Bis(4-hydroxy­pyridinium) sulfate monohydrate

Xu, Y.-M.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809048521

organic compounds

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Volume 65| Part 12| December 2009| Page o3146

doi:10.1107/S1600536809048521

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Bis(4-hydroxypyridinium) sulfate monohydrate

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)

In the crystal structure of the title salt, 2C₅H₆NO⁺·SO₄²⁻·H₂O, one planar (r.m.s. deviation = 0.01 Å) cation is stacked approximately over the other [dihedral angle between planes = 8.6 (1)°]. The pyridinium and hydroxy H atoms are hydrogen-bond donor atoms to the O atoms of the sulfate anion; the cations, anions and water molecules are consolidated into a three-dimensional network through O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For the crystal structures of 4-hydroxypyridinium salts, see: Fukunaga et al. (2004 ); Gao et al. (2004 ); Kiviniemi et al. (2001 ); Wang et al. (2006 ).

Experimental

Crystal data

2C₅H₆NO⁺·SO₄²⁻·H₂O
M_r = 306.29
Monoclinic, P 2₁ /n
a = 7.1404 (2) Å
b = 19.9797 (5) Å
c = 9.5148 (2) Å
β = 102.557 (1)°
V = 1324.94 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.25 × 0.18 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.934, T_max = 0.957
12868 measured reflections
3032 independent reflections
2693 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.103
S = 1.05
3032 reflections
197 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O1w	0.85 (1)	1.71 (1)	2.552 (2)	171 (2)
O6—H6⋯O2	0.86 (1)	1.68 (1)	2.539 (1)	177 (2)
O1w—H11⋯O1	0.84 (1)	1.93 (1)	2.765 (2)	170 (3)
O1w—H12⋯O3ⁱ	0.85 (1)	1.99 (2)	2.783 (2)	157 (3)
N1—H1n⋯O4ⁱⁱ	0.86	1.95	2.766 (2)	158
N2—H2n⋯O3ⁱⁱⁱ	0.86	1.87	2.705 (2)	163
Symmetry codes: (i) x-1, y, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536809048521/xu2675sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048521/xu2675Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of 4-hydroxypyridinium salts, see: Fukunaga et al. (2004); Gao et al. (2004); Kiviniemi et al. (2001); Wang et al. (2006).

Experimental top

Copper nitrate (0.37 g, 2 mmol) and 4-hydroxypyridine-3-sulfonic acid (0.35 g, 2 mmol) were dissolved in hot water. The pH value was adjusted to 6 with 0.1 M sodium hydroxide. The solution was allowed to evaporate slowly at room temperature; colorless prismatic crystals were isolated from the blue-green solution after several days.

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 2[C₅H₆NO][SO₄]^.H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Bis(4-hydroxypyridinium) sulfate monohydrate top

Crystal data top

2C₅H₆NO⁺·SO₄²⁻·H₂O	F(000) = 640
M_r = 306.29	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11052 reflections
a = 7.1404 (2) Å	θ = 3.0–27.4°
b = 19.9797 (5) Å	µ = 0.28 mm⁻¹
c = 9.5148 (2) Å	T = 293 K
β = 102.557 (1)°	Prism, colorless
V = 1324.94 (6) Å³	0.25 × 0.18 × 0.16 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3032 independent reflections
Radiation source: fine-focus sealed tube	2693 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scan	θ_max = 27.4°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.934, T_max = 0.957	k = −25→25
12868 measured reflections	l = −12→12

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0703P)² + 0.2237P] where P = (F_o² + 2F_c²)/3
3032 reflections	(Δ/σ)_max = 0.001
197 parameters	Δρ_max = 0.42 e Å⁻³
6 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

