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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3146.
Published online 2009 November 21. doi:  10.1107/S1600536809048521
PMCID: PMC2971874

Bis(4-hydroxy­pyridinium) sulfate monohydrate

Abstract

In the crystal structure of the title salt, 2C5H6NO+·SO4 2−·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 [triangle]); Gao et al. (2004 [triangle]); Kiviniemi et al. (2001 [triangle]); Wang et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3146-scheme1.jpg

Experimental

Crystal data

  • 2C5H6NO+·SO4 2−·H2O
  • M r = 306.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3146-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

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.

supplementary crystallographic information

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H = 0.85±0.01 Å; their temperature factors were refined. The pyridinium H-atoms could be found in a difference Fourier map; however, their refinement led to somewhat unsatisfactory angles. As such, their positions were fixed and their temperatures tied to those of the parent atoms.

Figures

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.

Crystal data

2C5H6NO+·SO42·H2OF(000) = 640
Mr = 306.29Dx = 1.535 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 11052 reflections
a = 7.1404 (2) Åθ = 3.0–27.4°
b = 19.9797 (5) ŵ = 0.28 mm1
c = 9.5148 (2) ÅT = 293 K
β = 102.557 (1)°Prism, colorless
V = 1324.94 (6) Å30.25 × 0.18 × 0.16 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer3032 independent reflections
Radiation source: fine-focus sealed tube2693 reflections with I > 2σ(I)
graphiteRint = 0.020
ω scanθmax = 27.4°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −9→9
Tmin = 0.934, Tmax = 0.957k = −25→25
12868 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0703P)2 + 0.2237P] where P = (Fo2 + 2Fc2)/3
3032 reflections(Δ/σ)max = 0.001
197 parametersΔρmax = 0.42 e Å3
6 restraintsΔρmin = −0.43 e Å3

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

xyzUiso*/Ueq
S10.61983 (4)0.073598 (14)0.24878 (3)0.02657 (12)
O10.43221 (15)0.06385 (5)0.15168 (11)0.0397 (3)
O20.64861 (17)0.14531 (5)0.28579 (12)0.0436 (3)
O30.77259 (15)0.05185 (5)0.17503 (12)0.0388 (2)
O40.63392 (17)0.03440 (5)0.38109 (10)0.0417 (3)
O50.20084 (17)0.22956 (5)0.36294 (12)0.0425 (3)
O60.47857 (16)0.23613 (5)0.11899 (11)0.0373 (2)
O1W0.1093 (2)0.12590 (7)0.2064 (2)0.0645 (4)
N10.04132 (18)0.41179 (6)0.18890 (13)0.0356 (3)
H1N0.00880.45070.15320.043*
N20.62608 (18)0.42205 (6)0.27653 (15)0.0379 (3)
H2N0.65560.46170.30910.045*
C1−0.0033 (2)0.35736 (7)0.10572 (15)0.0355 (3)
H1−0.06860.36230.01050.043*
C20.0458 (2)0.29479 (7)0.15884 (14)0.0321 (3)
H20.01350.25730.10060.039*
C30.14570 (19)0.28776 (7)0.30255 (14)0.0304 (3)
C40.1913 (2)0.34564 (7)0.38645 (14)0.0340 (3)
H40.25850.34240.48160.041*
C50.1361 (2)0.40666 (7)0.32736 (16)0.0358 (3)
H5A0.16430.44510.38310.043*
C60.5135 (2)0.41430 (7)0.14439 (17)0.0382 (3)
H6A0.46880.45190.08970.046*
C70.4642 (2)0.35222 (7)0.08949 (14)0.0329 (3)
H70.38700.3474−0.00220.039*
C80.53127 (18)0.29565 (6)0.17300 (13)0.0271 (3)
C90.64828 (19)0.30528 (7)0.31067 (14)0.0304 (3)
H90.69460.26880.36850.036*
C100.6930 (2)0.36886 (8)0.35840 (15)0.0350 (3)
H100.77120.37550.44910.042*
H50.158 (3)0.1970 (8)0.308 (2)0.060 (6)*
H60.540 (3)0.2060 (8)0.1754 (18)0.053 (5)*
H110.204 (3)0.1028 (11)0.195 (3)0.076 (7)*
H120.021 (3)0.1002 (12)0.221 (3)0.093 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.03062 (19)0.01762 (17)0.02844 (18)0.00117 (10)−0.00024 (13)−0.00033 (10)
O10.0326 (5)0.0376 (5)0.0431 (6)0.0009 (4)−0.0045 (4)−0.0053 (4)
O20.0599 (7)0.0181 (5)0.0440 (6)0.0024 (4)−0.0081 (5)−0.0031 (4)
O30.0371 (5)0.0294 (5)0.0513 (6)0.0046 (4)0.0123 (5)0.0042 (4)
O40.0610 (7)0.0301 (5)0.0308 (5)−0.0052 (5)0.0030 (4)0.0034 (4)
O50.0543 (7)0.0295 (5)0.0406 (6)0.0081 (5)0.0032 (5)0.0031 (4)
O60.0479 (6)0.0239 (5)0.0354 (5)−0.0011 (4)−0.0010 (4)−0.0020 (4)
O1W0.0465 (7)0.0422 (7)0.1120 (11)−0.0086 (6)0.0328 (8)−0.0245 (7)
N10.0367 (6)0.0292 (6)0.0408 (6)0.0047 (5)0.0086 (5)0.0058 (5)
N20.0384 (7)0.0271 (6)0.0497 (7)−0.0089 (5)0.0132 (5)−0.0081 (5)
C10.0324 (7)0.0414 (8)0.0317 (6)0.0018 (6)0.0045 (5)0.0033 (5)
C20.0316 (7)0.0323 (6)0.0319 (6)−0.0015 (5)0.0056 (5)−0.0045 (5)
C30.0282 (6)0.0295 (6)0.0341 (6)0.0034 (5)0.0085 (5)0.0016 (5)
C40.0347 (7)0.0348 (7)0.0309 (6)0.0027 (5)0.0034 (5)−0.0028 (5)
C50.0369 (7)0.0305 (6)0.0396 (7)0.0012 (6)0.0077 (6)−0.0039 (6)
C60.0403 (8)0.0264 (6)0.0481 (8)0.0004 (6)0.0099 (6)0.0078 (6)
C70.0333 (7)0.0308 (6)0.0321 (6)0.0001 (5)0.0017 (5)0.0050 (5)
C80.0257 (6)0.0246 (6)0.0309 (6)−0.0005 (4)0.0060 (5)0.0000 (5)
C90.0285 (6)0.0323 (6)0.0294 (6)0.0011 (5)0.0042 (5)0.0022 (5)
C100.0288 (6)0.0408 (7)0.0350 (7)−0.0065 (5)0.0055 (5)−0.0072 (6)

