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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3147.
Published online 2009 November 21. doi:  10.1107/S1600536809048545
PMCID: PMC2972122

Tris(4-hydroxy­pyridinium) hydrogen sulfate–sulfate monohydrate

Abstract

In the crystal structure of the title salt, 3C5H6NO+·HSO4 ·SO4 2−·H2O, the hydrogen sulfate ion is linked to the sulfate ion by an O—H(...)O hydrogen bond. The hydrogen sulfate–sulfate anion is a hydrogen-bond acceptor for the three independent cations and the uncoordinated water mol­ecule, the hydrogen-bonding inter­actions giving rise to a three-dimensional hydrogen-bonded network. In the hydrogen sulfate–sulfate species, one of the sulfate groups is disordered in respect of its O atoms in a 2:1 ratio.

Related literature

For the crystal structure of bis­(4-hydroxy­pyridinium) sulfate monohydrate, see: Xu et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3147-scheme1.jpg

Experimental

Crystal data

  • 3C5H6NO+·HSO4 ·SO4 2−·H2O
  • M r = 499.47
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3147-efi1.jpg
  • a = 10.5622 (3) Å
  • b = 19.6760 (7) Å
  • c = 20.2980 (7) Å
  • V = 4218.4 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.32 mm−1
  • T = 293 K
  • 0.23 × 0.17 × 0.14 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.930, T max = 0.956
  • 38906 measured reflections
  • 4816 independent reflections
  • 3031 reflections with I > 2σ(I)
  • R int = 0.064

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.133
  • S = 1.08
  • 4816 reflections
  • 359 parameters
  • 151 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.31 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/S1600536809048545/xu2676sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048545/xu2676Isup2.hkl

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

Acknowledgments

We thank the Key Project of 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

Calcium chloride dihydrate (0.29 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 clear solution after a few days.

Refinement

One of the two independent sulfate ions is disordered over two positions. For the disorder ion, all sulfur–oxygen distances were restrained to within 0.01 Å of each other, as were the oxygen···oxygen distances. The aniosotropic temperature factors of the disordered oxygen atoms were restrained to be nearly isotropic. As the disordered refined to a 2:1 ratio, the ratio was then fixed as exactly 2:1.

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 amino and water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H = O–H = 0.85±0.01 Å; their temperature factors were refined. Additionally, for the water molecule, an H···H = 1.39 Å restrained was applied.

In the latter stages of the refinement, a hydrogen atom was located midway between one oxygen atom of the major-component sulfate ion and one oxygen atom of the ordered sulfate ion at a distance of 1.25 Å. This atom was then regarded as being 33% bonded to the first oxygen atoms and 67% bonded to the second oxygen atom. Although the two components could be refined, they were instead constrained to ride instead (O–H 0.85 Å).

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of 3[C5H6NO] [HSO4] [SO4].H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the sulfate is not shown.

Crystal data

3C5H6NO+·HSO4·SO42·H2OF(000) = 2080
Mr = 499.47Dx = 1.573 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 21088 reflections
a = 10.5622 (3) Åθ = 3.0–27.5°
b = 19.6760 (7) ŵ = 0.32 mm1
c = 20.2980 (7) ÅT = 293 K
V = 4218.4 (2) Å3Prism, colorless
Z = 80.23 × 0.17 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer4816 independent reflections
Radiation source: fine-focus sealed tube3031 reflections with I > 2σ(I)
graphiteRint = 0.064
ω scanθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −13→13
Tmin = 0.930, Tmax = 0.956k = −25→25
38906 measured reflectionsl = −26→25

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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0687P)2] where P = (Fo2 + 2Fc2)/3
4816 reflections(Δ/σ)max = 0.001
359 parametersΔρmax = 0.36 e Å3
151 restraintsΔρmin = −0.31 e Å3

