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ISSN: 2056-9890

Hydro­nium 4-oxo-1,4-di­hydro­pyridine-3-sulfonate dihydrate

aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 5 October 2009; accepted 6 October 2009; online 10 October 2009)

2-Hydroxy­pyridine when treated with concentrated sulfuric acid is sulfonated at the 3-position to yield the title hydrated salt, H3O+·C5H4NO3S·2H2O. In the crystal structure, the cations, anions and uncoordinated water mol­ecules are linked by extensive O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network. The crystal studied is a non-merohedral twin with a twin component of 36%.

Related literature

For the treatment of non-merohedral twins, see: Spek (2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]). For the cobalt salt of the anion, see: Zhu et al. (2007[Zhu, Z.-B., Gao, S., Huo, L.-H. & Zhao, H. (2007). Acta Cryst. E63, m3126-m3127.]).

[Scheme 1]

Experimental

Crystal data
  • H3O+·C5H4NO4S·2H2O

  • Mr = 229.21

  • Triclinic, [P \overline 1]

  • a = 6.6610 (8) Å

  • b = 7.4179 (10) Å

  • c = 10.0514 (11) Å

  • α = 90.922 (4)°

  • β = 94.543 (3)°

  • γ = 96.226 (4)°

  • V = 492.01 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.34 mm−1

  • T = 293 K

  • 0.25 × 0.22 × 0.20 mm

Data collection
  • Rigaku R-AXIS RAPID IP diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.856, Tmax = 0.932

  • 4711 measured reflections

  • 2234 independent reflections

  • 1719 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.049

  • wR(F2) = 0.170

  • S = 1.06

  • 2234 reflections

  • 152 parameters

  • 13 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.65 e Å−3

  • Δρmin = −0.59 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1w—H11⋯O1 0.85 (1) 1.90 (1) 2.745 (4) 175 (5)
O1w—H12⋯O2i 0.85 (1) 2.50 (4) 2.983 (4) 116 (3)
O2w—H21⋯O1w 0.85 (1) 1.89 (1) 2.741 (4) 175 (6)
O2w—H22⋯O4ii 0.85 (1) 2.07 (2) 2.910 (4) 168 (6)
O3w—H31⋯O2i 0.86 (1) 2.12 (2) 2.951 (4) 165 (5)
O3w—H32⋯O2ii 0.85 (1) 2.07 (2) 2.898 (4) 162 (5)
O3w—H33⋯O3iii 0.85 (1) 2.18 (2) 2.936 (4) 147 (4)
N1—H1⋯O3iv 0.86 (1) 2.05 (2) 2.857 (4) 156 (5)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y, z+1; (iii) -x+1, -y+1, -z+1; (iv) x+1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


Related literature top

For the treatment of non-merohedral twins, see: Spek (2003). For the cobalt salt of the anion, see: Zhu et al. (2007).

Experimental top

A 1:3 molar mixture of 4-hydroxypyridine and oleum (20%) was heated at 483 K for 3 h. Barium carbonate was added to the cool mixture until no more carbon dioxide evolved. Colorless crystals were isolated from the filtered solution after several days. CH&N elemental analysis. Calc. for C5H10NO7S: C 26.20, H 4.84, N 6.11%; found: C 26.36, H 4.48, N 6.11%.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The water, oxonium and amino H-atoms were located in a difference Fourier map and refined with a distance restraint of O–H = N–H 0.85±0.01 Å. The temperature factors of some of the atoms could not be refined; as such, all temperature factors were tied.

The crystal is a non-merohedral twin as shown by PLATON (Spek, 2003).