Geometric parameters (Å, °)

S1—O41.4674 (10)C1—C21.365 (2)
S1—O11.4656 (10)C1—H10.9300
S1—O21.4790 (10)C2—C31.4051 (18)
S1—O31.4845 (10)C2—H20.9300
O5—C31.3187 (16)C3—C41.4026 (19)
O5—H50.849 (9)C4—C51.364 (2)
O6—C81.3175 (15)C4—H40.9300
O6—H60.861 (9)C5—H5A0.9300
O1W—H110.844 (10)C6—C71.362 (2)
O1W—H120.847 (10)C6—H6A0.9300
N1—C11.3419 (19)C7—C81.4046 (18)
N1—C51.3479 (19)C7—H70.9300
N1—H1N0.8600C8—C91.4054 (18)
N2—C101.343 (2)C9—C101.3633 (19)
N2—C61.346 (2)C9—H90.9300
N2—H2N0.8600C10—H100.9300
O4—S1—O1110.65 (7)C4—C3—C2118.51 (12)
O4—S1—O2109.43 (6)C5—C4—C3119.46 (12)
O1—S1—O2109.85 (6)C5—C4—H4120.3
O4—S1—O3109.21 (6)C3—C4—H4120.3
O1—S1—O3109.15 (6)N1—C5—C4120.62 (13)
O2—S1—O3108.53 (7)N1—C5—H5A119.7
C3—O5—H5112.0 (15)C4—C5—H5A119.7
C8—O6—H6109.0 (14)N2—C6—C7121.01 (13)
H11—O1W—H12109 (3)N2—C6—H6A119.5
C1—N1—C5121.28 (12)C7—C6—H6A119.5
C1—N1—H1N119.4C6—C7—C8119.20 (13)
C5—N1—H1N119.4C6—C7—H7120.4
C10—N2—C6121.06 (12)C8—C7—H7120.4
C10—N2—H2N119.5O6—C8—C7118.19 (12)
C6—N2—H2N119.5O6—C8—C9123.28 (11)
N1—C1—C2120.98 (13)C7—C8—C9118.52 (12)
N1—C1—H1119.5C10—C9—C8119.13 (12)
C2—C1—H1119.5C10—C9—H9120.4
C1—C2—C3119.14 (12)C8—C9—H9120.4
C1—C2—H2120.4N2—C10—C9121.07 (12)
C3—C2—H2120.4N2—C10—H10119.5
O5—C3—C4117.95 (12)C9—C10—H10119.5
O5—C3—C2123.54 (12)
C5—N1—C1—C20.1 (2)C10—N2—C6—C7−0.1 (2)
N1—C1—C2—C3−0.5 (2)N2—C6—C7—C80.4 (2)
C1—C2—C3—O5−179.30 (13)C6—C7—C8—O6178.62 (13)
C1—C2—C3—C40.1 (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—C50.7 (2)C7—C8—C9—C10−0.1 (2)
C1—N1—C5—C40.7 (2)C6—N2—C10—C9−0.4 (2)
C3—C4—C5—N1−1.1 (2)C8—C9—C10—N20.5 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5···O1w0.85 (1)1.71 (1)2.552 (2)171 (2)
O6—H6···O20.86 (1)1.68 (1)2.539 (1)177 (2)
O1w—H11···O10.84 (1)1.93 (1)2.765 (2)170 (3)
O1w—H12···O3i0.85 (1)1.99 (2)2.783 (2)157 (3)
N1—H1n···O4ii0.861.952.766 (2)158
N2—H2n···O3iii0.861.872.705 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2675).

References

  • Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
  • Fukunaga, T., Kashino, S. & Ishida, H. (2004). Acta Cryst. C60, o718–o722. [PubMed]
  • Gao, S., Lu, Z.-Z., Huo, L.-H., Zain, S. M. & Ng, S. W. (2004). Acta Cryst. E60, o2195–o2196.
  • Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
  • Kiviniemi, S., Nissinen, M., Kolli, T., Jalonen, J., Rissanen, K. & Pursiainen, J. (2001). J. Inclusion Phenom. Macrocycl. Chem. 40, 153–159.
  • Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, Y., Tang, L. & Wang, Y. (2006). Chem. Lett. pp. 548–549.
  • Westrip, S. P. (2009). publCIF. In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography