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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1289.
Published online 2008 June 19. doi:  10.1107/S1600536808017777
PMCID: PMC2961784

Pyrazine­diium bis­(3-carb­oxy-4-hydroxy­benzene­sulfonate) dihydrate

Abstract

Pyrazine and 5-sulfosalicylic acid crystallize from a methanol solution containing water as the title salt, C4H6N2 2+·2C7H5O6S·2H2O. The pyrazine­diium cation sits on an inversion center. The component ions and water mol­ecules are linked by inter­molecular O—H(...)O, N—H(...)O and C—H(...)O hydrogen bonds into layers running parallel to the (10An external file that holds a picture, illustration, etc.
Object name is e-64-o1289-efi1.jpg) plane.

Related literature

For related literature, see: Smith et al. (2004 [triangle], 2005 [triangle]); Meng et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1289-scheme1.jpg

Experimental

Crystal data

  • C4H6N2 2+·2C7H5O6S·2H2O
  • M r = 552.48
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1289-efi3.jpg
  • a = 6.7887 (5) Å
  • b = 6.9256 (6) Å
  • c = 13.0349 (10) Å
  • α = 100.663 (7)°
  • β = 97.761 (9)°
  • γ = 107.735 (9)°
  • V = 561.52 (9) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.32 mm−1
  • T = 298 (2) K
  • 0.20 × 0.10 × 0.08 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1997 [triangle]) T min = 0.929, T max = 0.975
  • 5286 measured reflections
  • 2412 independent reflections
  • 1977 reflections with I > 2σ(I)
  • R int = 0.064

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.131
  • S = 1.08
  • 2412 reflections
  • 178 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2001 [triangle]; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017777/cs2079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017777/cs2079Isup2.hkl

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

Acknowledgments

The authors thank the Ningbo Natural Science Fund (No. 2006 A610075) for financial support of this work.

supplementary crystallographic information

Comment

5-sulfosalicylic acid is strong organic acid (pKa = 2.85) which can release its sulfonic acid H to Lewis base N atoms, forming 1:1 molecular adducts in general (Smith et al., 2004 and 2005). In order to gain more insight into these analogues, we have recently prepared an organic salt containing 5-H2SSA, whose crystal structure is reported here.

There are a half of a pyrazinediium cation, one each a 5-HSSA- anion and a water molecule in the asymmetric unit. Similarly to analogous organic adducts reported by others (Meng et al., 2008), the H atom is transferred from the sulfonic acid group to the pyrazine N atoms (Fig.1). Except for this, the other bond lengths and angles are usual.

By a combination of seven intermolecular hydrogen bonds (Table 1), these components are linked into a two-dimensional layers (Fig.2) running parallel to the (102) plane in the crystal.

Program PLATON (Spek, 2003) reports two distances indicating possible aromatic π-π stacking interactions between symmetry-center related benzene rings comprising atoms C1 to C6 in this crystal. Centroid distances between the closest symmetry-related benzene rings are 3.848 (2) and 4.239 (2) Å, respectively (symmetry codes: 1-x,1 -y, 1-z for the former one and 1-x, 2-y, 1-z for the latter one).

Experimental

All the reagents and solvents were used as obtained without further purification. Equimolar amount of pyrazine (0.2 mmol, 16.0 mg) and 5-sulfosalicylic acid dihydrate (0.2 mmol, 50.8 g) were dissolved in 95% methanol (10 ml). The mixture was stirred for ten minutes at ambient temperature and then filtered. The resulting colorless solution was kept in air for two weeks. Plate shaped colorless crystals suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solvent.

Refinement

H atoms bonded to C atoms were positioned geometrically with C–H = 0.93Å (aromatic) and refined in a riding mode [Uiso(H) = 1.2Ueq(aromatic C)]. H atoms bonded to N and O atoms were found in difference Fourier maps with N—H and O—H distances being refined freely [the refined distances are given in Table 1; Uiso(H)= 1.2Ueq(N) or 1.5Ueq(O)].

Figures

Fig. 1.
Molecular structure of the title salt showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H-bonds are shown in dashed lines. Symmetry code: (A) 2 - x, 1 - y, 2 - z.
Fig. 2.
Excerpt from the crystal structure showing the formation of the two-dimensional layers running parallel to the [102] direction. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted from ...

Crystal data

C4H6N22+·2C7H5O6S·2H2OZ = 1
Mr = 552.48F000 = 286
Triclinic, P1Dx = 1.634 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.7887 (5) ÅCell parameters from 2269 reflections
b = 6.9256 (6) Åθ = 1.6–25.2º
c = 13.0349 (10) ŵ = 0.32 mm1
α = 100.663 (7)ºT = 298 (2) K
β = 97.761 (9)ºPlate, colourless
γ = 107.735 (9)º0.20 × 0.10 × 0.08 mm
V = 561.52 (9) Å3

Data collection

Bruker SMART APEX CCD area-detector diffractometer2412 independent reflections
Radiation source: fine focus sealed Siemens Mo tube1977 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.064
T = 298(2) Kθmax = 27.0º
0.3° wide ω exposures scansθmin = 1.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1997)h = −8→8
Tmin = 0.929, Tmax = 0.975k = −5→8
5286 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131  w = 1/[σ2(Fo2) + (0.0732P)2 + 0.0236P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2412 reflectionsΔρmax = 0.32 e Å3
178 parametersΔρmin = −0.51 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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

xyzUiso*/Ueq
C10.4240 (3)0.7285 (3)0.48381 (14)0.0311 (4)
C20.6433 (3)0.7939 (3)0.48820 (17)0.0361 (5)
C30.7816 (3)0.8439 (3)0.58633 (18)0.0439 (5)
H30.92650.88510.58950.053*
C40.7052 (3)0.8328 (3)0.67817 (17)0.0425 (5)
H40.79850.86710.74320.051*
C50.4881 (3)0.7704 (3)0.67421 (15)0.0338 (4)
C60.3486 (3)0.7183 (3)0.57800 (14)0.0323 (4)
H60.20400.67620.57580.039*
C70.2761 (3)0.6708 (3)0.38006 (15)0.0362 (5)
C80.9086 (4)0.6243 (4)0.96127 (19)0.0543 (6)
H80.84590.71190.93460.065*
C90.8819 (4)0.3018 (4)0.99291 (18)0.0511 (6)
H90.80120.16410.98840.061*
N10.7935 (3)0.4275 (3)0.95466 (13)0.0466 (5)
H1B0.658 (4)0.377 (4)0.928 (2)0.056*
O10.0776 (2)0.6158 (3)0.38832 (11)0.0484 (4)
H1A−0.005 (5)0.578 (5)0.331 (2)0.073*
O20.3328 (3)0.6740 (3)0.29528 (11)0.0531 (4)
O30.7255 (3)0.8128 (3)0.40112 (14)0.0523 (4)
H3A0.633 (5)0.788 (5)0.348 (3)0.078*
O40.2517 (3)0.8910 (3)0.79365 (12)0.0535 (4)
O50.2546 (2)0.5428 (2)0.78053 (11)0.0467 (4)
O60.5615 (3)0.8329 (3)0.88036 (11)0.0522 (4)
O70.3909 (3)0.2940 (3)0.88232 (12)0.0475 (4)
H7A0.346 (5)0.362 (5)0.844 (2)0.071*
H7B0.340 (5)0.169 (5)0.849 (2)0.071*
S10.38501 (8)0.76139 (8)0.79128 (3)0.0378 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0308 (9)0.0259 (10)0.0391 (9)0.0108 (8)0.0074 (8)0.0115 (8)
C20.0321 (10)0.0272 (10)0.0533 (11)0.0111 (8)0.0152 (8)0.0130 (9)
C30.0247 (10)0.0414 (12)0.0655 (13)0.0105 (9)0.0075 (9)0.0150 (10)
C40.0325 (10)0.0412 (12)0.0495 (11)0.0106 (9)−0.0022 (9)0.0113 (9)
C50.0319 (10)0.0293 (10)0.0391 (9)0.0103 (8)0.0030 (8)0.0090 (8)
C60.0265 (9)0.0316 (11)0.0391 (9)0.0101 (8)0.0044 (7)0.0103 (8)
C70.0369 (11)0.0349 (11)0.0396 (10)0.0125 (9)0.0085 (8)0.0145 (8)
C80.0648 (16)0.0550 (16)0.0518 (13)0.0315 (13)0.0084 (11)0.0173 (11)
C90.0617 (15)0.0454 (14)0.0481 (12)0.0214 (12)0.0105 (11)0.0113 (10)
N10.0443 (10)0.0565 (13)0.0383 (9)0.0203 (10)0.0045 (8)0.0073 (9)
O10.0322 (8)0.0695 (12)0.0376 (7)0.0083 (8)0.0005 (6)0.0184 (7)
O20.0521 (9)0.0701 (12)0.0390 (8)0.0189 (9)0.0136 (7)0.0176 (7)
O30.0404 (9)0.0604 (11)0.0606 (10)0.0151 (8)0.0235 (7)0.0190 (8)
O40.0572 (10)0.0634 (11)0.0488 (8)0.0343 (9)0.0092 (7)0.0126 (7)
O50.0447 (9)0.0477 (10)0.0400 (7)0.0053 (7)0.0014 (6)0.0148 (7)
O60.0515 (9)0.0557 (10)0.0383 (7)0.0133 (8)−0.0093 (7)0.0064 (7)
O70.0571 (10)0.0444 (10)0.0467 (8)0.0238 (8)0.0082 (7)0.0152 (7)
S10.0369 (3)0.0405 (3)0.0328 (3)0.0128 (2)−0.0006 (2)0.0074 (2)

Geometric parameters (Å, °)

C1—C61.398 (3)C8—N11.329 (3)
C1—C21.408 (3)C8—C9i1.363 (4)
C1—C71.478 (2)C8—H80.9300
C2—O31.341 (3)C9—N11.329 (3)
C2—C31.397 (3)C9—C8i1.363 (4)
C3—C41.373 (3)C9—H90.9300
C3—H30.9300N1—H1B0.87 (3)
C4—C51.395 (3)O1—H1A0.82 (3)
C4—H40.9300O3—H3A0.83 (3)
C5—C61.380 (2)O4—S11.4556 (17)
C5—S11.766 (2)O5—S11.4721 (15)
C6—H60.9300O6—S11.4421 (14)
C7—O21.220 (2)O7—H7A0.83 (3)
C7—O11.310 (2)O7—H7B0.83 (3)
C6—C1—C2119.40 (17)O1—C7—C1113.11 (16)
C6—C1—C7120.76 (17)N1—C8—C9i120.2 (2)
C2—C1—C7119.84 (17)N1—C8—H8119.9
O3—C2—C3118.37 (18)C9i—C8—H8119.9
O3—C2—C1122.21 (19)N1—C9—C8i119.6 (2)
C3—C2—C1119.41 (18)N1—C9—H9120.2
C4—C3—C2120.51 (19)C8i—C9—H9120.2
C4—C3—H3119.7C8—N1—C9120.2 (2)
C2—C3—H3119.7C8—N1—H1B122.3 (17)
C3—C4—C5120.19 (19)C9—N1—H1B117.4 (18)
C3—C4—H4119.9C7—O1—H1A113 (2)
C5—C4—H4119.9C2—O3—H3A111 (2)
C6—C5—C4120.25 (18)H7A—O7—H7B107 (3)
C6—C5—S1118.43 (15)O6—S1—O4114.02 (10)
C4—C5—S1121.30 (15)O6—S1—O5111.78 (9)
C5—C6—C1120.23 (17)O4—S1—O5109.60 (10)
C5—C6—H6119.9O6—S1—C5107.54 (10)
C1—C6—H6119.9O4—S1—C5106.61 (9)
O2—C7—O1123.31 (18)O5—S1—C5106.90 (9)
O2—C7—C1123.58 (18)
C6—C1—C2—O3−177.99 (18)C6—C1—C7—O2−179.0 (2)
C7—C1—C2—O32.2 (3)C2—C1—C7—O20.8 (3)
C6—C1—C2—C31.1 (3)C6—C1—C7—O11.0 (3)
C7—C1—C2—C3−178.71 (18)C2—C1—C7—O1−179.17 (18)
O3—C2—C3—C4178.12 (19)C9i—C8—N1—C90.2 (4)
C1—C2—C3—C4−1.0 (3)C8i—C9—N1—C8−0.2 (4)
C2—C3—C4—C50.3 (3)C6—C5—S1—O6−176.94 (15)
C3—C4—C5—C60.3 (3)C4—C5—S1—O61.7 (2)
C3—C4—C5—S1−178.24 (16)C6—C5—S1—O4−54.28 (18)
C4—C5—C6—C1−0.2 (3)C4—C5—S1—O4124.33 (19)
S1—C5—C6—C1178.39 (14)C6—C5—S1—O562.88 (17)
C2—C1—C6—C5−0.5 (3)C4—C5—S1—O5−118.51 (18)
C7—C1—C6—C5179.32 (17)

Symmetry codes: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8···O60.932.403.273 (3)156
C9—H9···O6ii0.932.413.240 (3)149
C6—H6···O1iii0.932.493.249 (2)139
N1—H1B···O70.87 (3)1.71 (3)2.580 (3)176 (3)
O7—H7A···O50.83 (3)1.84 (3)2.659 (2)171 (3)
O7—H7B···O4ii0.83 (3)1.81 (3)2.631 (3)172 (3)
O3—H3A···O20.83 (3)1.92 (3)2.625 (2)143 (3)
O1—H1A···O5iii0.82 (3)1.92 (3)2.719 (2)163 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CS2079).

References

  • Bruker (2001). SAINT-Plus and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Meng, X.-G., Xiao, Y.-L., Wang, Z.-L. & Liu, C.-L. (2008). Acta Cryst. C64, o53–o57. [PubMed]
  • Sheldrick, G. M. (1997). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smith, G., Wermuth, U. D. & Healy, P. C. (2005). Acta Cryst. C61, o555–o558. [PubMed]
  • Smith, G., Wermuth, U. D. & White, J. M. (2004). Acta Cryst. C60, o575–o581. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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