Bis(2-amino-3-carb­oxy­pyrazin-1-ium) sulfate dihydrate

Berrah, F.; Ouakkaf, A.; Bouacida, S.; Roisnel, T.

doi:10.1107/S1600536811005824

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Pages o677-o678

doi:10.1107/S1600536811005824

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Bis(2-amino-3-carboxypyrazin-1-ium) sulfate dihydrate

Fadila Berrah,^a,^b ^* Amira Ouakkaf,^a Sofiane Bouacida ^b,^c and Thierry Roisnel ^d

^aLaboratoire de Chimie Appliquée et Technologie des Matériaux LCATM, Université Larbi Ben M'Hidi, 04000 Oum El Bouaghi, Algeria, ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Larbi Ben M'hidi, 04000 Oum El Bouaghi, Algeria, ^cUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Faculté des Sciences Exactes, Université Mentouri Constantine 25000, Algeria, and ^dCentre de Difractométrie X, UMR 6226 CNRS Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du Général Leclerc, 35042 Rennes, France
^*Correspondence e-mail: fadilaber@yahoo.fr

(Received 7 February 2011; accepted 16 February 2011; online 23 February 2011)

The crystal structure of the title compound, 2C₅H₆N₃O₂⁺·SO₄²⁻·2H₂O, displays a variety of N—H⋯O and O—H⋯O hydrogen bonds in which all potential donors and acceptors are involved. In the crystal, cations and anions are interconnected, forming R₃³(10) and R₂²(8) ring motifs whereas the anions and water molecules form R₂³(10) rings, which develop in chains running along [100]. The resulting three-dimensional network exhibits undulating sheets parallel to (011), marked by the presence of R₆⁶(26) rings in which six cations are involved.

Related literature

For related compounds, see: Berrah et al. (2005a ,b , 2011 ); Bouacida et al. (2005 , 2009 ); Dobson & Gerkin (1996 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ); Etter et al. (1990 ). For similar intermolecular interactions, see: Dorn et al. (2005 ), Janiak (2000 ); Desiraju (2003 ).

Experimental

Crystal data

2C₅H₆N₃O₂⁺·SO₄²⁻·2H₂O
M_r = 412.36
Monoclinic, P 2₁ /a
a = 7.7214 (4) Å
b = 20.7043 (14) Å
c = 10.6398 (7) Å
β = 109.299 (2)°
V = 1605.36 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 150 K
0.55 × 0.36 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.708, T_max = 0.960
13466 measured reflections
3675 independent reflections
3146 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.03
3675 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A1⋯O4	0.88	1.92	2.7970 (18)	175
N1A—H1A2⋯O6A	0.88	2.04	2.6741 (18)	128
N1A—H1A2⋯O6Bⁱ	0.88	2.30	3.0158 (18)	138
N2A—H2A⋯O1	0.88	1.83	2.6915 (18)	167
N1B—H1B1⋯O2	0.88	2.34	3.0827 (18)	142
N1B—H1B2⋯O6B	0.88	2.08	2.7144 (19)	129
N1B—H1B2⋯O6Aⁱⁱ	0.88	2.10	2.8237 (18)	139
N2B—H2B⋯O1W	0.88	1.81	2.6705 (18)	167
O5B—H5B⋯O2W	0.84	1.67	2.5046 (17)	174
O5A—H5A⋯O2ⁱ	0.84	1.78	2.6192 (16)	175
O1W—H1W⋯O3	0.85	1.95	2.7934 (19)	175
O1W—H2W⋯O2ⁱⁱⁱ	0.85	2.06	2.8996 (18)	167
O1W—H2W⋯O4ⁱⁱⁱ	0.85	2.65	3.2856 (17)	133
O2W—H3W⋯O4ⁱⁱ	0.85	1.88	2.7351 (17)	177
O2W—H4W⋯O3^iv	0.86	1.91	2.7633 (17)	171
Symmetry codes: (i) x, y, z-1; (ii) x, y, z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+1]$ .

