4-Hy­droxy­pyridinium-3-sulfonate

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

doi:10.1107/S1600536810049603

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o11

https://doi.org/10.1107/S1600536810049603

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4-Hydroxypyridinium-3-sulfonate

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 15 November 2010; accepted 26 November 2010; online 4 December 2010)

The reaction of 4-hydroxypyridine and oleum produces 4-hydroxypyridinium-3-sulfonate, C₅H₅NO₄S, which shows delocalized bonds in the six-membered ring. In the crystal, adjacent zwitterions are linked by N—H⋯O and O—H⋯O hydrogen bonds into a layer motif. The crystal studied was a racemic twin.

Related literature

A previous synthesis yielded hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate; see: Zhu et al. (2009 ).

Experimental

Crystal data

C₅H₅NO₄S
M_r = 175.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.7980 (2) Å
b = 8.7618 (3) Å
c = 10.6797 (3) Å
V = 636.11 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 293 K
0.28 × 0.23 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.880, T_max = 0.925
6216 measured reflections
1449 independent reflections
1403 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.068
S = 1.09
1449 reflections
121 parameters
5 restraints
All H-atom parameters refined
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 785 Friedel pairs
Flack parameter: 0.31 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2ⁱ	0.83 (1)	1.76 (1)	2.581 (2)	166 (3)
N1—H1n⋯O3ⁱⁱ	0.87 (1)	1.91 (1)	2.762 (2)	166 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810049603/im2249sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049603/im2249Isup2.hkl

checkCIF report

Comment top

A previous reaction of 4-hydroxpyridine and oleum gave the salt, hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate (Zhu et al., 2009). Repeating this synthesis instead produced the zwitterionic title compound (Scheme I, Fig. 1). The bonds in the ring are delocalized bonds. Adjacent zwitterions are linked by N–H···O and O–H···O hydrogen bonds into a layer motif (Fig. 2).

Related literature top

A previous synthesis yielded hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate; see: Zhu et al. (2009).

Experimental top

4-Hydroxypyridine (10 mmol) was dissolved in 20% oleum (10 ml). The solution was heated to 393 K for 4 days. After it was cooled to room temperature, the excess oleum was decanted. Recrystallization of the solid from ethanol gave colorless crystals.

Structure description top

A previous synthesis yielded hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate; see: Zhu et al. (2009).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (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, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₅H₅NO₄S at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded layer structure.

4-Hydroxypyridinium-3-sulfonate top

Crystal data top

C₅H₅NO₄S	F(000) = 360
M_r = 175.16	D_x = 1.829 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6017 reflections
a = 6.7980 (2) Å	θ = 3.0–27.4°
b = 8.7618 (3) Å	µ = 0.47 mm⁻¹
c = 10.6797 (3) Å	T = 293 K
V = 636.11 (3) Å³	Prism, colorless
Z = 4	0.28 × 0.23 × 0.17 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1449 independent reflections
Radiation source: fine-focus sealed tube	1403 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.4°, θ_min = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
T_min = 0.880, T_max = 0.925	l = −13→13
6216 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	All H-atom parameters refined
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0488P)² + 0.0899P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1449 reflections	Δρ_max = 0.25 e Å⁻³
121 parameters	Δρ_min = −0.23 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 785 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.31 (8)

Crystal data top

C₅H₅NO₄S	V = 636.11 (3) Å³
M_r = 175.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.7980 (2) Å	µ = 0.47 mm⁻¹
b = 8.7618 (3) Å	T = 293 K
c = 10.6797 (3) Å	0.28 × 0.23 × 0.17 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1449 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1403 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.925	R_int = 0.017
6216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	All H-atom parameters refined
wR(F²) = 0.068	Δρ_max = 0.25 e Å⁻³
S = 1.09	Δρ_min = −0.23 e Å⁻³
1449 reflections	Absolute structure: Flack (1983), 785 Friedel pairs
121 parameters	Absolute structure parameter: 0.31 (8)
5 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.84628 (5)	0.31587 (4)	0.15713 (3)	0.02340 (12)
O1	0.81623 (18)	0.44053 (16)	0.41523 (12)	0.0304 (3)
O2	0.7512 (2)	0.46465 (15)	0.13994 (12)	0.0348 (3)
O3	0.71610 (16)	0.20834 (15)	0.21966 (11)	0.0307 (3)
O4	0.9407 (2)	0.25936 (17)	0.04580 (11)	0.0344 (3)
N1	1.37517 (19)	0.33180 (18)	0.31720 (15)	0.0310 (3)
C1	1.3417 (3)	0.3866 (2)	0.43239 (17)	0.0317 (4)
C2	1.1563 (3)	0.42245 (19)	0.47075 (15)	0.0282 (3)
C3	0.9993 (2)	0.40609 (18)	0.38677 (14)	0.0224 (3)
C4	1.0389 (2)	0.34817 (17)	0.26608 (14)	0.0216 (3)
C5	1.2292 (2)	0.3108 (2)	0.23489 (15)	0.0274 (3)
H1O	0.794 (5)	0.485 (3)	0.4827 (16)	0.064 (9)*
H1N	1.4924 (18)	0.306 (3)	0.2930 (19)	0.036 (6)*
H1	1.456 (2)	0.394 (3)	0.4826 (19)	0.038 (6)*
H2	1.138 (3)	0.463 (2)	0.5519 (11)	0.021 (4)*
H5	1.267 (3)	0.263 (3)	0.1575 (14)	0.042 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02372 (18)	0.02877 (19)	0.01770 (17)	0.00307 (16)	−0.00047 (14)	−0.00191 (14)
O1	0.0236 (6)	0.0426 (7)	0.0249 (6)	0.0052 (5)	0.0026 (5)	−0.0082 (5)
O2	0.0429 (7)	0.0352 (7)	0.0262 (6)	0.0118 (5)	−0.0080 (6)	0.0003 (5)
O3	0.0259 (5)	0.0354 (6)	0.0308 (6)	−0.0021 (5)	0.0030 (5)	−0.0030 (5)
O4	0.0361 (6)	0.0460 (7)	0.0212 (5)	0.0012 (6)	0.0036 (5)	−0.0086 (5)
N1	0.0174 (6)	0.0363 (8)	0.0393 (8)	0.0029 (6)	0.0028 (5)	0.0047 (6)
C1	0.0258 (8)	0.0326 (8)	0.0368 (9)	−0.0014 (7)	−0.0071 (8)	0.0052 (7)
C2	0.0298 (8)	0.0321 (7)	0.0227 (7)	−0.0004 (8)	−0.0030 (7)	0.0001 (6)
C3	0.0211 (7)	0.0237 (7)	0.0224 (7)	0.0004 (6)	0.0014 (6)	0.0017 (5)
C4	0.0210 (7)	0.0249 (7)	0.0189 (6)	0.0016 (5)	0.0009 (5)	0.0011 (6)
C5	0.0253 (7)	0.0296 (7)	0.0273 (7)	0.0022 (7)	0.0063 (6)	0.0018 (7)

