Bis(2-amino-3-carb­oxy­pyridinium) sulfate trihydrate

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

doi:10.1107/S1600536811010191

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o953-o954

doi:10.1107/S1600536811010191

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Bis(2-amino-3-carboxypyridinium) sulfate trihydrate

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

^aLaboratoire de Chimie Appliquée et Technologie des Matériaux LCATM, Université Larbi Ben M'Hidi, 04000 Oum El Bouaghi, Algeria, ^bUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Faculté des Sciences Exactes, Université Mentouri Constantine 25000, Algeria, and ^cCentre 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 9 March 2011; accepted 17 March 2011; online 23 March 2011)

In the title compound, 2C₆H₇N₂O₂⁺·SO₄²⁻·3H₂O, there are two independent cations which are connected into N—H⋯O hydrogen-bonded dimers. In the crystal, O—H⋯O hydrogen-bonded sulfate–water sheets run parallel to (001) and are linked into a three-dimensional network via intermolecular N—H⋯O and O—H⋯O hydrogen bonds through the 2-aminonicotinium dimers. Further stabilization is provided by weak intermolecular C—H⋯O hydrogen bonds. R₄³(10) and R₂²(8) graph-set rings are observed. The crystal studied was an inversion twin with refined components of 0.45 (6) and 0.55 (6).

Related literature

For related compounds, see: Athimoolam & Rajaram (2005 ); Berrah et al. (2005, 2011a ,b ); Dobson & Gerkin (1997 ); Giantsidis & Turnbull (2000 ); Pawlukojc et al. (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ); Etter et al. (1990 ). For background to hydrogen bonding, see: Desiraju (2003 ).

Experimental

Crystal data

2C₆H₇N₂O₂⁺·SO₄²⁻·3H₂O
M_r = 428.39
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.5372 (5) Å
b = 12.3141 (10) Å
c = 23.0274 (19) Å
V = 1853.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 150 K
0.58 × 0.13 × 0.04 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.845, T_max = 0.970
23588 measured reflections
4229 independent reflections
3669 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 1.06
4229 reflections
274 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 1790 Friedel pairs
Flack parameter: 0.45 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯O3Wⁱ	0.84	1.69	2.5152 (18)	167
O1B—H1B⋯O1W	0.84	1.69	2.5138 (18)	168
O1W—H1W⋯O2Wⁱⁱ	0.82 (4)	1.93 (3)	2.754 (2)	177 (4)
O3W—H5W⋯O2W	0.77 (3)	1.98 (3)	2.750 (2)	176 (3)
O1W—H2W⋯O4	0.75 (4)	2.03 (4)	2.752 (2)	164 (3)
O2W—H3W⋯O3ⁱⁱⁱ	0.80 (3)	1.92 (3)	2.7151 (19)	169 (3)
O2W—H4W⋯O4	0.90 (3)	1.87 (3)	2.7675 (19)	175 (3)
O3W—H6W⋯O2^iv	0.84 (2)	1.88 (2)	2.720 (2)	171 (3)
N2A—H2A⋯O1	0.88	1.92	2.7681 (18)	163
N2B—H2B⋯O1^v	0.88	1.88	2.7419 (19)	167
N1A—H11A⋯O4	0.88	2.05	2.915 (2)	166
N1B—H11B⋯O2^v	0.88	1.94	2.817 (2)	173
N1A—H12A⋯O2A	0.88	2.09	2.726 (2)	129
N1A—H12A⋯O2B	0.88	2.27	2.979 (2)	138
N1B—H12B⋯O2A	0.88	2.25	2.963 (2)	138
N1B—H12B⋯O2B	0.88	2.10	2.733 (2)	128
C4A—H4A⋯O3^vi	0.95	2.46	3.143 (2)	129
C4B—H4B⋯O3^vii	0.95	2.31	3.169 (2)	150
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (vi) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

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/S1600536811010191/lh5219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010191/lh5219Isup2.hkl

checkCIF report

Comment top

Hydrogen bonds are the object of several studies, which aim to elucidate their influence on crystal construction and compounds propreties (Desiraju, 2003). Pyridine and its derivatives well known for their various chemical and biological activities, have proved their aptitude to built new edifices involving original hydrogen-bonding patterns due to their variety of potential hydrogen donors and acceptors (Athimoolam et al., 2005; Dobson & Gerkin, 1997; Giantsidis & Turnbull, 2000). The title compound was obtained from 2-aminonicotinic acid and is a part of our search for new hybrid compounds based on protonated N-heterocyclic compounds and inorganic acids (Berrah et al., 2005;2011a,b).