Data collection: APEX2 (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005824/dn2656sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005824/dn2656Isup2.hkl

checkCIF report

Comment top

Hydrogen bonds are object of several studies, that aim at elucidate their influence on crystal construction and compounds properties (Desiraju, 2003). N-heterocyclic compounds such as pyrazine and its derivatives may be interesting units to built new edifices involving original hydrogen-bonding scheme since they include a variety of potential hydrogen donors and acceptors. In this perspective and as a part of our search for new hybrid compounds based on protonated amines and imines (Berrah et al. 2011, 2005a,b; Bouacida et al. 2005,2009), we present here the structure of Bis (2-Amino-3-carboxypyrazin-1-ium) sulfate dihydrate.

The asymmetric units of (I) includes two symmetry- independent cations and water molecules, and one sulfate anion. Cations and anions are interconnected to form R₃³(10) and R₂²(8) ring motifs (Etter et al., 1990; Bernstein et al., 1995) (Fig 1). Bond lengths and angles are as expected (Berrah et al. 2011; Dobson & Gerkin, 1996).

The three-dimensional structure of (I), results from undulating sheets of cations dimmers parallel to (011) plane(Fig.2 and Fig.3 )and sulfate-water chains extending along [100](Fig.3). An interesting hydrogen bonds network, in which all potential donors and acceptors are involved, and especially marked by the presence of R₆⁶(26)and R₂³(10) set-graph motifs (Etter et al., 1990; Bernstein et al., 1995), ensures the coherence of the structure(Fig.2 and Fig.3, table 1). This later is reinforced by the contribution of π-π, S—O··· π and C—O··· π interactions (Dorn et al. 2005; Janiak, 2000) (table 2,3).

Related literature top

For related compounds, see: Berrah et al. (2005a,b, 2011); Bouacida et al. (2005, 2009); Dobson & Gerkin (1996). For hydrogen-bond motifs, see: Bernstein et al. (1995); Etter et al. (1990). For similar intermolecular interactions, see: Dorn et al. (2005), Janiak (2000); Desiraju (2003).

Experimental top

The title compound was synthesized by reacting 3-amino-pyrazine 2- carboxylic acid with some excess of sulphiric acid in aqueous solution. Slow evaporation leads to well crystallized yellow needles.

Computing details top

Data collection: APEX2 (Bruker,2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick,2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atomic labelling scheme.Displacement are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Partial packing view showing undulating sheets parallel to (011) plane and R₆⁶(26) rings set motif. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in H-bonds have been omitted for clarity
	Fig. 3. Partial packing view showing sulfate-water chains extending along [100] direction and undulating sheets. Hydrogen bonds are shown as dashed lines.Hydrogen atoms not involved in H-bonds have been omitted for clarity.

Bis(2-amino-3-carboxypyrazin-1-ium) sulfate dihydrate top

Crystal data top

2C₅H₆N₃O₂⁺·SO₄²⁻·2H₂O	F(000) = 856
M_r = 412.36	D_x = 1.706 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71073 Å
a = 7.7214 (4) Å	Cell parameters from 5179 reflections
b = 20.7043 (14) Å	θ = 2.8–27.5°
c = 10.6398 (7) Å	µ = 0.27 mm⁻¹
β = 109.299 (2)°	T = 150 K
V = 1605.36 (17) Å³	Prism, yellow
Z = 4	0.55 × 0.36 × 0.15 mm

Data collection top

Bruker APEXII diffractometer	3146 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
CCD rotation images, thin slices scans	θ_max = 27.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→9
T_min = 0.708, T_max = 0.960	k = −26→26
13466 measured reflections	l = −13→13
3675 independent reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0491P)² + 0.7394P] where P = (F_o² + 2F_c²)/3
3675 reflections	(Δ/σ)_max = 0.001
246 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

