0.056 (8) | 0.173 (6) | 0.822 (5) | 0.057 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0405 (11) | 0.0264 (8) | 0.0464 (10) | −0.0019 (7) | 0.0115 (8) | −0.0030 (7) |
O2 | 0.0425 (11) | 0.0396 (9) | 0.0301 (8) | 0.0109 (8) | 0.0059 (7) | 0.0062 (7) |
O3 | 0.0235 (9) | 0.0476 (10) | 0.0538 (11) | 0.0009 (7) | 0.0125 (8) | 0.0028 (8) |
S4 | 0.0229 (3) | 0.0261 (3) | 0.0297 (3) | 0.0012 (2) | 0.0060 (2) | 0.0014 (2) |
C5 | 0.0289 (12) | 0.0297 (11) | 0.0271 (10) | −0.0025 (9) | 0.0059 (9) | 0.0034 (8) |
O6 | 0.0415 (13) | 0.0454 (11) | 0.0535 (12) | 0.0046 (9) | 0.0092 (10) | 0.0046 (9) |
O1—S4 | 1.4625 (17) | C5—H5A | 0.99 (3) |
O2—S4 | 1.4509 (18) | C5—H5B | 0.94 (4) |
O3—S4 | 1.4532 (19) | O6—H61 | 1.07 (4) |
S4—C5 | 1.777 (2) | O6—H62 | 1.02 (4) |
C5—C5i | 1.519 (4) | O6—H63 | 1.02 (4) |
O2—S4—O3 | 112.00 (12) | S4—C5—H5A | 109.0 (18) |
O2—S4—O1 | 113.45 (11) | C5i—C5—H5B | 110 (2) |
O3—S4—O1 | 111.31 (11) | S4—C5—H5B | 113 (2) |
O2—S4—C5 | 106.21 (10) | H5A—C5—H5B | 98 (3) |
O3—S4—C5 | 107.20 (12) | H61—O6—H62 | 111 (3) |
O1—S4—C5 | 106.16 (11) | H61—O6—H63 | 127 (3) |
C5i—C5—S4 | 111.0 (2) | H62—O6—H63 | 107 (3) |
C5i—C5—H5A | 114.8 (19) | ||
O2—S4—C5—C5i | 61.3 (3) | O1—S4—C5—C5i | −177.6 (2) |
O3—S4—C5—C5i | −58.6 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H61···O1ii | 1.07 (4) | 1.93 (4) | 2.991 (3) | 170 (4) |
O6—H62···O2iii | 1.02 (4) | 2.52 (3) | 3.002 (3) | 108 (2) |
O6—H62···O3 | 1.02 (4) | 1.97 (4) | 2.945 (3) | 158 (3) |
O6—H63···O1iv | 1.02 (4) | 1.89 (4) | 2.899 (3) | 173 (3) |
Symmetry codes: (ii) x, y−1, z; (iii) x−1, y, z; (iv) x−1, y−1, z. |
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