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

xyzUiso*/UeqOcc. (<1)
S10.47437 (6)0.72762 (4)0.42526 (3)0.0411 (2)
S20.70661 (6)0.53636 (3)0.42933 (3)0.03703 (19)
O10.3908 (3)0.77692 (16)0.45160 (13)0.0526 (8)0.67
O20.4603 (3)0.66376 (14)0.46657 (13)0.0534 (7)0.67
H2O0.48990.63000.44550.080*0.33
O30.6093 (2)0.74804 (17)0.43084 (14)0.0526 (7)0.67
O40.4463 (6)0.7087 (3)0.35765 (17)0.057 (2)0.67
O1'0.4860 (6)0.7986 (2)0.4441 (3)0.0619 (17)0.33
O2'0.3670 (5)0.6974 (3)0.4642 (3)0.0687 (18)0.33
O3'0.5908 (4)0.6914 (3)0.4441 (3)0.0594 (16)0.33
O4'0.4480 (10)0.7201 (6)0.3559 (3)0.050 (4)0.33
O50.79101 (16)0.57990 (11)0.46790 (8)0.0564 (5)
O60.57405 (16)0.55782 (10)0.43845 (10)0.0520 (5)
H6O0.57160.60020.44640.078*0.67
O70.71622 (18)0.46548 (9)0.45195 (9)0.0516 (5)
O80.73894 (17)0.53979 (11)0.35927 (8)0.0557 (5)
O90.61528 (17)0.78290 (11)0.76401 (9)0.0525 (5)
O100.5361 (2)0.61193 (12)0.77445 (10)0.0622 (6)
O110.92913 (18)0.45490 (11)0.76645 (9)0.0516 (5)
O1W0.8138 (3)0.36629 (14)0.37081 (11)0.0745 (7)
N10.4461 (2)0.79165 (14)0.58566 (11)0.0523 (6)
N20.6911 (2)0.60986 (12)0.59204 (11)0.0477 (6)
N30.7757 (2)0.44865 (13)0.58375 (11)0.0486 (6)
C10.3737 (3)0.79553 (16)0.63918 (13)0.0526 (7)
H10.28660.80060.63460.063*
C20.4252 (2)0.79225 (14)0.70003 (12)0.0442 (6)
H20.37400.79430.73720.053*
C30.5562 (2)0.78579 (13)0.70632 (11)0.0377 (6)
C40.6297 (2)0.78230 (13)0.64949 (12)0.0406 (6)
H40.71730.77820.65240.049*
C50.5724 (3)0.78489 (14)0.58982 (12)0.0466 (7)
H50.62070.78200.55160.056*
C60.5672 (3)0.59812 (15)0.60013 (14)0.0514 (7)
H60.51660.58920.56360.062*
C70.5147 (2)0.59914 (15)0.66110 (13)0.0512 (7)
H70.42850.59120.66630.061*
C80.5901 (2)0.61199 (14)0.71564 (12)0.0434 (6)
C90.7191 (2)0.62398 (14)0.70587 (13)0.0449 (6)
H90.77180.63290.74150.054*
C100.7664 (3)0.62247 (14)0.64387 (13)0.0461 (7)
H100.85220.63030.63710.055*
C110.6988 (2)0.44270 (14)0.63582 (13)0.0466 (7)
H110.61230.43730.62930.056*
C120.7455 (2)0.44448 (13)0.69802 (12)0.0402 (6)
H120.69150.44010.73390.048*
C130.8755 (2)0.45294 (13)0.70767 (11)0.0367 (6)
C140.9534 (2)0.45910 (14)0.65243 (12)0.0447 (6)
H141.04030.46470.65740.054*
C150.9007 (3)0.45679 (15)0.59115 (13)0.0489 (7)
H150.95210.46090.55420.059*
H1N0.415 (3)0.7950 (17)0.5474 (8)0.082 (11)*
H2N0.721 (3)0.6063 (15)0.5534 (7)0.062 (9)*
H3N0.747 (3)0.4507 (18)0.5449 (8)0.088 (12)*
H1W0.789 (3)0.3988 (12)0.3951 (14)0.093 (13)*
H2W0.848 (4)0.3357 (14)0.3939 (15)0.115 (17)*
H9O0.556 (2)0.7852 (18)0.7929 (14)0.089 (13)*
H10O0.592 (2)0.6200 (17)0.8044 (12)0.076 (12)*