As shown in figure 1, the asymmetric unit includes two crystallographically independent 2-aminonicotinium cations (A and B), one sulfate anion and three water molecules. The cation geometry is similar to that reported for the structure of 2-aminonicotinic acid (Dobson & Gerkin, 1997; Pawlukojc et al., 2007) except for C—O distances in the carboxylic group. In the 2-aminonicotinic acid structure, the two C—O distances are 1.234 (2) and 1.266 (2)Å since the carboxylic group transfers its proton to the hetero-ring nitrogen atom leading to a zwitterionic molecule.

The crystal packing of the title compound (Fig. 2) results from sulfate-water sheets extending parallel to (001) (Fig. 3) and linked together via 2-aminonicotinium dimers (Fig. 4). In one sheet, sulfate anions and H₂O2W molecules alternate, leading to infinite chains running parallel to the a axis. These chains are further connected through H₂O1W and H₂O3W molecules in a way that R³₄(10) rings are formed (Fig. 3). The structure is stabilized via N—H···O, O—H···O and C—H···O Hydrogen bonds that link each dimer to its neighbors (Table 1, Fig. 4). R³₄ (10) and R²₂(8) graph-set rings are observed (Fig. 4)(Etter et al., 1990; Bernstein et al., 1995).

Related literature top

For related compounds, see: Athimoolam & Rajaram (2005); Berrah et al. (2005, 2011a,b); Dobson & Gerkin (1997); Giantsidis & Turnbull (2000); Pawlukojc et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995); Etter et al. (1990). For background to hydrogen bonding, see: Desiraju (2003).

Experimental top

Colorless crystal of the title compound was obtained by slow evaporation of an aqueous solution of 2-amino-pyridine-3-carboxylic acid and sulfuric acid in 2:1 stoichiometric ratio.

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. (Farrugia, 1997) The asymmetric unit of the title compound. Displacement are drawn at the 50% probability level.
	Fig. 2. (Brandenburg & Berndt, 2001) A diagram of the three-dimentonal packing of (I) viewed along [010]. Hydrogen bonds are shown as dashed lines
	Fig. 3. (Brandenburg & Berndt, 2001) A view of one sulfate-water sheet parallel to (001) and the R³₄(10) rings. Hydrogen bonds are shown as dashed lines.
	Fig. 4. (Brandenburg & Berndt, 2001) Part of crystal packing showing cation dimers and R³₄(10) and R²₂(8) rings. Hydrogen bonds are shown as dashed lines.

Bis(2-amino-3-carboxypyridinium) sulfate trihydrate top

Crystal data top

2C₆H₇N₂O₂⁺·SO₄²⁻·3H₂O	D_x = 1.535 Mg m⁻³
M_r = 428.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 8735 reflections
a = 6.5372 (5) Å	θ = 2.4–27.2°
b = 12.3141 (10) Å	µ = 0.24 mm⁻¹
c = 23.0274 (19) Å	T = 150 K
V = 1853.7 (3) Å³	Needle, colourless
Z = 4	0.58 × 0.13 × 0.04 mm
F(000) = 896

Data collection top

Bruker APEXII diffractometer	3669 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
CCD rotation images, thin slices scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→5
T_min = 0.845, T_max = 0.970	k = −15→15
23588 measured reflections	l = −29→29
4229 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0369P)² + 0.4264P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4229 reflections	Δρ_max = 0.27 e Å⁻³
274 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1790 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.45 (6)

Crystal data top

2C₆H₇N₂O₂⁺·SO₄²⁻·3H₂O	V = 1853.7 (3) Å³
M_r = 428.39	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.5372 (5) Å	µ = 0.24 mm⁻¹
b = 12.3141 (10) Å	T = 150 K
c = 23.0274 (19) Å	0.58 × 0.13 × 0.04 mm