2C₅H₆NO⁺·SO₄²⁻·H₂O	V = 1324.94 (6) Å³
M_r = 306.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1404 (2) Å	µ = 0.28 mm⁻¹
b = 19.9797 (5) Å	T = 293 K
c = 9.5148 (2) Å	0.25 × 0.18 × 0.16 mm
β = 102.557 (1)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3032 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2693 reflections with I > 2σ(I)
T_min = 0.934, T_max = 0.957	R_int = 0.020
12868 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	6 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.42 e Å⁻³
3032 reflections	Δρ_min = −0.43 e Å⁻³
197 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.61983 (4)	0.073598 (14)	0.24878 (3)	0.02657 (12)
O1	0.43221 (15)	0.06385 (5)	0.15168 (11)	0.0397 (3)
O2	0.64861 (17)	0.14531 (5)	0.28579 (12)	0.0436 (3)
O3	0.77259 (15)	0.05185 (5)	0.17503 (12)	0.0388 (2)
O4	0.63392 (17)	0.03440 (5)	0.38109 (10)	0.0417 (3)
O5	0.20084 (17)	0.22956 (5)	0.36294 (12)	0.0425 (3)
O6	0.47857 (16)	0.23613 (5)	0.11899 (11)	0.0373 (2)
O1W	0.1093 (2)	0.12590 (7)	0.2064 (2)	0.0645 (4)
N1	0.04132 (18)	0.41179 (6)	0.18890 (13)	0.0356 (3)
H1N	0.0088	0.4507	0.1532	0.043*
N2	0.62608 (18)	0.42205 (6)	0.27653 (15)	0.0379 (3)
H2N	0.6556	0.4617	0.3091	0.045*
C1	−0.0033 (2)	0.35736 (7)	0.10572 (15)	0.0355 (3)
H1	−0.0686	0.3623	0.0105	0.043*
C2	0.0458 (2)	0.29479 (7)	0.15884 (14)	0.0321 (3)
H2	0.0135	0.2573	0.1006	0.039*
C3	0.14570 (19)	0.28776 (7)	0.30255 (14)	0.0304 (3)
C4	0.1913 (2)	0.34564 (7)	0.38645 (14)	0.0340 (3)
H4	0.2585	0.3424	0.4816	0.041*
C5	0.1361 (2)	0.40666 (7)	0.32736 (16)	0.0358 (3)
H5A	0.1643	0.4451	0.3831	0.043*
C6	0.5135 (2)	0.41430 (7)	0.14439 (17)	0.0382 (3)
H6A	0.4688	0.4519	0.0897	0.046*
C7	0.4642 (2)	0.35222 (7)	0.08949 (14)	0.0329 (3)
H7	0.3870	0.3474	−0.0022	0.039*
C8	0.53127 (18)	0.29565 (6)	0.17300 (13)	0.0271 (3)
C9	0.64828 (19)	0.30528 (7)	0.31067 (14)	0.0304 (3)
H9	0.6946	0.2688	0.3685	0.036*
C10	0.6930 (2)	0.36886 (8)	0.35840 (15)	0.0350 (3)
H10	0.7712	0.3755	0.4491	0.042*
H5	0.158 (3)	0.1970 (8)	0.308 (2)	0.060 (6)*
H6	0.540 (3)	0.2060 (8)	0.1754 (18)	0.053 (5)*
H11	0.204 (3)	0.1028 (11)	0.195 (3)	0.076 (7)*
H12	0.021 (3)	0.1002 (12)	0.221 (3)	0.093 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.03062 (19)	0.01762 (17)	0.02844 (18)	0.00117 (10)	−0.00024 (13)	−0.00033 (10)
O1	0.0326 (5)	0.0376 (5)	0.0431 (6)	0.0009 (4)	−0.0045 (4)	−0.0053 (4)
O2	0.0599 (7)	0.0181 (5)	0.0440 (6)	0.0024 (4)	−0.0081 (5)	−0.0031 (4)
O3	0.0371 (5)	0.0294 (5)	0.0513 (6)	0.0046 (4)	0.0123 (5)	0.0042 (4)
O4	0.0610 (7)	0.0301 (5)	0.0308 (5)	−0.0052 (5)	0.0030 (4)	0.0034 (4)
O5	0.0543 (7)	0.0295 (5)	0.0406 (6)	0.0081 (5)	0.0032 (5)	0.0031 (4)
O6	0.0479 (6)	0.0239 (5)	0.0354 (5)	−0.0011 (4)	−0.0010 (4)	−0.0020 (4)
O1W	0.0465 (7)	0.0422 (7)	0.1120 (11)	−0.0086 (6)	0.0328 (8)	−0.0245 (7)
N1	0.0367 (6)	0.0292 (6)	0.0408 (6)	0.0047 (5)	0.0086 (5)	0.0058 (5)
N2	0.0384 (7)	0.0271 (6)	0.0497 (7)	−0.0089 (5)	0.0132 (5)	−0.0081 (5)
C1	0.0324 (7)	0.0414 (8)	0.0317 (6)	0.0018 (6)	0.0045 (5)	0.0033 (5)
C2	0.0316 (7)	0.0323 (6)	0.0319 (6)	−0.0015 (5)	0.0056 (5)	−0.0045 (5)
C3	0.0282 (6)	0.0295 (6)	0.0341 (6)	0.0034 (5)	0.0085 (5)	0.0016 (5)
C4	0.0347 (7)	0.0348 (7)	0.0309 (6)	0.0027 (5)	0.0034 (5)	−0.0028 (5)
C5	0.0369 (7)	0.0305 (6)	0.0396 (7)	0.0012 (6)	0.0077 (6)	−0.0039 (6)
C6	0.0403 (8)	0.0264 (6)	0.0481 (8)	0.0004 (6)	0.0099 (6)	0.0078 (6)
C7	0.0333 (7)	0.0308 (6)	0.0321 (6)	0.0001 (5)	0.0017 (5)	0.0050 (5)
C8	0.0257 (6)	0.0246 (6)	0.0309 (6)	−0.0005 (4)	0.0060 (5)	0.0000 (5)
C9	0.0285 (6)	0.0323 (6)	0.0294 (6)	0.0011 (5)	0.0042 (5)	0.0022 (5)
C10	0.0288 (6)	0.0408 (7)	0.0350 (7)	−0.0065 (5)	0.0055 (5)	−0.0072 (6)

