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

Zhu, Z.-B.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809040641

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2687

https://doi.org/10.1107/S1600536809040641

Open

access

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

Zhi-Biao Zhu,^a Shan Gao ^a and Seik Weng Ng ^b ^*

^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 ). For the cobalt salt of the anion, see: Zhu et al. (2007 ).

Experimental

Crystal data

H₃O⁺·C₅H₄NO₄S⁻·2H₂O
M_r = 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 ) T_min = 0.856, T_max = 0.932
4711 measured reflections
2234 independent reflections
1719 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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⋯O3^iv	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 ); cell refinement: RAPID-AUTO; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040641/xu2628sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040641/xu2628Isup2.hkl

checkCIF report

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%.

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

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⁻·2H₂O	Z = 2
M_r = 229.21	F(000) = 240
Triclinic, P1	D_x = 1.547 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6610 (8) Å	Cell parameters from 3881 reflections
b = 7.4179 (10) Å	θ = 3.1–27.5°
c = 10.0514 (11) Å	µ = 0.34 mm⁻¹
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 tube	1719 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.856, T_max = 0.932	k = −9→9
4711 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0803P)² + 0.6366P] where P = (F_o² + 2F_c²)/3
2234 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.65 e Å⁻³
13 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

H₃O⁺·C₅H₄NO₄S⁻·2H₂O	γ = 96.226 (4)°
M_r = 229.21	V = 492.01 (10) Å³
Triclinic, P1	Z = 2
a = 6.6610 (8) Å	Mo Kα radiation
b = 7.4179 (10) Å	µ = 0.34 mm⁻¹
c = 10.0514 (11) Å	T = 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)
T_min = 0.856, T_max = 0.932	R_int = 0.022
4711 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	13 restraints
wR(F²) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.65 e Å⁻³
2234 reflections	Δρ_min = −0.59 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.68686 (13)	0.38798 (11)	0.16672 (8)	0.0280 (2)
O1	0.6502 (4)	0.2383 (4)	0.4423 (2)	0.0363 (6)
O2	0.5597 (4)	0.2165 (3)	0.1408 (2)	0.0365 (6)
O3	0.5787 (4)	0.5226 (3)	0.2300 (2)	0.0350 (6)
O4	0.7845 (4)	0.4562 (4)	0.0509 (2)	0.0402 (6)
O1W	0.5750 (5)	0.0846 (4)	0.6825 (3)	0.0479 (7)
H11	0.605 (9)	0.135 (5)	0.610 (3)	0.072*
H12	0.523 (8)	−0.024 (3)	0.664 (4)	0.072*
O2W	0.8700 (5)	0.1491 (5)	0.8890 (3)	0.0582 (8)
H21	0.783 (7)	0.132 (7)	0.822 (4)	0.087*
H22	0.855 (9)	0.249 (5)	0.928 (5)	0.087*
O3W	0.2908 (5)	0.1387 (4)	0.9010 (3)	0.0540 (8)
H31	0.310 (8)	0.028 (2)	0.887 (4)	0.081*
H32	0.350 (7)	0.176 (5)	0.976 (2)	0.081*
H33	0.338 (7)	0.204 (5)	0.839 (3)	0.081*
N1	1.2314 (5)	0.3608 (5)	0.3510 (3)	0.0403 (7)
H1	1.351 (3)	0.385 (7)	0.327 (5)	0.060*
C1	1.1944 (6)	0.2958 (6)	0.4722 (4)	0.0405 (9)
H1A	1.3022	0.2809	0.5342	0.049*
C2	1.0013 (5)	0.2520 (5)	0.5047 (4)	0.0346 (8)
H2	0.9795	0.2068	0.5887	0.042*
C3	0.8321 (5)	0.2734 (4)	0.4136 (3)	0.0278 (6)
C4	0.8828 (5)	0.3435 (4)	0.2858 (3)	0.0264 (7)
C5	1.0802 (6)	0.3834 (5)	0.2586 (4)	0.0334 (7)
H5	1.1100	0.4267	0.1752	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0305 (4)	0.0281 (4)	0.0249 (4)	0.0000 (3)	0.0025 (3)	0.0033 (3)
O1	0.0272 (12)	0.0504 (15)	0.0308 (12)	−0.0019 (11)	0.0066 (10)	0.0093 (11)
O2	0.0385 (13)	0.0313 (13)	0.0367 (13)	−0.0032 (11)	−0.0062 (11)	0.0012 (10)
O3	0.0367 (13)	0.0310 (12)	0.0389 (13)	0.0080 (11)	0.0072 (11)	0.0049 (10)
O4	0.0465 (16)	0.0461 (15)	0.0281 (12)	−0.0003 (13)	0.0082 (11)	0.0093 (11)
O1W	0.0621 (19)	0.0438 (16)	0.0346 (14)	−0.0083 (15)	0.0032 (14)	0.0057 (11)
O2W	0.0456 (17)	0.066 (2)	0.062 (2)	0.0103 (17)	−0.0055 (16)	−0.0101 (16)
O3W	0.063 (2)	0.0457 (17)	0.0525 (18)	0.0037 (15)	0.0025 (16)	0.0059 (13)
N1	0.0244 (14)	0.0515 (19)	0.0452 (18)	0.0016 (14)	0.0100 (14)	−0.0040 (14)
C1	0.0287 (18)	0.050 (2)	0.043 (2)	0.0081 (16)	−0.0009 (16)	−0.0059 (17)
C2	0.0309 (18)	0.043 (2)	0.0300 (16)	0.0057 (15)	0.0013 (14)	0.0019 (14)
C3	0.0269 (15)	0.0281 (15)	0.0274 (15)	−0.0018 (13)	0.0031 (13)	0.0003 (12)
C4	0.0233 (14)	0.0282 (16)	0.0275 (15)	0.0017 (12)	0.0030 (12)	−0.0005 (12)
C5	0.0325 (17)	0.0332 (17)	0.0347 (17)	0.0002 (15)	0.0087 (15)	−0.0017 (13)