Structure description top

For the treatment of non-merohedral twins, see: Spek (2003). For the cobalt salt of the anion, see: Zhu et al. (2007).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [H3O][C5H4NO3S].2H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate top
Crystal data top
H3O+·C5H4NO4S·2H2OZ = 2
Mr = 229.21F(000) = 240
Triclinic, P1Dx = 1.547 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6610 (8) ÅCell parameters from 3881 reflections
b = 7.4179 (10) Åθ = 3.1–27.5°
c = 10.0514 (11) ŵ = 0.34 mm1
α = 90.922 (4)°T = 293 K
β = 94.543 (3)°Block, colorless
γ = 96.226 (4)°0.25 × 0.22 × 0.20 mm
V = 492.01 (10) Å3
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
2234 independent reflections
Radiation source: fine-focus sealed tube1719 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 88
Tmin = 0.856, Tmax = 0.932k = 99
4711 measured reflectionsl = 1313
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0803P)2 + 0.6366P]
where P = (Fo2 + 2Fc2)/3
2234 reflections(Δ/σ)max < 0.001
152 parametersΔρmax = 0.65 e Å3
13 restraintsΔρmin = 0.59 e Å3
Crystal data top
H3O+·C5H4NO4S·2H2Oγ = 96.226 (4)°
Mr = 229.21V = 492.01 (10) Å3
Triclinic, P1Z = 2
a = 6.6610 (8) ÅMo Kα radiation
b = 7.4179 (10) ŵ = 0.34 mm1
c = 10.0514 (11) ÅT = 293 K
α = 90.922 (4)°0.25 × 0.22 × 0.20 mm
β = 94.543 (3)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
2234 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1719 reflections with I > 2σ(I)
Tmin = 0.856, Tmax = 0.932Rint = 0.022
4711 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04913 restraints
wR(F2) = 0.170H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.65 e Å3
2234 reflectionsΔρmin = 0.59 e Å3
152 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.68686 (13)0.38798 (11)0.16672 (8)0.0280 (2)
O10.6502 (4)0.2383 (4)0.4423 (2)0.0363 (6)
O20.5597 (4)0.2165 (3)0.1408 (2)0.0365 (6)
O30.5787 (4)0.5226 (3)0.2300 (2)0.0350 (6)
O40.7845 (4)0.4562 (4)0.0509 (2)0.0402 (6)
O1W0.5750 (5)0.0846 (4)0.6825 (3)0.0479 (7)
H110.605 (9)0.135 (5)0.610 (3)0.072*
H120.523 (8)0.024 (3)0.664 (4)0.072*
O2W0.8700 (5)0.1491 (5)0.8890 (3)0.0582 (8)
H210.783 (7)0.132 (7)0.822 (4)0.087*
H220.855 (9)0.249 (5)0.928 (5)0.087*
O3W0.2908 (5)0.1387 (4)0.9010 (3)0.0540 (8)
H310.310 (8)0.028 (2)0.887 (4)0.081*
H320.350 (7)0.176 (5)0.976 (2)0.081*
H330.338 (7)0.204 (5)0.839 (3)0.081*
N11.2314 (5)0.3608 (5)0.3510 (3)0.0403 (7)
H11.351 (3)0.385 (7)0.327 (5)0.060*
C11.1944 (6)0.2958 (6)0.4722 (4)0.0405 (9)
H1A1.30220.28090.53420.049*
C21.0013 (5)0.2520 (5)0.5047 (4)0.0346 (8)
H20.97950.20680.58870.042*
C30.8321 (5)0.2734 (4)0.4136 (3)0.0278 (6)
C40.8828 (5)0.3435 (4)0.2858 (3)0.0264 (7)
C51.0802 (6)0.3834 (5)0.2586 (4)0.0334 (7)
H51.11000.42670.17520.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0305 (4)0.0281 (4)0.0249 (4)0.0000 (3)0.0025 (3)0.0033 (3)
O10.0272 (12)0.0504 (15)0.0308 (12)0.0019 (11)0.0066 (10)0.0093 (11)
O20.0385 (13)0.0313 (13)0.0367 (13)0.0032 (11)0.0062 (11)0.0012 (10)
O30.0367 (13)0.0310 (12)0.0389 (13)0.0080 (11)0.0072 (11)0.0049 (10)
O40.0465 (16)0.0461 (15)0.0281 (12)0.0003 (13)0.0082 (11)0.0093 (11)
O1W0.0621 (19)0.0438 (16)0.0346 (14)0.0083 (15)0.0032 (14)0.0057 (11)
O2W0.0456 (17)0.066 (2)0.062 (2)0.0103 (17)0.0055 (16)0.0101 (16)
O3W0.063 (2)0.0457 (17)0.0525 (18)0.0037 (15)0.0025 (16)0.0059 (13)
N10.0244 (14)0.0515 (19)0.0452 (18)0.0016 (14)0.0100 (14)0.0040 (14)
C10.0287 (18)0.050 (2)0.043 (2)0.0081 (16)0.0009 (16)0.0059 (17)
C20.0309 (18)0.043 (2)0.0300 (16)0.0057 (15)0.0013 (14)0.0019 (14)
