Bis(4-hydroxy-pyridinium) sulfate monohydrate.

In the crystal structure of the title salt, 2C(5)H(6)NO(+)·SO(4) (2-)·H(2)O, 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 hydr-oxy H atoms are hydrogen-bond donor atoms to the O atoms of the sulfate anion; the cations, anions and water mol-ecules 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+·SO4 2−·H2O

M = 306.29

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.103

S = 1.05

3032 reflections

197 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.43 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048521/xu2675sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C5H6NO+·SO42−·H2O	F(000) = 640
Mr = 306.29	Dx = 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

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

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(Fo2) + (0.0703P)2 + 0.2237P] where P = (Fo2 + 2Fc2)/3
3032 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.42 e Å−3
6 restraints	Δρmin = −0.43 e Å−3

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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

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) ; (ii) ; (iii) .