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

Wang, J.-R.; Yang, Z.-H.; Liu, C.-H.; Li, L.-L.

doi:10.1107/S1600536808017777

organic compounds

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Volume 64| Part 7| July 2008| Page o1289

doi:10.1107/S1600536808017777

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

Jia-Rong Wang,^a ^* Ze-Hui Yang,^a Chun-Hai Liu ^b and Ling-Lan Li ^a

^aCollege of Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang 315016, People's Republic of China, and ^bHunan Jiuzhitang Co. Ltd, Changsha, Hunan 410008, People's Republic of China
^*Correspondence e-mail: jr_wang@126.com

(Received 17 May 2008; accepted 12 June 2008; online 19 June 2008)

Pyrazine and 5-sulfosalicylic acid crystallize from a methanol solution containing water as the title salt, C₄H₆N₂²⁺·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 (10 $[\overline{2}]$ ) plane.

Related literature

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

Experimental

Crystal data

C₄H₆N₂²⁺·2C₇H₅O₆S⁻·2H₂O
M_r = 552.48
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.045
wR(F²) = 0.131
S = 1.08
2412 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O6	0.93	2.40	3.273 (3)	156
C9—H9⋯O6ⁱ	0.93	2.41	3.240 (3)	149
C6—H6⋯O1ⁱⁱ	0.93	2.49	3.249 (2)	139
N1—H1B⋯O7	0.87 (3)	1.71 (3)	2.580 (3)	176 (3)
O7—H7A⋯O5	0.83 (3)	1.84 (3)	2.659 (2)	171 (3)
O7—H7B⋯O4ⁱ	0.83 (3)	1.81 (3)	2.631 (3)	172 (3)
O3—H3A⋯O2	0.83 (3)	1.92 (3)	2.625 (2)	143 (3)
O1—H1A⋯O5ⁱⁱ	0.82 (3)	1.92 (3)	2.719 (2)	163 (3)
Symmetry codes: (i) x, y-1, z; (ii) -x, -y+1, -z+1.

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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 the drawing.