2C₅H₆N₃O₂⁺·SO₄²⁻·2H₂O	V = 1605.36 (17) Å³
M_r = 412.36	Z = 4
Monoclinic, P2₁/a	Mo Kα radiation
a = 7.7214 (4) Å	µ = 0.27 mm⁻¹
b = 20.7043 (14) Å	T = 150 K
c = 10.6398 (7) Å	0.55 × 0.36 × 0.15 mm
β = 109.299 (2)°

Data collection top

Bruker APEXII diffractometer	3675 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3146 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.960	R_int = 0.039
13466 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	Δρ_max = 0.47 e Å⁻³
3675 reflections	Δρ_min = −0.48 e Å⁻³
246 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O5A	0.17659 (16)	0.04617 (6)	0.03501 (11)	0.0221 (3)
H5A	0.1515	0.0732	−0.0273	0.033*
O6A	0.03846 (18)	0.11842 (6)	0.12557 (11)	0.0258 (3)
N1A	0.0567 (2)	0.10587 (7)	0.37979 (13)	0.0231 (3)
H1A1	0.0399	0.1167	0.4549	0.028*
H1A2	0.0122	0.1303	0.3087	0.028*
N2A	0.21592 (19)	0.01604 (6)	0.48490 (13)	0.0195 (3)
H2A	0.1989	0.0288	0.5588	0.023*
N3A	0.27826 (19)	−0.02410 (6)	0.25952 (13)	0.0194 (3)
C1A	0.1266 (2)	0.06905 (7)	0.13275 (15)	0.0185 (3)
C2A	0.1875 (2)	0.02980 (7)	0.25829 (15)	0.0177 (3)
C3A	0.1485 (2)	0.05305 (7)	0.37379 (15)	0.0183 (3)
C4A	0.3079 (2)	−0.03946 (8)	0.48622 (16)	0.0207 (3)
H4A	0.3518	−0.0644	0.5654	0.025*
C5A	0.3374 (2)	−0.05941 (8)	0.37264 (16)	0.0214 (3)
H5C	0.4006	−0.0988	0.3731	0.026*
O5B	−0.03794 (19)	0.32977 (6)	1.37046 (12)	0.0273 (3)
H5B	−0.0768	0.3055	1.4185	0.041*
O6B	−0.03786 (17)	0.23824 (5)	1.25812 (11)	0.0241 (3)
N1B	0.0619 (2)	0.24559 (7)	1.03668 (14)	0.0238 (3)
H1B1	0.0821	0.2313	0.9649	0.029*
H1B2	0.0315	0.2184	1.0895	0.029*
N2B	0.12393 (19)	0.34886 (7)	0.98346 (13)	0.0205 (3)
H2B	0.1422	0.3332	0.912	0.025*
N3B	0.07073 (19)	0.39911 (6)	1.20349 (13)	0.0206 (3)
C1B	−0.0126 (2)	0.29617 (8)	1.27448 (15)	0.0196 (3)
C2B	0.0482 (2)	0.33663 (7)	1.17934 (14)	0.0178 (3)
C3B	0.0773 (2)	0.30786 (8)	1.06522 (15)	0.0187 (3)
C4B	0.1438 (2)	0.41269 (8)	1.00633 (16)	0.0227 (3)
H4B	0.1752	0.4403	0.9458	0.027*
C5B	0.1180 (2)	0.43737 (8)	1.11810 (16)	0.0233 (3)
H5D	0.1338	0.4824	1.1357	0.028*
S1	0.15317 (5)	0.131125 (18)	0.73117 (4)	0.01813 (11)
O1	0.2146 (2)	0.06509 (6)	0.71883 (12)	0.0337 (3)
O2	0.09536 (18)	0.13565 (6)	0.85065 (12)	0.0262 (3)
O3	0.30149 (17)	0.17773 (7)	0.74478 (12)	0.0306 (3)