H11O0.869 (2)0.4553 (18)0.7952 (13)0.087 (12)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0440 (4)0.0531 (4)0.0263 (3)0.0036 (3)−0.0035 (3)−0.0001 (3)
S20.0342 (3)0.0518 (4)0.0250 (3)−0.0001 (3)−0.0003 (2)0.0013 (3)
O10.0608 (19)0.063 (2)0.0335 (14)0.0284 (16)−0.0029 (14)−0.0034 (14)
O20.0640 (19)0.0522 (19)0.0440 (16)0.0061 (16)0.0156 (14)0.0115 (13)
O30.0423 (15)0.063 (2)0.0523 (17)−0.0059 (15)−0.0035 (13)0.0008 (15)
O40.059 (4)0.085 (4)0.028 (3)−0.009 (3)−0.003 (3)−0.006 (2)
O1'0.086 (5)0.048 (4)0.052 (3)0.000 (3)−0.018 (3)−0.006 (3)
O2'0.054 (4)0.107 (5)0.045 (3)−0.016 (4)0.010 (3)0.005 (3)
O3'0.043 (3)0.067 (4)0.068 (4)0.016 (3)−0.017 (3)−0.005 (3)
O4'0.038 (6)0.088 (7)0.023 (6)0.007 (5)−0.001 (5)−0.007 (5)
O50.0520 (11)0.0785 (15)0.0388 (10)−0.0227 (10)−0.0029 (8)−0.0068 (10)
O60.0376 (10)0.0588 (13)0.0597 (12)0.0082 (9)0.0023 (9)−0.0031 (10)
O70.0676 (12)0.0504 (12)0.0368 (10)0.0132 (9)−0.0048 (9)0.0025 (8)
O80.0460 (10)0.0943 (16)0.0268 (9)−0.0045 (10)0.0017 (8)0.0067 (9)
O90.0397 (10)0.0872 (16)0.0306 (10)0.0037 (10)−0.0050 (8)0.0019 (9)
O100.0547 (13)0.0897 (17)0.0422 (11)−0.0062 (12)0.0121 (10)−0.0051 (11)
O110.0415 (10)0.0806 (15)0.0326 (10)−0.0052 (10)−0.0041 (8)−0.0032 (9)
O1W0.1018 (19)0.0718 (18)0.0498 (13)0.0291 (15)0.0102 (13)−0.0019 (12)
N10.0538 (14)0.0726 (18)0.0306 (12)0.0034 (13)−0.0085 (10)0.0002 (11)
N20.0551 (15)0.0519 (15)0.0361 (12)−0.0027 (11)0.0071 (11)0.0024 (11)
N30.0600 (15)0.0511 (15)0.0346 (12)0.0046 (12)−0.0121 (11)0.0001 (10)
C10.0375 (14)0.076 (2)0.0438 (15)0.0026 (14)−0.0051 (12)0.0008 (14)
C20.0378 (14)0.0608 (18)0.0339 (13)0.0014 (12)0.0016 (11)−0.0008 (12)
C30.0383 (13)0.0455 (16)0.0292 (12)0.0000 (11)−0.0035 (10)0.0012 (10)
C40.0366 (13)0.0484 (16)0.0369 (13)0.0025 (11)0.0035 (11)−0.0019 (11)
C50.0537 (16)0.0541 (18)0.0320 (13)0.0028 (13)0.0066 (12)−0.0020 (11)
C60.0482 (16)0.0606 (19)0.0453 (15)−0.0073 (14)−0.0031 (13)−0.0012 (14)
C70.0413 (14)0.064 (2)0.0479 (16)−0.0049 (14)0.0012 (12)−0.0013 (14)
C80.0452 (15)0.0466 (16)0.0384 (14)0.0018 (12)0.0048 (11)0.0001 (12)
C90.0407 (14)0.0531 (18)0.0409 (14)−0.0012 (12)−0.0039 (11)0.0020 (12)
C100.0414 (14)0.0493 (17)0.0476 (16)−0.0043 (12)0.0027 (12)0.0052 (12)
C110.0386 (14)0.0513 (18)0.0498 (16)0.0022 (12)−0.0077 (12)−0.0040 (13)
C120.0356 (13)0.0473 (16)0.0378 (13)−0.0021 (11)0.0023 (11)−0.0016 (12)
C130.0367 (13)0.0413 (15)0.0321 (12)−0.0008 (11)−0.0009 (10)−0.0014 (10)
C140.0375 (13)0.0581 (18)0.0386 (14)−0.0031 (12)0.0006 (11)0.0020 (12)
C150.0572 (18)0.0556 (18)0.0340 (13)−0.0003 (14)0.0066 (12)0.0031 (12)