Data collection top

Bruker APEXII diffractometer	4229 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3669 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.970	R_int = 0.042
23588 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.079	Δρ_max = 0.27 e Å⁻³
S = 1.06	Δρ_min = −0.28 e Å⁻³
4229 reflections	Absolute structure: Flack (1983), 1790 Friedel pairs
274 parameters	Absolute structure parameter: 0.45 (6)
0 restraints

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
C1A	0.7166 (3)	0.27959 (15)	0.00318 (8)	0.0216 (4)
C1B	0.6471 (3)	0.70977 (15)	0.03679 (8)	0.0200 (4)
C2A	0.7181 (3)	0.23143 (14)	0.06245 (7)	0.0207 (4)
C2B	0.6478 (3)	0.75822 (15)	−0.02254 (7)	0.0190 (4)
C3A	0.7116 (3)	0.29935 (14)	0.11251 (7)	0.0201 (3)
C3B	0.6631 (3)	0.68958 (14)	−0.07242 (7)	0.0190 (4)
C4A	0.7238 (3)	0.14018 (15)	0.17195 (8)	0.0263 (4)
H4A	0.726	0.1102	0.21	0.032*
C4B	0.6481 (3)	0.84839 (16)	−0.13233 (8)	0.0262 (4)
H4B	0.6479	0.8782	−0.1704	0.031*
C5A	0.7264 (3)	0.07309 (16)	0.12519 (8)	0.0312 (5)
H5A	0.728	−0.0036	0.1297	0.037*
C5B	0.6322 (3)	0.91558 (16)	−0.08559 (8)	0.0282 (4)
H5B	0.6211	0.992	−0.0904	0.034*
C6A	0.7268 (3)	0.12083 (16)	0.07029 (9)	0.0279 (4)
H6A	0.7333	0.0752	0.0371	0.034*
C6B	0.6326 (3)	0.86880 (16)	−0.03039 (8)	0.0247 (4)
H6B	0.6222	0.9145	0.0027	0.03*
N1A	0.7020 (3)	0.40640 (12)	0.11129 (7)	0.0278 (3)
H11A	0.7	0.4434	0.144	0.033*
H12A	0.6976	0.4407	0.0778	0.033*
N1B	0.6788 (3)	0.58296 (12)	−0.07142 (7)	0.0270 (4)
H11B	0.6894	0.5465	−0.1041	0.032*
H12B	0.6785	0.5482	−0.038	0.032*
N2A	0.7181 (2)	0.24906 (12)	0.16507 (6)	0.0215 (3)
H2A	0.7187	0.2899	0.1964	0.026*
N2B	0.6642 (2)	0.73990 (13)	−0.12524 (6)	0.0225 (3)
H2B	0.6761	0.6992	−0.1565	0.027*
O1	0.7971 (2)	0.35697 (10)	0.26811 (5)	0.0259 (3)
O1A	0.7192 (2)	0.20503 (10)	−0.03781 (5)	0.0294 (3)
H1A	0.714	0.2352	−0.0705	0.044*
O1B	0.6533 (2)	0.78383 (10)	0.07796 (5)	0.0277 (3)
H1B	0.6398	0.7538	0.1105	0.042*
O2	0.7597 (2)	0.52317 (11)	0.32163 (5)	0.0311 (3)
O1W	0.6295 (3)	0.71875 (14)	0.18121 (6)	0.0467 (5)
H1W	0.652 (5)	0.765 (3)	0.2061 (14)	0.07*
H2W	0.653 (5)	0.664 (3)	0.1933 (14)	0.07*
O2A	0.7137 (2)	0.37665 (11)	−0.00595 (5)	0.0296 (3)
O2B	0.6414 (2)	0.61242 (10)	0.04572 (5)	0.0266 (3)
O3	0.9930 (2)	0.51502 (12)	0.24034 (6)	0.0301 (3)
O2W	0.3026 (2)	0.36878 (11)	0.23220 (6)	0.0270 (3)
H3W	0.201 (4)	0.405 (2)	0.2347 (11)	0.04*