O4	−0.00482 (16)	0.14708 (6)	0.61180 (11)	0.0236 (3)
O1W	0.23309 (17)	0.30737 (6)	0.78406 (12)	0.0262 (3)
H1W	0.2465	0.2676	0.7697	0.039*
H2W	0.3352	0.3253	0.7903	0.039*
O2W	−0.15818 (19)	0.26453 (6)	1.52193 (12)	0.0296 (3)
H3W	−0.1068	0.2285	1.5511	0.044*
H4W	−0.1653	0.2863	1.5886	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5A	0.0332 (7)	0.0213 (6)	0.0140 (5)	0.0044 (5)	0.0109 (5)	0.0030 (4)
O6A	0.0400 (7)	0.0206 (6)	0.0184 (6)	0.0076 (5)	0.0115 (5)	0.0036 (4)
N1A	0.0340 (8)	0.0227 (7)	0.0140 (6)	0.0063 (6)	0.0100 (6)	0.0012 (5)
N2A	0.0269 (7)	0.0193 (6)	0.0128 (6)	−0.0002 (5)	0.0072 (5)	0.0001 (5)
N3A	0.0253 (7)	0.0168 (6)	0.0158 (6)	−0.0013 (5)	0.0063 (5)	−0.0003 (5)
C1A	0.0232 (8)	0.0172 (7)	0.0153 (7)	−0.0026 (6)	0.0065 (6)	−0.0007 (6)
C2A	0.0225 (8)	0.0159 (7)	0.0154 (7)	−0.0020 (6)	0.0072 (6)	−0.0008 (6)
C3A	0.0229 (8)	0.0175 (7)	0.0144 (7)	−0.0027 (6)	0.0062 (6)	−0.0007 (6)
C4A	0.0259 (8)	0.0177 (7)	0.0168 (7)	−0.0016 (6)	0.0048 (6)	0.0035 (6)
C5A	0.0279 (9)	0.0163 (7)	0.0186 (7)	0.0011 (6)	0.0056 (6)	0.0000 (6)
O5B	0.0480 (8)	0.0198 (6)	0.0201 (6)	−0.0009 (5)	0.0194 (5)	−0.0004 (5)
O6B	0.0355 (7)	0.0185 (6)	0.0193 (6)	−0.0015 (5)	0.0104 (5)	0.0003 (4)
N1B	0.0372 (8)	0.0188 (7)	0.0167 (6)	−0.0035 (6)	0.0105 (6)	−0.0037 (5)
N2B	0.0267 (7)	0.0221 (7)	0.0128 (6)	−0.0027 (5)	0.0069 (5)	−0.0024 (5)
N3B	0.0267 (7)	0.0172 (6)	0.0167 (6)	0.0005 (5)	0.0056 (5)	−0.0008 (5)
C1B	0.0231 (8)	0.0198 (8)	0.0141 (7)	0.0019 (6)	0.0039 (6)	0.0008 (6)
C2B	0.0216 (8)	0.0173 (7)	0.0127 (7)	0.0005 (6)	0.0033 (6)	0.0001 (5)
C3B	0.0203 (8)	0.0194 (7)	0.0142 (7)	−0.0010 (6)	0.0029 (6)	−0.0014 (6)
C4B	0.0276 (9)	0.0201 (8)	0.0195 (7)	−0.0035 (6)	0.0068 (6)	0.0020 (6)
C5B	0.0324 (9)	0.0177 (7)	0.0193 (7)	−0.0019 (6)	0.0077 (7)	0.0004 (6)
S1	0.0259 (2)	0.01758 (19)	0.01276 (18)	0.00290 (14)	0.00883 (15)	0.00224 (13)
O1	0.0605 (9)	0.0245 (6)	0.0186 (6)	0.0188 (6)	0.0163 (6)	0.0047 (5)
O2	0.0429 (7)	0.0230 (6)	0.0193 (6)	0.0051 (5)	0.0192 (5)	0.0035 (5)
O3	0.0291 (7)	0.0384 (7)	0.0238 (6)	−0.0067 (5)	0.0080 (5)	0.0029 (5)
O4	0.0266 (6)	0.0246 (6)	0.0179 (6)	0.0031 (5)	0.0049 (5)	0.0017 (4)
O1W	0.0294 (6)	0.0273 (6)	0.0252 (6)	−0.0009 (5)	0.0136 (5)	−0.0005 (5)
O2W	0.0460 (8)	0.0244 (6)	0.0229 (6)	0.0086 (5)	0.0174 (6)	0.0061 (5)

