4-Amino­pyridinium-3-sulfonate monohydrate

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

doi:10.1107/S1600536811002145

organic compounds

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Volume 67| Part 2| February 2011| Page o456

doi:10.1107/S1600536811002145

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4-Aminopyridinium-3-sulfonate monohydrate

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 14 January 2011; online 22 January 2011)

The reaction of 4-aminopyridine and oleum yielded the title hydrated zwitterion, C₅H₆N₂O₃S·H₂O. There are two formula units in the asymmetric unit. The H and non-H atoms of both zwitterions lie on a mirror plane except for one sulfonate O atom. The water molecules are also situated on a mirror plane. In the crystal, the zwitterions and water molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

The analogous reaction of 4-hydroxypyridine with oleum yielded hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate and 4-hydroxypyridinium-3-sulfonate; see: Zhu et al. (2009 , 2011 ).

Experimental

Crystal data

C₅H₆N₂O₃S·H₂O
M_r = 192.19
Orthorhombic, P n m a
a = 31.6739 (13) Å
b = 6.5824 (3) Å
c = 7.3204 (3) Å
V = 1526.23 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.921, T_max = 0.939
22965 measured reflections
1898 independent reflections
1325 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.137
S = 1.17
1898 reflections
157 parameters
8 restraints
All H-atom parameters refined
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1wⁱ	0.88 (2)	1.99 (2)	2.820 (4)	158 (3)
N2—H22⋯O2ⁱⁱ	0.88 (2)	2.01 (2)	2.886 (3)	172 (3)
N3—H3⋯O1wⁱⁱⁱ	0.88 (2)	2.15 (3)	2.871 (4)	139 (3)
N4—H42⋯O4^iv	0.88 (2)	1.99 (2)	2.869 (3)	173 (4)
O1w—H1w⋯O1	0.84 (2)	1.99 (2)	2.826 (3)	173 (3)
O2w—H2w⋯O3	0.85 (2)	2.02 (2)	2.864 (2)	171 (3)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x, y, z-1; (iii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) x, y, z+1.

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: 10.1107/S1600536811002145/im2250sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002145/im2250Isup2.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); a later repeat of the synthesis gave zwitterionic 4-hydroxypyridinium-3-sulfonate (Zhu et al., 2011). The studies were extended to 4-aminopyridine which upon reaction with oleum gave zwitterionic 4-aminopyridinium-3-sulfonate as a monohydrate (Scheme I, Fig. 1). The bonds in the ring are delocalized bonds. Adjacent zwitterions and water molecues are linked by N–H···O and O–H···O hydrogen bonds into a three-dimensional network (Tablel 1).

Related literature top

The analogous reaction of 4-hydroxypyridine with oleum yielded hydronium 4-oxo-1,4-dihydropyridine-3-sulfonate dihydrate and 4-hydroxypyridinium-3-sulfonate; see: Zhu et al. (2009, 2011).

Experimental top

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

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 the two independent molecules of C₅H₆N₂O₃S^.H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-Aminopyridinium-3-sulfonate monohydrate top