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

Crystal data top

C₄H₆N₂²⁺·2C₇H₅O₆S⁻·2H₂O	Z = 1
M_r = 552.48	F(000) = 286
Triclinic, P1	D_x = 1.634 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7887 (5) Å	Cell parameters from 2269 reflections
b = 6.9256 (6) Å	θ = 1.6–25.2°
c = 13.0349 (10) Å	µ = 0.32 mm⁻¹
α = 100.663 (7)°	T = 298 K
β = 97.761 (9)°	Plate, colourless
γ = 107.735 (9)°	0.20 × 0.10 × 0.08 mm
V = 561.52 (9) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1977 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
0.3° wide ω exposures scans	θ_max = 27.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −8→8
T_min = 0.929, T_max = 0.975	k = −5→8
5286 measured reflections	l = −16→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0732P)² + 0.0236P] where P = (F_o² + 2F_c²)/3
2412 reflections	(Δ/σ)_max = 0.001
178 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₄H₆N₂²⁺·2C₇H₅O₆S⁻·2H₂O	γ = 107.735 (9)°
M_r = 552.48	V = 561.52 (9) Å³
Triclinic, P1	Z = 1
a = 6.7887 (5) Å	Mo Kα radiation
b = 6.9256 (6) Å	µ = 0.32 mm⁻¹
c = 13.0349 (10) Å	T = 298 K
α = 100.663 (7)°	0.20 × 0.10 × 0.08 mm
β = 97.761 (9)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1977 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.975	R_int = 0.064
5286 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.32 e Å⁻³
2412 reflections	Δρ_min = −0.51 e Å⁻³
178 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.4240 (3)	0.7285 (3)	0.48381 (14)	0.0311 (4)
C2	0.6433 (3)	0.7939 (3)	0.48820 (17)	0.0361 (5)
C3	0.7816 (3)	0.8439 (3)	0.58633 (18)	0.0439 (5)
H3	0.9265	0.8851	0.5895	0.053*
C4	0.7052 (3)	0.8328 (3)	0.67817 (17)	0.0425 (5)
H4	0.7985	0.8671	0.7432	0.051*
C5	0.4881 (3)	0.7704 (3)	0.67421 (15)	0.0338 (4)
C6	0.3486 (3)	0.7183 (3)	0.57800 (14)	0.0323 (4)
H6	0.2040	0.6762	0.5758	0.039*
C7	0.2761 (3)	0.6708 (3)	0.38006 (15)	0.0362 (5)
C8	0.9086 (4)	0.6243 (4)	0.96127 (19)	0.0543 (6)
H8	0.8459	0.7119	0.9346	0.065*
C9	0.8819 (4)	0.3018 (4)	0.99291 (18)	0.0511 (6)
H9	0.8012	0.1641	0.9884	0.061*
N1	0.7935 (3)	0.4275 (3)	0.95466 (13)	0.0466 (5)
H1B	0.658 (4)	0.377 (4)	0.928 (2)	0.056*
O1	0.0776 (2)	0.6158 (3)	0.38832 (11)	0.0484 (4)
H1A	−0.005 (5)	0.578 (5)	0.331 (2)	0.073*
O2	0.3328 (3)	0.6740 (3)	0.29528 (11)	0.0531 (4)
O3	0.7255 (3)	0.8128 (3)	0.40112 (14)	0.0523 (4)
H3A	0.633 (5)	0.788 (5)	0.348 (3)	0.078*
O4	0.2517 (3)	0.8910 (3)	0.79365 (12)	0.0535 (4)
O5	0.2546 (2)	0.5428 (2)	0.78053 (11)	0.0467 (4)
O6	0.5615 (3)	0.8329 (3)	0.88036 (11)	0.0522 (4)
O7	0.3909 (3)	0.2940 (3)	0.88232 (12)	0.0475 (4)
H7A	0.346 (5)	0.362 (5)	0.844 (2)	0.071*
H7B	0.340 (5)	0.169 (5)	0.849 (2)	0.071*
S1	0.38501 (8)	0.76139 (8)	0.79128 (3)	0.0378 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0308 (9)	0.0259 (10)	0.0391 (9)	0.0108 (8)	0.0074 (8)	0.0115 (8)
C2	0.0321 (10)	0.0272 (10)	0.0533 (11)	0.0111 (8)	0.0152 (8)	0.0130 (9)
C3	0.0247 (10)	0.0414 (12)	0.0655 (13)	0.0105 (9)	0.0075 (9)	0.0150 (10)
C4	0.0325 (10)	0.0412 (12)	0.0495 (11)	0.0106 (9)	−0.0022 (9)	0.0113 (9)
C5	0.0319 (10)	0.0293 (10)	0.0391 (9)	0.0103 (8)	0.0030 (8)	0.0090 (8)
C6	0.0265 (9)	0.0316 (11)	0.0391 (9)	0.0101 (8)	0.0044 (7)	0.0103 (8)
C7	0.0369 (11)	0.0349 (11)	0.0396 (10)	0.0125 (9)	0.0085 (8)	0.0145 (8)
C8	0.0648 (16)	0.0550 (16)	0.0518 (13)	0.0315 (13)	0.0084 (11)	0.0173 (11)
C9	0.0617 (15)	0.0454 (14)	0.0481 (12)	0.0214 (12)	0.0105 (11)	0.0113 (10)
N1	0.0443 (10)	0.0565 (13)	0.0383 (9)	0.0203 (10)	0.0045 (8)	0.0073 (9)
O1	0.0322 (8)	0.0695 (12)	0.0376 (7)	0.0083 (8)	0.0005 (6)	0.0184 (7)
O2	0.0521 (9)	0.0701 (12)	0.0390 (8)	0.0189 (9)	0.0136 (7)	0.0176 (7)
O3	0.0404 (9)	0.0604 (11)	0.0606 (10)	0.0151 (8)	0.0235 (7)	0.0190 (8)
O4	0.0572 (10)	0.0634 (11)	0.0488 (8)	0.0343 (9)	0.0092 (7)	0.0126 (7)
O5	0.0447 (9)	0.0477 (10)	0.0400 (7)	0.0053 (7)	0.0014 (6)	0.0148 (7)
O6	0.0515 (9)	0.0557 (10)	0.0383 (7)	0.0133 (8)	−0.0093 (7)	0.0064 (7)
O7	0.0571 (10)	0.0444 (10)	0.0467 (8)	0.0238 (8)	0.0082 (7)	0.0152 (7)
S1	0.0369 (3)	0.0405 (3)	0.0328 (3)	0.0128 (2)	−0.0006 (2)	0.0074 (2)

Geometric parameters (Å, º) top

C1—C6	1.398 (3)	C8—N1	1.329 (3)
C1—C2	1.408 (3)	C8—C9ⁱ	1.363 (4)
C1—C7	1.478 (2)	C8—H8	0.9300
C2—O3	1.341 (3)	C9—N1	1.329 (3)
C2—C3	1.397 (3)	C9—C8ⁱ	1.363 (4)
C3—C4	1.373 (3)	C9—H9	0.9300
C3—H3	0.9300	N1—H1B	0.87 (3)
C4—C5	1.395 (3)	O1—H1A	0.82 (3)
C4—H4	0.9300	O3—H3A	0.83 (3)
C5—C6	1.380 (2)	O4—S1	1.4556 (17)
C5—S1	1.766 (2)	O5—S1	1.4721 (15)
C6—H6	0.9300	O6—S1	1.4421 (14)
C7—O2	1.220 (2)	O7—H7A	0.83 (3)
C7—O1	1.310 (2)	O7—H7B	0.83 (3)