Geometric parameters (Å, º) top

S1—O4	1.4390 (12)	N1—H1N	0.868 (10)
S1—O3	1.4549 (12)	C1—C2	1.362 (3)
S1—O2	1.4666 (13)	C1—H1	0.947 (10)
S1—C4	1.7747 (15)	C2—C3	1.402 (2)
O1—C3	1.316 (2)	C2—H2	0.943 (9)
O1—H1O	0.834 (10)	C3—C4	1.411 (2)
N1—C5	1.338 (2)	C4—C5	1.375 (2)
N1—C1	1.340 (2)	C5—H5	0.961 (10)

O4—S1—O3	115.32 (8)	C1—C2—C3	119.25 (16)
O4—S1—O2	113.52 (8)	C1—C2—H2	119.0 (13)
O3—S1—O2	111.40 (8)	C3—C2—H2	121.6 (13)
O4—S1—C4	105.51 (7)	O1—C3—C2	123.29 (15)
O3—S1—C4	104.55 (7)	O1—C3—C4	118.31 (14)
O2—S1—C4	105.41 (7)	C2—C3—C4	118.40 (15)
C3—O1—H1O	118 (2)	C5—C4—C3	119.11 (14)
C5—N1—C1	121.76 (14)	C5—C4—S1	119.83 (12)
C5—N1—H1N	116.7 (15)	C3—C4—S1	121.01 (11)
C1—N1—H1N	121.5 (15)	N1—C5—C4	120.37 (15)
N1—C1—C2	121.07 (16)	N1—C5—H5	115.2 (14)
N1—C1—H1	113.9 (15)	C4—C5—H5	124.4 (14)
C2—C1—H1	125.0 (15)

C5—N1—C1—C2	0.4 (3)	O3—S1—C4—C5	118.79 (15)
N1—C1—C2—C3	−2.0 (3)	O2—S1—C4—C5	−123.66 (15)
C1—C2—C3—O1	−178.80 (16)	O4—S1—C4—C3	179.33 (13)
C1—C2—C3—C4	1.9 (2)	O3—S1—C4—C3	−58.62 (15)
O1—C3—C4—C5	−179.69 (15)	O2—S1—C4—C3	58.93 (15)
C2—C3—C4—C5	−0.4 (2)	C1—N1—C5—C4	1.2 (3)
O1—C3—C4—S1	−2.3 (2)	C3—C4—C5—N1	−1.2 (3)
C2—C3—C4—S1	177.04 (12)	S1—C4—C5—N1	−178.64 (12)
O4—S1—C4—C5	−3.26 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2ⁱ	0.83 (1)	1.76 (1)	2.581 (2)	166 (3)
N1—H1n···O3ⁱⁱ	0.87 (1)	1.91 (1)	2.762 (2)	166 (2)

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₅H₅NO₄S
M_r	175.16
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.7980 (2), 8.7618 (3), 10.6797 (3)
V (Å³)	636.11 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.28 × 0.23 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.880, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	6216, 1449, 1403
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.068, 1.09
No. of reflections	1449
No. of parameters	121
No. of restraints	5
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23
Absolute structure	Flack (1983), 785 Friedel pairs
Absolute structure parameter	0.31 (8)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2ⁱ	0.83 (1)	1.76 (1)	2.581 (2)	166 (3)
N1—H1n···O3ⁱⁱ	0.87 (1)	1.91 (1)	2.762 (2)	166 (2)

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x+1, y, z.

Acknowledgements

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), Heilongjiang University and the University of Malaya for supporting this study.

References

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