Geometric parameters (Å, °)

S1—O11.416 (2)N3—C111.338 (3)
S1—O4'1.444 (5)N3—C151.339 (4)
S1—O41.452 (3)N3—H3N0.847 (11)
S1—O1'1.453 (4)C1—C21.351 (3)
S1—O3'1.473 (4)C1—H10.9300
S1—O31.485 (2)C2—C31.396 (3)
S1—O2'1.505 (4)C2—H20.9300
S1—O21.518 (3)C3—C41.392 (3)
S2—O51.4633 (18)C4—C51.355 (3)
S2—O81.4641 (17)C4—H40.9300
S2—O71.4717 (19)C5—H50.9300
S2—O61.4740 (18)C6—C71.356 (4)
O2—H2O0.8501C6—H60.9300
O6—H6O0.8501C7—C81.386 (3)
O9—C31.328 (3)C7—H70.9300
O9—H9O0.860 (11)C8—C91.397 (3)
O10—C81.323 (3)C9—C101.355 (3)
O10—H10O0.862 (11)C9—H90.9300
O11—C131.321 (3)C10—H100.9300
O11—H11O0.863 (11)C11—C121.356 (3)
O1W—H1W0.847 (11)C11—H110.9300
O1W—H2W0.844 (11)C12—C131.397 (3)
N1—C11.330 (3)C12—H120.9300
N1—C51.343 (4)C13—C141.396 (3)
N1—H1N0.846 (11)C14—C151.363 (3)
N2—C61.339 (3)C14—H140.9300
N2—C101.342 (3)C15—H150.9300
N2—H2N0.848 (11)
O4'—S1—O1'111.8 (5)O9—C3—C4117.8 (2)
O4—S1—O1'120.8 (4)O9—C3—C2123.4 (2)
O4'—S1—O3'111.4 (4)C4—C3—C2118.8 (2)
O1'—S1—O3'109.1 (3)C5—C4—C3119.3 (2)
O1—S1—O3112.58 (19)C5—C4—H4120.3
O4—S1—O3109.7 (3)C3—C4—H4120.3
O4'—S1—O2'109.1 (4)N1—C5—C4120.2 (2)
O1'—S1—O2'107.8 (3)N1—C5—H5119.9
O3'—S1—O2'107.5 (3)C4—C5—H5119.9
O1—S1—O2107.29 (17)N2—C6—C7120.6 (3)
O4—S1—O2106.8 (3)N2—C6—H6119.7
O3—S1—O2106.03 (17)C7—C6—H6119.7
O5—S2—O8110.52 (11)C6—C7—C8119.8 (2)
O5—S2—O7110.23 (12)C6—C7—H7120.1
O8—S2—O7109.31 (12)C8—C7—H7120.1
O5—S2—O6110.11 (12)O10—C8—C7118.2 (2)
O8—S2—O6109.29 (11)O10—C8—C9123.3 (2)
O7—S2—O6107.32 (11)C7—C8—C9118.5 (2)
S1—O2—H2O109.5C10—C9—C8119.2 (2)
S2—O6—H6O109.5C10—C9—H9120.4
C3—O9—H9O105 (2)C8—C9—H9120.4
C8—O10—H10O110 (2)N2—C10—C9120.9 (3)
C13—O11—H11O107 (2)N2—C10—H10119.5
H1w—O1w—H2W110.3 (18)C9—C10—H10119.5
C1—N1—C5121.7 (2)N3—C11—C12120.9 (2)
C1—N1—H1N122 (2)N3—C11—H11119.6
C5—N1—H1N117 (2)C12—C11—H11119.6