H4W	0.405 (4)	0.417 (2)	0.2307 (11)	0.04*
O4	0.6310 (2)	0.50965 (11)	0.22342 (5)	0.0259 (3)
O3W	0.2063 (3)	0.23235 (12)	0.14171 (6)	0.0325 (3)
H5W	0.239 (4)	0.271 (2)	0.1664 (11)	0.049*
H6W	0.227 (4)	0.170 (2)	0.1557 (11)	0.049*
S1	0.79804 (7)	0.47766 (4)	0.263808 (18)	0.01992 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0196 (8)	0.0255 (10)	0.0197 (8)	−0.0003 (8)	−0.0009 (7)	−0.0008 (7)
C1B	0.0188 (9)	0.0236 (10)	0.0176 (8)	0.0009 (7)	−0.0004 (7)	−0.0013 (7)
C2A	0.0205 (9)	0.0210 (9)	0.0207 (8)	−0.0023 (7)	−0.0018 (7)	−0.0009 (7)
C2B	0.0192 (9)	0.0212 (9)	0.0165 (8)	−0.0012 (7)	−0.0016 (7)	−0.0003 (7)
C3A	0.0203 (8)	0.0203 (8)	0.0196 (8)	−0.0009 (8)	−0.0001 (8)	0.0007 (7)
C3B	0.0205 (9)	0.0199 (9)	0.0167 (8)	0.0008 (7)	−0.0006 (7)	0.0007 (7)
C4A	0.0318 (10)	0.0239 (9)	0.0232 (9)	0.0002 (8)	−0.0036 (8)	0.0062 (8)
C4B	0.0300 (11)	0.0261 (10)	0.0225 (9)	0.0020 (8)	−0.0008 (8)	0.0081 (8)
C5A	0.0451 (12)	0.0192 (9)	0.0293 (10)	−0.0003 (9)	−0.0034 (9)	0.0025 (8)
C5B	0.0336 (11)	0.0214 (10)	0.0294 (10)	0.0018 (8)	−0.0012 (8)	0.0047 (8)
C6A	0.0354 (11)	0.0218 (9)	0.0266 (10)	0.0000 (8)	−0.0017 (9)	−0.0036 (8)
C6B	0.0278 (10)	0.0221 (9)	0.0241 (9)	0.0003 (8)	−0.0007 (8)	−0.0021 (8)
N1A	0.0465 (9)	0.0181 (8)	0.0188 (7)	0.0007 (8)	−0.0003 (8)	−0.0004 (6)
N1B	0.0436 (10)	0.0204 (8)	0.0171 (7)	0.0013 (8)	−0.0001 (7)	−0.0006 (6)
N2A	0.0256 (8)	0.0214 (7)	0.0175 (7)	0.0004 (7)	−0.0014 (6)	0.0000 (6)
N2B	0.0270 (8)	0.0243 (8)	0.0162 (7)	0.0004 (6)	0.0004 (6)	−0.0011 (6)
O1	0.0404 (7)	0.0191 (6)	0.0181 (6)	−0.0016 (6)	−0.0021 (6)	0.0004 (5)
O1A	0.0454 (8)	0.0252 (7)	0.0176 (6)	0.0011 (7)	−0.0006 (6)	−0.0015 (5)
O1B	0.0414 (8)	0.0250 (7)	0.0166 (6)	0.0008 (6)	−0.0005 (6)	−0.0018 (5)
O2	0.0508 (9)	0.0240 (7)	0.0184 (6)	0.0046 (6)	0.0021 (6)	−0.0021 (6)
O1W	0.0970 (15)	0.0245 (8)	0.0185 (7)	0.0102 (9)	−0.0078 (8)	−0.0008 (6)
O2A	0.0453 (8)	0.0226 (7)	0.0208 (6)	0.0020 (6)	0.0017 (6)	0.0026 (5)
O2B	0.0363 (8)	0.0224 (7)	0.0212 (7)	0.0017 (6)	0.0004 (6)	0.0031 (6)
O3	0.0274 (7)	0.0295 (8)	0.0332 (8)	−0.0038 (6)	0.0025 (6)	0.0054 (7)
O2W	0.0264 (7)	0.0248 (7)	0.0297 (7)	−0.0016 (6)	0.0013 (7)	−0.0017 (6)
O4	0.0284 (7)	0.0260 (7)	0.0234 (7)	−0.0015 (6)	−0.0034 (5)	0.0041 (6)
O3W	0.0538 (9)	0.0244 (8)	0.0193 (7)	−0.0026 (7)	−0.0042 (7)	−0.0014 (6)
S1	0.0259 (2)	0.0184 (2)	0.01552 (19)	−0.00133 (19)	−0.00044 (18)	0.00021 (17)