C6—C1—C2	119.40 (17)	O1—C7—C1	113.11 (16)
C6—C1—C7	120.76 (17)	N1—C8—C9ⁱ	120.2 (2)
C2—C1—C7	119.84 (17)	N1—C8—H8	119.9
O3—C2—C3	118.37 (18)	C9ⁱ—C8—H8	119.9
O3—C2—C1	122.21 (19)	N1—C9—C8ⁱ	119.6 (2)
C3—C2—C1	119.41 (18)	N1—C9—H9	120.2
C4—C3—C2	120.51 (19)	C8ⁱ—C9—H9	120.2
C4—C3—H3	119.7	C8—N1—C9	120.2 (2)
C2—C3—H3	119.7	C8—N1—H1B	122.3 (17)
C3—C4—C5	120.19 (19)	C9—N1—H1B	117.4 (18)
C3—C4—H4	119.9	C7—O1—H1A	113 (2)
C5—C4—H4	119.9	C2—O3—H3A	111 (2)
C6—C5—C4	120.25 (18)	H7A—O7—H7B	107 (3)
C6—C5—S1	118.43 (15)	O6—S1—O4	114.02 (10)
C4—C5—S1	121.30 (15)	O6—S1—O5	111.78 (9)
C5—C6—C1	120.23 (17)	O4—S1—O5	109.60 (10)
C5—C6—H6	119.9	O6—S1—C5	107.54 (10)
C1—C6—H6	119.9	O4—S1—C5	106.61 (9)
O2—C7—O1	123.31 (18)	O5—S1—C5	106.90 (9)
O2—C7—C1	123.58 (18)

C6—C1—C2—O3	−177.99 (18)	C6—C1—C7—O2	−179.0 (2)
C7—C1—C2—O3	2.2 (3)	C2—C1—C7—O2	0.8 (3)
C6—C1—C2—C3	1.1 (3)	C6—C1—C7—O1	1.0 (3)
C7—C1—C2—C3	−178.71 (18)	C2—C1—C7—O1	−179.17 (18)
O3—C2—C3—C4	178.12 (19)	C9ⁱ—C8—N1—C9	0.2 (4)
C1—C2—C3—C4	−1.0 (3)	C8ⁱ—C9—N1—C8	−0.2 (4)
C2—C3—C4—C5	0.3 (3)	C6—C5—S1—O6	−176.94 (15)
C3—C4—C5—C6	0.3 (3)	C4—C5—S1—O6	1.7 (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—O4	124.33 (19)
S1—C5—C6—C1	178.39 (14)	C6—C5—S1—O5	62.88 (17)
C2—C1—C6—C5	−0.5 (3)	C4—C5—S1—O5	−118.51 (18)
C7—C1—C6—C5	179.32 (17)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O6	0.93	2.40	3.273 (3)	156
C9—H9···O6ⁱⁱ	0.93	2.41	3.240 (3)	149
C6—H6···O1ⁱⁱⁱ	0.93	2.49	3.249 (2)	139
N1—H1B···O7	0.87 (3)	1.71 (3)	2.580 (3)	176 (3)
O7—H7A···O5	0.83 (3)	1.84 (3)	2.659 (2)	171 (3)
O7—H7B···O4ⁱⁱ	0.83 (3)	1.81 (3)	2.631 (3)	172 (3)
O3—H3A···O2	0.83 (3)	1.92 (3)	2.625 (2)	143 (3)
O1—H1A···O5ⁱⁱⁱ	0.82 (3)	1.92 (3)	2.719 (2)	163 (3)

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

Experimental details

Crystal data
Chemical formula	C₄H₆N₂²⁺·2C₇H₅O₆S⁻·2H₂O
M_r	552.48
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.7887 (5), 6.9256 (6), 13.0349 (10)
α, β, γ (°)	100.663 (7), 97.761 (9), 107.735 (9)
V (Å³)	561.52 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.20 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.929, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	5286, 2412, 1977
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.131, 1.08
No. of reflections	2412
No. of parameters	178
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.51

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O6	0.93	2.40	3.273 (3)	156
C9—H9···O6ⁱ	0.93	2.41	3.240 (3)	149
C6—H6···O1ⁱⁱ	0.93	2.49	3.249 (2)	139
N1—H1B···O7	0.87 (3)	1.71 (3)	2.580 (3)	176 (3)
O7—H7A···O5	0.83 (3)	1.84 (3)	2.659 (2)	171 (3)
O7—H7B···O4ⁱ	0.83 (3)	1.81 (3)	2.631 (3)	172 (3)
O3—H3A···O2	0.83 (3)	1.92 (3)	2.625 (2)	143 (3)
O1—H1A···O5ⁱⁱ	0.82 (3)	1.92 (3)	2.719 (2)	163 (3)

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

Acknowledgements

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

References

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