C30.0269 (15)0.0281 (15)0.0274 (15)0.0018 (13)0.0031 (13)0.0003 (12)
C40.0233 (14)0.0282 (16)0.0275 (15)0.0017 (12)0.0030 (12)0.0005 (12)
C50.0325 (17)0.0332 (17)0.0347 (17)0.0002 (15)0.0087 (15)0.0017 (13)
Geometric parameters (Å, º) top
S1—O41.449 (2)O3W—H330.854 (10)
S1—O21.457 (2)N1—C51.341 (5)
S1—O31.459 (3)N1—C11.348 (5)
S1—C41.762 (3)N1—H10.855 (10)
O1—C31.268 (4)C1—C21.358 (5)
O1W—H110.850 (10)C1—H1A0.9300
O1W—H120.854 (10)C2—C31.419 (5)
O2W—H210.854 (10)C2—H20.9300
O2W—H220.851 (10)C3—C41.445 (4)
O3W—H310.855 (10)C4—C51.367 (5)
O3W—H320.853 (10)C5—H50.9300
O4—S1—O2113.46 (15)N1—C1—H1A119.7
O4—S1—O3112.83 (16)C2—C1—H1A119.7
O2—S1—O3111.76 (16)C1—C2—C3121.7 (3)
O4—S1—C4106.31 (16)C1—C2—H2119.2
O2—S1—C4106.22 (15)C3—C2—H2119.2
O3—S1—C4105.54 (15)O1—C3—C2123.1 (3)
H11—O1W—H12108.9 (17)O1—C3—C4122.2 (3)
H21—O2W—H22108.9 (17)C2—C3—C4114.7 (3)
H31—O3W—H32109.7 (17)C5—C4—C3120.9 (3)
H31—O3W—H33109.4 (17)C5—C4—S1119.7 (3)
H32—O3W—H33109.9 (17)C3—C4—S1119.3 (2)
C5—N1—C1121.5 (3)N1—C5—C4120.5 (3)
C5—N1—H1116 (3)N1—C5—H5119.7
C1—N1—H1122 (3)C4—C5—H5119.7
N1—C1—C2120.7 (4)
C5—N1—C1—C20.4 (6)O2—S1—C4—C5124.1 (3)
N1—C1—C2—C30.3 (6)O3—S1—C4—C5117.1 (3)
C1—C2—C3—O1178.0 (4)O4—S1—C4—C3179.9 (3)
C1—C2—C3—C40.4 (5)O2—S1—C4—C358.9 (3)
O1—C3—C4—C5178.7 (3)O3—S1—C4—C359.8 (3)
C2—C3—C4—C50.3 (5)C1—N1—C5—C41.0 (6)
O1—C3—C4—S11.8 (5)C3—C4—C5—N11.0 (5)
C2—C3—C4—S1176.6 (2)S1—C4—C5—N1175.9 (3)
O4—S1—C4—C52.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O10.85 (1)1.90 (1)2.745 (4)175 (5)
O1w—H12···O2i0.85 (1)2.50 (4)2.983 (4)116 (3)
O2w—H21···O1w0.85 (1)1.89 (1)2.741 (4)175 (6)
O2w—H22···O4ii0.85 (1)2.07 (2)2.910 (4)168 (6)
O3w—H31···O2i0.86 (1)2.12 (2)2.951 (4)165 (5)
O3w—H32···O2ii0.85 (1)2.07 (2)2.898 (4)162 (5)
O3w—H33···O3iii0.85 (1)2.18 (2)2.936 (4)147 (4)
N1—H1···O3iv0.86 (1)2.05 (2)2.857 (4)156 (5)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z+1; (iii) x+1, y+1, z+1; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formulaH3O+·C5H4NO4S·2H2O
Mr229.21
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.6610 (8), 7.4179 (10), 10.0514 (11)
α, β, γ (°)90.922 (4), 94.543 (3), 96.226 (4)
V3)492.01 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.34
Crystal size (mm)0.25 × 0.22 × 0.20
Data collection
DiffractometerRigaku R-AXIS RAPID IP
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.856, 0.932
No. of measured, independent and
observed [I > 2σ(I)] reflections
4711, 2234, 1719
Rint0.022
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.170, 1.06
No. of reflections2234
No. of parameters152
No. of restraints13
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.65, 0.59

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O10.85 (1)1.90 (1)2.745 (4)175 (5)
O1w—H12···O2i0.85 (1)2.50 (4)2.983 (4)116 (3)
O2w—H21···O1w0.85 (1)1.89 (1)2.741 (4)175 (6)
O2w—H22···O4ii0.85 (1)2.07 (2)2.910 (4)168 (6)
O3w—H31···O2i0.86 (1)2.12 (2)2.951 (4)165 (5)
O3w—H32···O2ii0.85 (1)2.07 (2)2.898 (4)162 (5)
O3w—H33···O3iii0.85 (1)2.18 (2)2.936 (4)147 (4)
N1—H1···O3iv0.86 (1)2.05 (2)2.857 (4)156 (5)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z+1; (iii) x+1, y+1, z+1; (iv) x+1, y, z.
 

Acknowledgements

We thank the Natural Science Foundation of Heilongjiang Province (No. B200501), Heilongjiang University, China, and the University of Malaya for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar
First citationZhu, Z.-B., Gao, S., Huo, L.-H. & Zhao, H. (2007). Acta Cryst. E63, m3126–m3127.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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