4-Hydroxy­pyridinium hydrogen sulfate

Huo, L.-H.; Xu, Y.-M.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809048533

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3148

doi:10.1107/S1600536809048533

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4-Hydroxypyridinium hydrogen sulfate

Li-Hua Huo,^a Ying-Ming Xu,^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 14 November 2009; accepted 15 November 2009; online 21 November 2009)

The crystal structure of the title salt, C₅H₆NO⁺·HSO₄⁻, consists of planar(r.m.s. deviation = 0.001 Å) 4-hydroxypyridinium cations and hydrogen sulfate anions which are hydrogen bonded into a layer motif. In the anion, the S—O bond [1.551 (2) Å] involving the O atom bearing the acid H atom is longer than the other three S—O bonds, which range from 1.437 (1) to 1.454 (1) Å.

Related literature

For the crystal structures of bis(4-hydroxypyridinium) sulfate monohydrate and tris(4-hydroxypyridinium) hydrogen disulfate monohydrate, see: Xu et al. (2009a ,b ).

Experimental

Crystal data

C₅H₆NO⁺·HSO₄⁻
M_r = 193.18
Monoclinic, P 2₁ /c
a = 10.4541 (7) Å
b = 10.7017 (6) Å
c = 6.8397 (4) Å
β = 96.503 (2)°
V = 760.28 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 293 K
0.27 × 0.21 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.898, T_max = 0.941
7273 measured reflections
1729 independent reflections
1612 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.03
1729 reflections
137 parameters
7 restraints
All H-atom parameters refined
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

S1—O1	1.445 (1)
S1—O2	1.551 (2)
S1—O3	1.437 (1)
S1—O4	1.454 (1)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4ⁱ	0.85 (1)	1.77 (1)	2.603 (2)	168 (3)
O5—H5⋯O1	0.85 (1)	1.77 (1)	2.6166 (19)	175 (3)
N1—H1⋯O3ⁱⁱ	0.84 (1)	2.04 (1)	2.8529 (19)	163 (2)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) 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: 10.1107/S1600536809048533/xu2677sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048533/xu2677Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of bis(4-hydroxypyridinium) sulfate monohydrate and tris(4-hydroxypyridinium) hydrogen disulfate monohydrate, see: Xu et al. (2009a,b).

Experimental top

The compound is a side product that was obtained when commercially available 4-hydroxypyridine-3-sulfonic acid was recrystallized from water. Its crystals were obtained from a water solution.

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 [C₅H₆NO]⁺ [HSO₄]^- at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-Hydroxypyridinium hydrogen sulfate top

Crystal data top

C₅H₆NO⁺·HSO₄⁻	F(000) = 400
M_r = 193.18	D_x = 1.688 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6627 reflections
a = 10.4541 (7) Å	θ = 3.6–27.4°
b = 10.7017 (6) Å	µ = 0.41 mm⁻¹
c = 6.8397 (4) Å	T = 293 K
β = 96.503 (2)°	Prism, colorless
V = 760.28 (8) Å³	0.27 × 0.21 × 0.15 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1729 independent reflections
Radiation source: fine-focus sealed tube	1612 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scan	θ_max = 27.4°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
T_min = 0.898, T_max = 0.941	k = −13→13
7273 measured reflections	l = −8→8

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	All H-atom parameters refined
S = 1.03	w = 1/[σ²(F_o²) + (0.0587P)² + 0.3712P] where P = (F_o² + 2F_c²)/3
1729 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.52 e Å⁻³
7 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₅H₆NO⁺·HSO₄⁻	V = 760.28 (8) Å³
M_r = 193.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4541 (7) Å	µ = 0.41 mm⁻¹
b = 10.7017 (6) Å	T = 293 K
c = 6.8397 (4) Å	0.27 × 0.21 × 0.15 mm
β = 96.503 (2)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1729 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1612 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.941	R_int = 0.017
7273 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	7 restraints
wR(F²) = 0.098	All H-atom parameters refined
S = 1.03	Δρ_max = 0.52 e Å⁻³
1729 reflections	Δρ_min = −0.39 e Å⁻³
137 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.15352 (4)	0.36664 (3)	0.22053 (6)	0.02984 (15)
O1	0.28767 (13)	0.37320 (14)	0.2986 (3)	0.0580 (4)
O2	0.1438 (2)	0.41518 (14)	0.0056 (2)	0.0657 (5)
O3	0.07735 (11)	0.45271 (12)	0.3196 (2)	0.0423 (3)
O4	0.10415 (14)	0.23950 (12)	0.21136 (18)	0.0430 (3)
O5	0.46894 (12)	0.20467 (13)	0.2977 (2)	0.0486 (4)
N1	0.82340 (14)	0.36324 (15)	0.3509 (2)	0.0416 (4)
C1	0.72047 (18)	0.43863 (17)	0.3364 (3)	0.0388 (4)
C2	0.59869 (16)	0.39037 (16)	0.3180 (3)	0.0351 (4)
C3	0.58308 (15)	0.26042 (15)	0.3148 (2)	0.0320 (3)
C4	0.69235 (16)	0.18433 (16)	0.3312 (3)	0.0359 (4)
C5	0.81115 (16)	0.23848 (19)	0.3484 (3)	0.0410 (4)
H1	0.8975 (14)	0.395 (2)	0.366 (4)	0.063 (7)*
H2	0.134 (3)	0.357 (2)	−0.078 (4)	0.079 (9)*
H5	0.412 (2)	0.2615 (19)	0.293 (4)	0.063 (7)*
H1A	0.735 (2)	0.5257 (10)	0.338 (3)	0.044 (6)*
H2A	0.5283 (16)	0.4452 (18)	0.302 (3)	0.049 (6)*
H4	0.6824 (19)	0.0967 (9)	0.330 (3)	0.040 (5)*
H5A	0.8881 (16)	0.191 (2)	0.356 (4)	0.061 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0273 (2)	0.0272 (2)	0.0352 (2)	−0.00275 (13)	0.00428 (15)	−0.00138 (13)
O1	0.0264 (7)	0.0495 (9)	0.0963 (12)	0.0041 (5)	−0.0012 (7)	−0.0159 (8)
O2	0.1253 (16)	0.0347 (7)	0.0384 (7)	−0.0135 (9)	0.0154 (8)	0.0017 (6)
O3	0.0312 (6)	0.0428 (7)	0.0538 (8)	0.0005 (5)	0.0090 (5)	−0.0101 (6)
O4	0.0581 (8)	0.0317 (6)	0.0391 (6)	−0.0130 (5)	0.0045 (5)	0.0004 (5)
O5	0.0254 (6)	0.0346 (7)	0.0852 (11)	−0.0021 (5)	0.0041 (6)	−0.0049 (6)
N1	0.0289 (7)	0.0507 (9)	0.0457 (8)	−0.0105 (6)	0.0064 (6)	−0.0084 (7)
C1	0.0439 (9)	0.0337 (8)	0.0397 (9)	−0.0068 (7)	0.0086 (7)	−0.0045 (7)
C2	0.0329 (8)	0.0303 (8)	0.0424 (9)	0.0037 (6)	0.0052 (7)	−0.0022 (6)
C3	0.0268 (7)	0.0316 (8)	0.0376 (8)	−0.0003 (6)	0.0037 (6)	−0.0026 (6)
C4	0.0315 (8)	0.0308 (8)	0.0454 (9)	0.0034 (6)	0.0037 (7)	−0.0031 (7)
C5	0.0279 (8)	0.0485 (10)	0.0466 (9)	0.0043 (7)	0.0040 (7)	−0.0058 (8)