Crystal data top

C₅H₆N₂O₃S·H₂O	F(000) = 800
M_r = 192.19	D_x = 1.673 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 13913 reflections
a = 31.6739 (13) Å	θ = 3.1–27.5°
b = 6.5824 (3) Å	µ = 0.40 mm⁻¹
c = 7.3204 (3) Å	T = 293 K
V = 1526.23 (11) Å³	Prism, colorless
Z = 8	0.21 × 0.19 × 0.16 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1898 independent reflections
Radiation source: fine-focus sealed tube	1325 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −41→41
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −8→8
T_min = 0.921, T_max = 0.939	l = −9→8
22965 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	All H-atom parameters refined
S = 1.17	w = 1/[σ²(F_o²) + (0.0795P)²] where P = (F_o² + 2F_c²)/3
1898 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.45 e Å⁻³
8 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₅H₆N₂O₃S·H₂O	V = 1526.23 (11) Å³
M_r = 192.19	Z = 8
Orthorhombic, Pnma	Mo Kα radiation
a = 31.6739 (13) Å	µ = 0.40 mm⁻¹
b = 6.5824 (3) Å	T = 293 K
c = 7.3204 (3) Å	0.21 × 0.19 × 0.16 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1898 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1325 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.939	R_int = 0.049
22965 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	8 restraints
wR(F²) = 0.137	All H-atom parameters refined
S = 1.17	Δρ_max = 0.45 e Å⁻³
1898 reflections	Δρ_min = −0.49 e Å⁻³
157 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.55812 (2)	0.2500	0.86929 (9)	0.0348 (3)
S2	0.66689 (2)	0.2500	0.36003 (10)	0.0360 (3)
O1	0.58140 (6)	0.4293 (3)	0.8206 (3)	0.0647 (6)
O2	0.54212 (8)	0.2500	1.0518 (3)	0.0712 (10)
O1W	0.62156 (8)	0.7500	1.0095 (3)	0.0451 (6)
H1W	0.6107 (9)	0.648 (4)	0.959 (4)	0.068*
O2W	0.67561 (10)	−0.2500	0.6401 (4)	0.0573 (8)
H2W	0.6649 (10)	−0.151 (4)	0.582 (4)	0.086*
O3	0.64409 (5)	0.0686 (3)	0.4112 (2)	0.0496 (5)
O4	0.68205 (8)	0.2500	0.1750 (3)	0.0570 (8)
N1	0.43845 (8)	0.2500	0.7058 (4)	0.0413 (7)
H1	0.4151 (7)	0.2500	0.770 (4)	0.050*
N2	0.55273 (8)	0.2500	0.4434 (3)	0.0366 (7)
H21	0.5763 (6)	0.2500	0.505 (4)	0.044*
H22	0.5522 (11)	0.2500	0.3234 (14)	0.044*
N3	0.78781 (8)	0.2500	0.5065 (4)	0.0416 (7)
H3	0.8121 (6)	0.2500	0.449 (4)	0.050*
N4	0.67536 (8)	0.2500	0.7841 (4)	0.0443 (8)
H41	0.6504 (6)	0.2500	0.731 (5)	0.053*
H42	0.6752 (12)	0.2500	0.9046 (15)	0.053*
C1	0.47379 (9)	0.2500	0.8053 (4)	0.0367 (8)
H1A	0.4717	0.2500	0.9320	0.044*
C2	0.51300 (9)	0.2500	0.7265 (4)	0.0296 (7)
C3	0.51604 (9)	0.2500	0.5320 (4)	0.0285 (7)
C4	0.47767 (9)	0.2500	0.4337 (4)	0.0330 (7)
H4	0.4783	0.2500	0.3067	0.040*
C5	0.44023 (11)	0.2500	0.5209 (4)	0.0408 (8)
H5	0.4153	0.2500	0.4535	0.049*
C6	0.78747 (10)	0.2500	0.6914 (5)	0.0449 (9)
H6	0.8129	0.2500	0.7549	0.054*
C7	0.75061 (10)	0.2500	0.7851 (4)	0.0399 (8)
H7	0.7510	0.2500	0.9121	0.048*
C8	0.71128 (9)	0.2500	0.6911 (4)	0.0344 (7)
C9	0.71321 (10)	0.2500	0.4964 (4)	0.0332 (7)
C10	0.75175 (10)	0.2500	0.4121 (4)	0.0368 (8)
H10	0.7529	0.2500	0.2852	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0304 (4)	0.0518 (6)	0.0223 (4)	0.000	−0.0034 (3)	0.000
S2	0.0287 (4)	0.0574 (6)	0.0219 (4)	0.000	−0.0017 (3)	0.000
O1	0.0602 (11)	0.0694 (15)	0.0644 (12)	−0.0289 (10)	−0.0289 (10)	0.0189 (10)
O2	0.0466 (15)	0.144 (3)	0.0225 (12)	0.000	−0.0016 (11)	0.000
O1W	0.0354 (13)	0.0573 (18)	0.0428 (14)	0.000	0.0008 (10)	0.000
O2W	0.0606 (18)	0.065 (2)	0.0457 (16)	0.000	−0.0179 (12)	0.000
O3	0.0365 (9)	0.0631 (13)	0.0493 (10)	−0.0121 (9)	−0.0081 (7)	0.0079 (9)
O4	0.0438 (14)	0.104 (2)	0.0237 (11)	0.000	−0.0003 (10)	0.000
N1	0.0255 (13)	0.059 (2)	0.0388 (15)	0.000	0.0049 (11)	0.000
N2	0.0287 (13)	0.0584 (19)	0.0227 (12)	0.000	−0.0021 (11)	0.000
N3	0.0240 (13)	0.055 (2)	0.0452 (16)	0.000	0.0040 (11)	0.000
N4	0.0337 (15)	0.076 (2)	0.0228 (13)	0.000	0.0004 (11)	0.000
C1	0.0335 (16)	0.050 (2)	0.0265 (14)	0.000	0.0026 (13)	0.000
C2	0.0280 (14)	0.0379 (19)	0.0227 (14)	0.000	−0.0013 (11)	0.000
C3	0.0303 (15)	0.0324 (18)	0.0227 (13)	0.000	0.0013 (11)	0.000
C4	0.0311 (15)	0.041 (2)	0.0267 (14)	0.000	−0.0032 (12)	0.000
C5	0.0325 (16)	0.054 (2)	0.0363 (17)	0.000	−0.0078 (13)	0.000
C6	0.0307 (16)	0.058 (2)	0.0461 (18)	0.000	−0.0103 (15)	0.000
C7	0.0372 (17)	0.052 (2)	0.0304 (16)	0.000	−0.0086 (14)	0.000
C8	0.0314 (16)	0.045 (2)	0.0270 (14)	0.000	−0.0013 (12)	0.000
C9	0.0279 (15)	0.046 (2)	0.0261 (14)	0.000	0.0004 (11)	0.000
C10	0.0333 (16)	0.045 (2)	0.0322 (16)	0.000	0.0038 (13)	0.000

