The crystal structures of two novel polymorphs of bis­(oxonium) ethane-1,2-di­sulfonate

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.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.121
• Data-to-parameter ratio = 24.3

Structure: II

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.058
• wR factor = 0.163
• Data-to-parameter ratio = 22.5

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT313_ALERT_2_C Oxygen with Three Covalent Bonds (rare) ........         O6 Check
PLAT355_ALERT_3_C Long   O-H (X0.82,N0.98A)  O6       - H62      .       1.06 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H63      ..O2       .       2.62 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          8 Report
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  1.01A   From O6              0.62 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.46A   From O6             -0.88 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  1.09A   From O6             -0.44 eA-3
PLAT977_ALERT_2_C Check Negative Difference Density on H63              -0.40 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT019_ALERT_1_G _diffrn_measured_fraction_theta_full/*_max < 1.0      0.994 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          3 Report
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          2 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   9 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: II


Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.131
PLAT313_ALERT_2_C Oxygen with Three Covalent Bonds (rare) ........         O6 Check
PLAT355_ALERT_3_C Long   O-H (X0.82,N0.98A)  O6       - H61      .       1.07 Ang.
PLAT355_ALERT_3_C Long   O-H (X0.82,N0.98A)  O6       - H62      .       1.03 Ang.
PLAT355_ALERT_3_C Long   O-H (X0.82,N0.98A)  O6       - H63      .       1.02 Ang.
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  1.08A   From O6              0.66 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.58A   From O6             -0.69 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.53A   From O6             -0.58 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.51A   From O6             -0.53 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.58A   From O6             -0.46 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT012_ALERT_1_G N.O.K.   _shelx_res_checksum Found in CIF ......     Please Check
PLAT020_ALERT_3_G The Value of Rint is Greater Than 0.12 .........      0.131 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         15 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

For both structures, data collection: COLLECT (Hooft, 1998); cell refinement: 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).

Bis(oxonium) ethane-1,2-disulfonate (I)

Crystal data

2H3O^+·C2H4O6S2^2^−	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) Å^3	Prism, pale yellow
Z = 2	0.45 × 0.32 × 0.23 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	All H-atom parameters refined
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0797P)^2 + 0.1864P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.20 (2)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C5^i	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)	C5^i—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)
C5^i—C5—S4	111.82 (11)	H62—O6—H63	93 (2)
C5^i—C5—H5A	114.1 (17)
O3—S4—C5—C5^i	−57.98 (14)	O2—S4—C5—C5^i	61.12 (14)
O1—S4—C5—C5^i	−178.48 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

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···O2^ii	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···O3^iii	1.00 (2)	2.60 (3)	2.9857 (16)	103 (2)
O6—H63···O1^iv	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.

Bis(oxonium) ethane-1,2-disulfonate (II)

Crystal data

2H3O^+·C2H4O6S2^2^−	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) Å^3	0.30 × 0.12 × 0.11 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	All H-atom parameters refined
wR(F^2) = 0.163	w = 1/[σ^2(Fo^2) + (0.0869P)^2 + 0.0186P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.19 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C5^i	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)	C5^i—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)
C5^i—C5—S4	111.0 (2)	H62—O6—H63	107 (3)
C5^i—C5—H5A	114.8 (19)
O2—S4—C5—C5^i	61.3 (3)	O1—S4—C5—C5^i	−177.6 (2)
O3—S4—C5—C5^i	−58.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H61···O1^ii	1.07 (4)	1.93 (4)	2.991 (3)	170 (4)
O6—H62···O2^iii	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···O1^iv	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.