Geometric parameters (Å, º) top

S1—O4	1.449 (2)	O3W—H33	0.854 (10)
S1—O2	1.457 (2)	N1—C5	1.341 (5)
S1—O3	1.459 (3)	N1—C1	1.348 (5)
S1—C4	1.762 (3)	N1—H1	0.855 (10)
O1—C3	1.268 (4)	C1—C2	1.358 (5)
O1W—H11	0.850 (10)	C1—H1A	0.9300
O1W—H12	0.854 (10)	C2—C3	1.419 (5)
O2W—H21	0.854 (10)	C2—H2	0.9300
O2W—H22	0.851 (10)	C3—C4	1.445 (4)
O3W—H31	0.855 (10)	C4—C5	1.367 (5)
O3W—H32	0.853 (10)	C5—H5	0.9300

O4—S1—O2	113.46 (15)	N1—C1—H1A	119.7
O4—S1—O3	112.83 (16)	C2—C1—H1A	119.7
O2—S1—O3	111.76 (16)	C1—C2—C3	121.7 (3)
O4—S1—C4	106.31 (16)	C1—C2—H2	119.2
O2—S1—C4	106.22 (15)	C3—C2—H2	119.2
O3—S1—C4	105.54 (15)	O1—C3—C2	123.1 (3)
H11—O1W—H12	108.9 (17)	O1—C3—C4	122.2 (3)
H21—O2W—H22	108.9 (17)	C2—C3—C4	114.7 (3)
H31—O3W—H32	109.7 (17)	C5—C4—C3	120.9 (3)
H31—O3W—H33	109.4 (17)	C5—C4—S1	119.7 (3)
H32—O3W—H33	109.9 (17)	C3—C4—S1	119.3 (2)
C5—N1—C1	121.5 (3)	N1—C5—C4	120.5 (3)
C5—N1—H1	116 (3)	N1—C5—H5	119.7
C1—N1—H1	122 (3)	C4—C5—H5	119.7
N1—C1—C2	120.7 (4)

C5—N1—C1—C2	−0.4 (6)	O2—S1—C4—C5	124.1 (3)
N1—C1—C2—C3	−0.3 (6)	O3—S1—C4—C5	−117.1 (3)
C1—C2—C3—O1	−178.0 (4)	O4—S1—C4—C3	179.9 (3)
C1—C2—C3—C4	0.4 (5)	O2—S1—C4—C3	−58.9 (3)
O1—C3—C4—C5	178.7 (3)	O3—S1—C4—C3	59.8 (3)
C2—C3—C4—C5	0.3 (5)	C1—N1—C5—C4	1.0 (6)
O1—C3—C4—S1	1.8 (5)	C3—C4—C5—N1	−1.0 (5)
C2—C3—C4—S1	−176.6 (2)	S1—C4—C5—N1	175.9 (3)
O4—S1—C4—C5	2.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···O3^iv	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.

Experimental details

Crystal data
Chemical formula	H₃O⁺·C₅H₄NO₄S⁻·2H₂O
M_r	229.21
Crystal system, space group	Triclinic, 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)
V (Å³)	492.01 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.25 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.856, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	4711, 2234, 1719
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.170, 1.06
No. of reflections	2234
No. of parameters	152
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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···O3^iv	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.

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

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