Geometric parameters (Å, º) top

S1—O4	1.4674 (10)	C1—C2	1.365 (2)
S1—O1	1.4656 (10)	C1—H1	0.9300
S1—O2	1.4790 (10)	C2—C3	1.4051 (18)
S1—O3	1.4845 (10)	C2—H2	0.9300
O5—C3	1.3187 (16)	C3—C4	1.4026 (19)
O5—H5	0.849 (9)	C4—C5	1.364 (2)
O6—C8	1.3175 (15)	C4—H4	0.9300
O6—H6	0.861 (9)	C5—H5A	0.9300
O1W—H11	0.844 (10)	C6—C7	1.362 (2)
O1W—H12	0.847 (10)	C6—H6A	0.9300
N1—C1	1.3419 (19)	C7—C8	1.4046 (18)
N1—C5	1.3479 (19)	C7—H7	0.9300
N1—H1N	0.8600	C8—C9	1.4054 (18)
N2—C10	1.343 (2)	C9—C10	1.3633 (19)
N2—C6	1.346 (2)	C9—H9	0.9300
N2—H2N	0.8600	C10—H10	0.9300

O4—S1—O1	110.65 (7)	C4—C3—C2	118.51 (12)
O4—S1—O2	109.43 (6)	C5—C4—C3	119.46 (12)
O1—S1—O2	109.85 (6)	C5—C4—H4	120.3
O4—S1—O3	109.21 (6)	C3—C4—H4	120.3
O1—S1—O3	109.15 (6)	N1—C5—C4	120.62 (13)
O2—S1—O3	108.53 (7)	N1—C5—H5A	119.7
C3—O5—H5	112.0 (15)	C4—C5—H5A	119.7
C8—O6—H6	109.0 (14)	N2—C6—C7	121.01 (13)
H11—O1W—H12	109 (3)	N2—C6—H6A	119.5
C1—N1—C5	121.28 (12)	C7—C6—H6A	119.5
C1—N1—H1N	119.4	C6—C7—C8	119.20 (13)
C5—N1—H1N	119.4	C6—C7—H7	120.4
C10—N2—C6	121.06 (12)	C8—C7—H7	120.4
C10—N2—H2N	119.5	O6—C8—C7	118.19 (12)
C6—N2—H2N	119.5	O6—C8—C9	123.28 (11)
N1—C1—C2	120.98 (13)	C7—C8—C9	118.52 (12)
N1—C1—H1	119.5	C10—C9—C8	119.13 (12)
C2—C1—H1	119.5	C10—C9—H9	120.4
C1—C2—C3	119.14 (12)	C8—C9—H9	120.4
C1—C2—H2	120.4	N2—C10—C9	121.07 (12)
C3—C2—H2	120.4	N2—C10—H10	119.5
O5—C3—C4	117.95 (12)	C9—C10—H10	119.5
O5—C3—C2	123.54 (12)

C5—N1—C1—C2	0.1 (2)	C10—N2—C6—C7	−0.1 (2)
N1—C1—C2—C3	−0.5 (2)	N2—C6—C7—C8	0.4 (2)
C1—C2—C3—O5	−179.30 (13)	C6—C7—C8—O6	178.62 (13)
C1—C2—C3—C4	0.1 (2)	C6—C7—C8—C9	−0.3 (2)
O5—C3—C4—C5	−179.92 (13)	O6—C8—C9—C10	−179.00 (12)
C2—C3—C4—C5	0.7 (2)	C7—C8—C9—C10	−0.1 (2)
C1—N1—C5—C4	0.7 (2)	C6—N2—C10—C9	−0.4 (2)
C3—C4—C5—N1	−1.1 (2)	C8—C9—C10—N2	0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1w	0.85 (1)	1.71 (1)	2.552 (2)	171 (2)
O6—H6···O2	0.86 (1)	1.68 (1)	2.539 (1)	177 (2)
O1w—H11···O1	0.84 (1)	1.93 (1)	2.765 (2)	170 (3)
O1w—H12···O3ⁱ	0.85 (1)	1.99 (2)	2.783 (2)	157 (3)
N1—H1n···O4ⁱⁱ	0.86	1.95	2.766 (2)	158
N2—H2n···O3ⁱⁱⁱ	0.86	1.87	2.705 (2)	163

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

Experimental details

Crystal data
Chemical formula	2C₅H₆NO⁺·SO₄²⁻·H₂O
M_r	306.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.1404 (2), 19.9797 (5), 9.5148 (2)
β (°)	102.557 (1)
V (Å³)	1324.94 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.25 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.934, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	12868, 3032, 2693
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.103, 1.05
No. of reflections	3032
No. of parameters	197
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.43

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
O5—H5···O1w	0.85 (1)	1.71 (1)	2.552 (2)	171 (2)
O6—H6···O2	0.86 (1)	1.68 (1)	2.539 (1)	177 (2)
O1w—H11···O1	0.84 (1)	1.93 (1)	2.765 (2)	170 (3)
O1w—H12···O3ⁱ	0.85 (1)	1.99 (2)	2.783 (2)	157 (3)
N1—H1n···O4ⁱⁱ	0.86	1.95	2.766 (2)	158
N2—H2n···O3ⁱⁱⁱ	0.86	1.87	2.705 (2)	163

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

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.

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