Geometric parameters (Å, º) top

S1—O2	1.429 (2)	N3—H3	0.88 (2)
S1—O1	1.436 (2)	N4—C8	1.326 (4)
S1—O1ⁱ	1.436 (2)	N4—H41	0.88 (2)
S1—C2	1.771 (3)	N4—H42	0.88 (2
S2—O4	1.437 (2)	C1—C2	1.369 (4)
S2—O3	1.4451 (18)	C1—H1A	0.9300
S2—O3ⁱ	1.4451 (18)	C2—C3	1.427 (4)
S2—C9	1.775 (3)	C3—C4	1.412 (4)
O1W—H1W	0.84 (3)	C4—C5	1.347 (4)
O2W—H2W	0.85 (2)	C4—H4	0.9300
N1—C1	1.335 (4)	C5—H5	0.9300
N1—C5	1.355 (4)	C6—C7	1.354 (5)
N1—H1	0.878 (10)	C6—H6	0.9300
N2—C3	1.331 (4)	C7—C8	1.423 (4)
N2—H21	0.87 (2)	C7—H7	0.9300
N2—H22	0.88 (2)	C8—C9	1.427 (4)
N3—C10	1.335 (4)	C9—C10	1.368 (4)
N3—C6	1.354 (4)	C10—H10	0.9300

O2—S1—O1	114.46 (10)	C1—C2—C3	118.8 (3)
O2—S1—O1ⁱ	114.46 (10)	C1—C2—S1	118.9 (2)
O1—S1—O1ⁱ	110.5 (2)	C3—C2—S1	122.3 (2)
O2—S1—C2	105.40 (14)	N2—C3—C4	120.2 (2)
O1—S1—C2	105.54 (9)	N2—C3—C2	123.0 (3)
O1ⁱ—S1—C2	105.54 (9)	C4—C3—C2	116.8 (3)
O4—S2—O3	114.29 (9)	C5—C4—C3	121.1 (3)
O4—S2—O3ⁱ	114.29 (9)	C5—C4—H4	119.5
O3—S2—O3ⁱ	111.47 (16)	C3—C4—H4	119.5
O4—S2—C9	104.71 (14)	C4—C5—N1	120.7 (3)
O3—S2—C9	105.51 (8)	C4—C5—H5	119.7
O3ⁱ—S2—C9	105.51 (8)	N1—C5—H5	119.7
C1—N1—C5	120.7 (3)	N3—C6—C7	120.9 (3)
C1—N1—H1	114 (2)	N3—C6—H6	119.6
C5—N1—H1	125 (2)	C7—C6—H6	119.6
C3—N2—H21	120 (2)	C6—C7—C8	120.7 (3)
C3—N2—H22	118 (2)	C6—C7—H7	119.7
H21—N2—H22	122 (3)	C8—C7—H7	119.7
C10—N3—C6	120.7 (3)	N4—C8—C7	120.2 (3)
C10—N3—H3	120 (2)	N4—C8—C9	123.4 (3)
C6—N3—H3	119 (2)	C7—C8—C9	116.4 (3)
C8—N4—H41	123 (3)	C10—C9—C8	119.3 (3)
C8—N4—H42	121 (3)	C10—C9—S2	119.0 (2)
H41—N4—H42	116 (4)	C8—C9—S2	121.8 (2)
N1—C1—C2	122.0 (3)	N3—C10—C9	122.0 (3)
N1—C1—H1A	119.0	N3—C10—H10	119.0
C2—C1—H1A	119.0	C9—C10—H10	119.0