Geometric parameters (Å, º) top

O5A—C1A	1.3116 (19)	N1B—H1B1	0.88
O5A—H5A	0.84	N1B—H1B2	0.88
O6A—C1A	1.216 (2)	N2B—C4B	1.343 (2)
N1A—C3A	1.316 (2)	N2B—C3B	1.347 (2)
N1A—H1A1	0.88	N2B—H2B	0.88
N1A—H1A2	0.88	N3B—C2B	1.319 (2)
N2A—C4A	1.349 (2)	N3B—C5B	1.344 (2)
N2A—C3A	1.360 (2)	C1B—C2B	1.503 (2)
N2A—H2A	0.88	C2B—C3B	1.435 (2)
N3A—C2A	1.315 (2)	C4B—C5B	1.368 (2)
N3A—C5A	1.352 (2)	C4B—H4B	0.95
C1A—C2A	1.500 (2)	C5B—H5D	0.95
C2A—C3A	1.442 (2)	S1—O1	1.4670 (12)
C4A—C5A	1.365 (2)	S1—O3	1.4677 (13)
C4A—H4A	0.95	S1—O4	1.4786 (12)
C5A—H5C	0.95	S1—O2	1.4831 (12)
O5B—C1B	1.3028 (19)	O1W—H1W	0.8491
O5B—H5B	0.84	O1W—H2W	0.8542
O6B—C1B	1.218 (2)	O2W—H3W	0.8543
N1B—C3B	1.321 (2)	O2W—H4W	0.8582

C1A—O5A—H5A	109.5	C4B—N2B—C3B	122.81 (14)
C3A—N1A—H1A1	120	C4B—N2B—H2B	118.6
C3A—N1A—H1A2	120	C3B—N2B—H2B	118.6
H1A1—N1A—H1A2	120	C2B—N3B—C5B	119.63 (14)
C4A—N2A—C3A	122.57 (14)	O6B—C1B—O5B	125.38 (15)
C4A—N2A—H2A	118.7	O6B—C1B—C2B	121.55 (14)
C3A—N2A—H2A	118.7	O5B—C1B—C2B	113.05 (14)
C2A—N3A—C5A	119.32 (14)	N3B—C2B—C3B	121.62 (14)
O6A—C1A—O5A	123.99 (14)	N3B—C2B—C1B	117.76 (14)
O6A—C1A—C2A	121.03 (14)	C3B—C2B—C1B	120.62 (14)
O5A—C1A—C2A	114.98 (13)	N1B—C3B—N2B	119.31 (15)
N3A—C2A—C3A	122.39 (14)	N1B—C3B—C2B	124.91 (15)
N3A—C2A—C1A	118.54 (14)	N2B—C3B—C2B	115.78 (14)
C3A—C2A—C1A	119.06 (14)	N2B—C4B—C5B	118.98 (15)
N1A—C3A—N2A	118.94 (14)	N2B—C4B—H4B	120.5
N1A—C3A—C2A	125.91 (14)	C5B—C4B—H4B	120.5
N2A—C3A—C2A	115.15 (14)	N3B—C5B—C4B	121.17 (15)
N2A—C4A—C5A	119.33 (14)	N3B—C5B—H5D	119.4
N2A—C4A—H4A	120.3	C4B—C5B—H5D	119.4
C5A—C4A—H4A	120.3	O1—S1—O3	110.91 (9)
N3A—C5A—C4A	121.21 (15)	O1—S1—O4	109.31 (7)
N3A—C5A—H5C	119.4	O3—S1—O4	109.46 (7)
C4A—C5A—H5C	119.4	O1—S1—O2	109.47 (7)
C1B—O5B—H5B	109.5	O3—S1—O2	108.66 (7)
C3B—N1B—H1B1	120	O4—S1—O2	109.00 (7)
C3B—N1B—H1B2	120	H1W—O1W—H2W	105.7
H1B1—N1B—H1B2	120	H3W—O2W—H4W	108