C6—N2—C10121.0 (2)C11—C12—C13119.4 (2)
C6—N2—H2N118 (2)C11—C12—H12120.3
C10—N2—H2N121 (2)C13—C12—H12120.3
C11—N3—C15121.3 (2)O11—C13—C14118.1 (2)
C11—N3—H3N121 (2)O11—C13—C12123.5 (2)
C15—N3—H3N117 (2)C14—C13—C12118.5 (2)
N1—C1—C2120.9 (2)C15—C14—C13119.3 (2)
N1—C1—H1119.6C15—C14—H14120.3
C2—C1—H1119.6C13—C14—H14120.3
C1—C2—C3119.1 (2)N3—C15—C14120.6 (2)
C1—C2—H2120.4N3—C15—H15119.7
C3—C2—H2120.4C14—C15—H15119.7
C5—N1—C1—C2−0.5 (5)O10—C8—C9—C10179.4 (3)
N1—C1—C2—C31.0 (4)C7—C8—C9—C10−0.2 (4)
C1—C2—C3—O9179.3 (3)C6—N2—C10—C9−0.3 (4)
C1—C2—C3—C4−0.6 (4)C8—C9—C10—N20.2 (4)
O9—C3—C4—C5179.8 (2)C15—N3—C11—C12−0.3 (4)
C2—C3—C4—C5−0.3 (4)N3—C11—C12—C130.3 (4)
C1—N1—C5—C4−0.5 (4)C11—C12—C13—O11−179.6 (3)
C3—C4—C5—N10.9 (4)C11—C12—C13—C14−0.2 (4)
C10—N2—C6—C70.4 (4)O11—C13—C14—C15179.6 (2)
N2—C6—C7—C8−0.4 (5)C12—C13—C14—C150.1 (4)
C6—C7—C8—O10−179.3 (3)C11—N3—C15—C140.2 (4)
C6—C7—C8—C90.4 (4)C13—C14—C15—N3−0.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2o···O60.851.682.473 (3)154
O6—H6o···O20.851.762.473 (3)139
O9—H9o···O4i0.86 (1)1.76 (1)2.612 (6)174 (4)
O9—H9o···O4'i0.86 (1)1.72 (2)2.569 (9)172 (4)
O10—H10o···O1wii0.86 (1)1.70 (1)2.554 (3)172 (3)
O11—H11o···O8ii0.86 (1)1.73 (1)2.591 (3)173 (4)
O1w—H1w···O70.85 (1)1.91 (1)2.754 (3)173 (4)
O1w—H2w···O3iii0.84 (1)1.93 (2)2.749 (4)162 (4)
N1—H1n···O10.85 (1)1.99 (2)2.798 (3)159 (3)
N1—H1n···O1'0.85 (1)2.23 (3)2.907 (6)138 (3)
N2—H2n···O50.85 (1)1.96 (1)2.795 (3)169 (3)
N3—H3n···O70.85 (1)1.94 (1)2.768 (3)167 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2676).

References

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  • Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
  • Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.
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