Geometric parameters (Å, º) top

S1—O1	1.445 (1)	N1—H1	0.841 (10)
S1—O2	1.551 (2)	C1—C2	1.366 (2)
S1—O3	1.437 (1)	C1—H1A	0.945 (10)
S1—O4	1.454 (1)	C2—C3	1.400 (2)
S1—O2	1.5514 (15)	C2—H2A	0.938 (10)
O2—H2	0.848 (10)	C3—C4	1.397 (2)
O5—C3	1.3273 (19)	C4—C5	1.363 (2)
O5—H5	0.849 (10)	C4—H4	0.943 (9)
N1—C1	1.340 (2)	C5—H5A	0.947 (10)
N1—C5	1.341 (3)

O3—S1—O1	111.16 (8)	C2—C1—H1A	121.6 (13)
O3—S1—O4	114.04 (8)	C1—C2—C3	118.86 (16)
O1—S1—O4	112.73 (9)	C1—C2—H2A	119.0 (14)
O3—S1—O2	104.60 (9)	C3—C2—H2A	122.1 (14)
O1—S1—O2	106.91 (11)	O5—C3—C4	117.63 (15)
O4—S1—O2	106.71 (8)	O5—C3—C2	123.36 (15)
S1—O2—H2	113 (2)	C4—C3—C2	119.01 (15)
C3—O5—H5	107.5 (19)	C5—C4—C3	119.20 (16)
C1—N1—C5	121.59 (15)	C5—C4—H4	121.5 (12)
C1—N1—H1	119.2 (19)	C3—C4—H4	119.3 (12)
C5—N1—H1	119 (2)	N1—C5—C4	120.59 (16)
N1—C1—C2	120.75 (16)	N1—C5—H5A	116.9 (16)
N1—C1—H1A	117.6 (13)	C4—C5—H5A	122.5 (16)

C5—N1—C1—C2	−0.1 (3)	O5—C3—C4—C5	179.79 (17)
N1—C1—C2—C3	0.1 (3)	C2—C3—C4—C5	−0.4 (3)
C1—C2—C3—O5	179.94 (17)	C1—N1—C5—C4	−0.1 (3)
C1—C2—C3—C4	0.2 (2)	C3—C4—C5—N1	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ⁱ	0.85 (1)	1.77 (1)	2.603 (2)	168 (3)
O5—H5···O1	0.85 (1)	1.77 (1)	2.6166 (19)	175 (3)
N1—H1···O3ⁱⁱ	0.84 (1)	2.04 (1)	2.8529 (19)	163 (2)

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

Experimental details

Crystal data
Chemical formula	C₅H₆NO⁺·HSO₄⁻
M_r	193.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.4541 (7), 10.7017 (6), 6.8397 (4)
β (°)	96.503 (2)
V (Å³)	760.28 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.27 × 0.21 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.898, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	7273, 1729, 1612
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.03
No. of reflections	1729
No. of parameters	137
No. of restraints	7
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.39

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

Selected bond lengths (Å) top

S1—O1	1.445 (1)	S1—O3	1.437 (1)
S1—O2	1.551 (2)	S1—O4	1.454 (1)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ⁱ	0.85 (1)	1.77 (1)	2.603 (2)	168 (3)
O5—H5···O1	0.85 (1)	1.77 (1)	2.6166 (19)	175 (3)
N1—H1···O3ⁱⁱ	0.84 (1)	2.04 (1)	2.8529 (19)	163 (2)

Symmetry codes: (i) x, −y+1/2, 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 Scientific Fund of Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University 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
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Xu, Y.-M., Gao, S. & Ng, S. W. (2009a). Acta Cryst. E65, o3146. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, Y.-M., Gao, S. & Ng, S. W. (2009b). Acta Cryst. E65, o3147. Web of Science CSD CrossRef IUCr Journals Google Scholar