C5A—N3A—C2A—C3A	0.1 (2)	C5B—N3B—C2B—C3B	1.6 (2)
C5A—N3A—C2A—C1A	178.70 (14)	C5B—N3B—C2B—C1B	−177.43 (14)
O6A—C1A—C2A—N3A	178.18 (15)	O6B—C1B—C2B—N3B	179.35 (15)
O5A—C1A—C2A—N3A	−2.2 (2)	O5B—C1B—C2B—N3B	0.9 (2)
O6A—C1A—C2A—C3A	−3.2 (2)	O6B—C1B—C2B—C3B	0.3 (2)
O5A—C1A—C2A—C3A	176.41 (14)	O5B—C1B—C2B—C3B	−178.12 (14)
C4A—N2A—C3A—N1A	178.56 (15)	C4B—N2B—C3B—N1B	−179.42 (15)
C4A—N2A—C3A—C2A	−1.9 (2)	C4B—N2B—C3B—C2B	0.5 (2)
N3A—C2A—C3A—N1A	−179.04 (16)	N3B—C2B—C3B—N1B	178.17 (15)
C1A—C2A—C3A—N1A	2.4 (2)	C1B—C2B—C3B—N1B	−2.9 (2)
N3A—C2A—C3A—N2A	1.5 (2)	N3B—C2B—C3B—N2B	−1.7 (2)
C1A—C2A—C3A—N2A	−177.09 (13)	C1B—C2B—C3B—N2B	177.27 (14)
C3A—N2A—C4A—C5A	0.8 (2)	C3B—N2B—C4B—C5B	0.8 (2)
C2A—N3A—C5A—C4A	−1.4 (2)	C2B—N3B—C5B—C4B	−0.2 (3)
N2A—C4A—C5A—N3A	0.9 (2)	N2B—C4B—C5B—N3B	−1.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O4	0.88	1.92	2.7970 (18)	175
N1A—H1A2···O6A	0.88	2.04	2.6741 (18)	128
N1A—H1A2···O6Bⁱ	0.88	2.30	3.0158 (18)	138
N2A—H2A···O1	0.88	1.83	2.6915 (18)	167
N1B—H1B1···O2	0.88	2.34	3.0827 (18)	142
N1B—H1B2···O6B	0.88	2.08	2.7144 (19)	129
N1B—H1B2···O6Aⁱⁱ	0.88	2.10	2.8237 (18)	139
N2B—H2B···O1W	0.88	1.81	2.6705 (18)	167
O5B—H5B···O2W	0.84	1.67	2.5046 (17)	174
O5A—H5A···O2ⁱ	0.84	1.78	2.6192 (16)	175
O1W—H1W···O3	0.85	1.95	2.7934 (19)	175
O1W—H2W···O2ⁱⁱⁱ	0.85	2.06	2.8996 (18)	167
O1W—H2W···O4ⁱⁱⁱ	0.85	2.65	3.2856 (17)	133
O2W—H3W···O4ⁱⁱ	0.85	1.88	2.7351 (17)	177
O2W—H4W···O3^iv	0.86	1.91	2.7633 (17)	171
C4A—H4A···O5B^v	0.95	2.58	3.320 (2)	134
C4A—H4A···N3B^v	0.95	2.45	3.369 (2)	163
C4B—H4B···O5A^vi	0.95	2.45	3.187 (2)	134
C4B—H4B···N3A^vi	0.95	2.44	3.347 (2)	159
C5A—H5C···O1W^vii	0.95	2.55	3.175 (2)	124
C5B—H5D···O1^viii	0.95	2.35	3.192 (2)	148

Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) x+1/2, −y+1/2, z; (iv) x−1/2, −y+1/2, z+1; (v) −x+1/2, y−1/2, −z+2; (vi) −x+1/2, y+1/2, −z+1; (vii) −x+1/2, y−1/2, −z+1; (viii) −x+1/2, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	2C₅H₆N₃O₂⁺·SO₄²⁻·2H₂O
M_r	412.36
Crystal system, space group	Monoclinic, P2₁/a
Temperature (K)	150
a, b, c (Å)	7.7214 (4), 20.7043 (14), 10.6398 (7)
β (°)	109.299 (2)
V (Å³)	1605.36 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.55 × 0.36 × 0.15

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.708, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	13466, 3675, 3146
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.03
No. of reflections	3675
No. of parameters	246
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.48

Computer programs: APEX2 (Bruker,2001), SAINT (Bruker, 2001), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick,2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O4	0.88	1.92	2.7970 (18)	175.3
N1A—H1A2···O6A	0.88	2.04	2.6741 (18)	128.1
N1A—H1A2···O6Bⁱ	0.88	2.30	3.0158 (18)	138.4
N2A—H2A···O1	0.88	1.83	2.6915 (18)	166.5
N1B—H1B1···O2	0.88	2.34	3.0827 (18)	141.8
N1B—H1B2···O6B	0.88	2.08	2.7144 (19)	128.7
N1B—H1B2···O6Aⁱⁱ	0.88	2.10	2.8237 (18)	138.6
N2B—H2B···O1W	0.88	1.81	2.6705 (18)	166.8
O5B—H5B···O2W	0.84	1.67	2.5046 (17)	173.7
O5A—H5A···O2ⁱ	0.84	1.78	2.6192 (16)	174.9
O1W—H1W···O3	0.85	1.95	2.7934 (19)	174.7
O1W—H2W···O2ⁱⁱⁱ	0.85	2.06	2.8996 (18)	167
O1W—H2W···O4ⁱⁱⁱ	0.85	2.65	3.2856 (17)	132.5
O2W—H3W···O4ⁱⁱ	0.85	1.88	2.7351 (17)	177.2
O2W—H4W···O3^iv	0.86	1.91	2.7633 (17)	170.5

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

π–π stacking interactions (Å, °) top

Cg1 is the centroid of the N2A–C4A ring.

CgI	CgJ	CgI···CgJ^a	α	β	γ	CgI···P(J)^b	CgJ···P(I)^c	Slippage
Cg1	Cg1ⁱ	3.9678 (9)	0	34.94	34.94	3.2528 (6)	3.2527 (6)	2.272

Symmetry codes: (i)1-x,-y,1-z Notes: a : Distance between centroids b : Perpendicular distance of CgI on ring plan J c : Perpendicular distance of CgJ on ring plan I α = Dihedral Angle between the ring planes β = Angle between the centroid vector CgI···CgJ and the normal to the plane I. γ = Angle between the centroid vector CgI···CgJ and the normal to the plane J. Slippage = vertical displacement between ring centroids.

S—O···π and C—O···π interactions (Å, °). top

Cg1 and Cg2 are the centroids of the N2A–C4A and N2B–C4B rings, respectively.

X	I	J	I···J	X–I···J	X···J
S1	O1	Cg1ⁱ	3.5922 (17)	91.83 (7)	3.9233 (8)
S1	O2	Cg1ⁱ	3.9845 (14)	76.88 (5)	3.9233 (8)
S1	O2	Cg2ⁱⁱ	3.8831 (15)	92.77 (6)	4.2231 (8)
C1A	O6A	Cg2ⁱⁱⁱ	3.3136 (16)	125.62 (11)	4.1418 (18)

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

Acknowledgements

We are grateful to the LCATM laboratory, Université Larbi Ben M'Hidi, Oum El Bouaghi, Algeria, for financial support.

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