C5—N1—C1—C2	0.0	C10—N3—C6—C7	0.0
N1—C1—C2—C3	0.0	N3—C6—C7—C8	0.0
N1—C1—C2—S1	180.0	C6—C7—C8—N4	180.0
O2—S1—C2—C1	0.0	C6—C7—C8—C9	0.0
O1—S1—C2—C1	−121.49 (11)	N4—C8—C9—C10	180.0
O1ⁱ—S1—C2—C1	121.49 (11)	C7—C8—C9—C10	0.0
O2—S1—C2—C3	180.0	N4—C8—C9—S2	0.0
O1—S1—C2—C3	58.51 (11)	C7—C8—C9—S2	180.0
O1ⁱ—S1—C2—C3	−58.51 (11)	O4—S2—C9—C10	0.0
C1—C2—C3—N2	180.0	O3—S2—C9—C10	120.95 (9)
S1—C2—C3—N2	0.0	O3ⁱ—S2—C9—C10	−120.95 (9)
C1—C2—C3—C4	0.0	O4—S2—C9—C8	180.0
S1—C2—C3—C4	180.0	O3—S2—C9—C8	−59.05 (9)
N2—C3—C4—C5	180.0	O3ⁱ—S2—C9—C8	59.05 (9)
C2—C3—C4—C5	0.0	C6—N3—C10—C9	0.0
C3—C4—C5—N1	0.0	C8—C9—C10—N3	0.0
C1—N1—C5—C4	0.0	S2—C9—C10—N3	180.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1wⁱⁱ	0.88 (2)	1.99 (2)	2.820 (4)	158 (3)
N2—H22···O2ⁱⁱⁱ	0.88 (2)	2.01 (2)	2.886 (3)	172 (3)
N3—H3···O1w^iv	0.88 (2)	2.15 (3)	2.871 (4)	139 (3)
N4—H42···O4^v	0.88 (2)	1.99 (2)	2.869 (3)	173 (4)
O1w—H1w···O1	0.84 (2)	1.99 (2)	2.826 (3)	173 (3)
O2w—H2w···O3	0.85 (2)	2.02 (2)	2.864 (2)	171 (3)

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

Experimental details

Crystal data
Chemical formula	C₅H₆N₂O₃S·H₂O
M_r	192.19
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	31.6739 (13), 6.5824 (3), 7.3204 (3)
V (Å³)	1526.23 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.21 × 0.19 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.921, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	22965, 1898, 1325
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.137, 1.17
No. of reflections	1898
No. of parameters	157
No. of restraints	8
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.49

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
N1—H1···O1wⁱ	0.88 (2)	1.99 (2)	2.820 (4)	158 (3)
N2—H22···O2ⁱⁱ	0.88 (2)	2.01 (2)	2.886 (3)	172 (3)
N3—H3···O1wⁱⁱⁱ	0.88 (2)	2.15 (3)	2.871 (4)	139 (3)
N4—H42···O4^iv	0.88 (2)	1.99 (2)	2.869 (3)	173 (4)
O1w—H1w···O1	0.84 (2)	1.99 (2)	2.826 (3)	173 (3)
O2w—H2w···O3	0.85 (2)	2.02 (2)	2.864 (2)	171 (3)

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

Acknowledgements

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903) and 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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