Geometric parameters (Å, º) top

C1A—O2A	1.214 (2)	C5B—C6B	1.395 (3)
C1A—O1A	1.317 (2)	C5B—H5B	0.95
C1A—C2A	1.488 (2)	C6A—H6A	0.95
C1B—O2B	1.217 (2)	C6B—H6B	0.95
C1B—O1B	1.316 (2)	N1A—H11A	0.88
C1B—C2B	1.491 (2)	N1A—H12A	0.88
C2A—C6A	1.375 (3)	N1B—H11B	0.88
C2A—C3A	1.425 (2)	N1B—H12B	0.88
C2B—C6B	1.377 (3)	N2A—H2A	0.88
C2B—C3B	1.430 (2)	N2B—H2B	0.88
C3A—N1A	1.320 (2)	O1—S1	1.4895 (13)
C3A—N2A	1.360 (2)	O1A—H1A	0.84
C3B—N1B	1.317 (2)	O1B—H1B	0.84
C3B—N2B	1.365 (2)	O2—S1	1.4662 (13)
C4A—N2A	1.351 (2)	O1W—H1W	0.82 (3)
C4A—C5A	1.357 (3)	O1W—H2W	0.75 (3)
C4A—H4A	0.95	O3—S1	1.4591 (14)
C4B—N2B	1.350 (2)	O2W—H3W	0.80 (3)
C4B—C5B	1.362 (3)	O2W—H4W	0.89 (3)
C4B—H4B	0.95	O4—S1	1.4877 (13)
C5A—C6A	1.394 (3)	O3W—H5W	0.77 (3)
C5A—H5A	0.95	O3W—H6W	0.85 (3)

O2A—C1A—O1A	124.23 (16)	C2A—C6A—C5A	122.46 (18)
O2A—C1A—C2A	123.47 (16)	C2A—C6A—H6A	118.8
O1A—C1A—C2A	112.30 (15)	C5A—C6A—H6A	118.8
O2B—C1B—O1B	124.18 (16)	C2B—C6B—C5B	121.86 (18)
O2B—C1B—C2B	123.32 (16)	C2B—C6B—H6B	119.1
O1B—C1B—C2B	112.51 (15)	C5B—C6B—H6B	119.1
C6A—C2A—C3A	118.44 (16)	C3A—N1A—H11A	120
C6A—C2A—C1A	121.03 (16)	C3A—N1A—H12A	120
C3A—C2A—C1A	120.52 (15)	H11A—N1A—H12A	120
C6B—C2B—C3B	118.95 (16)	C3B—N1B—H11B	120
C6B—C2B—C1B	121.05 (16)	C3B—N1B—H12B	120
C3B—C2B—C1B	120.00 (15)	H11B—N1B—H12B	120
N1A—C3A—N2A	118.38 (15)	C4A—N2A—C3A	123.86 (15)
N1A—C3A—C2A	124.77 (15)	C4A—N2A—H2A	118.1
N2A—C3A—C2A	116.85 (15)	C3A—N2A—H2A	118.1
N1B—C3B—N2B	117.89 (16)	C4B—N2B—C3B	123.82 (16)
N1B—C3B—C2B	125.49 (15)	C4B—N2B—H2B	118.1
N2B—C3B—C2B	116.61 (15)	C3B—N2B—H2B	118.1
N2A—C4A—C5A	120.77 (17)	C1A—O1A—H1A	109.5
N2A—C4A—H4A	119.6	C1B—O1B—H1B	109.5
C5A—C4A—H4A	119.6	H1W—O1W—H2W	109 (3)
N2B—C4B—C5B	120.77 (17)	H3W—O2W—H4W	105 (2)
N2B—C4B—H4B	119.6	H5W—O3W—H6W	104 (3)
C5B—C4B—H4B	119.6	O3—S1—O2	111.42 (9)
C4A—C5A—C6A	117.56 (18)	O3—S1—O4	109.05 (8)
C4A—C5A—H5A	121.2	O2—S1—O4	109.93 (8)
C6A—C5A—H5A	121.2	O3—S1—O1	110.06 (9)
C4B—C5B—C6B	117.98 (18)	O2—S1—O1	108.68 (7)
C4B—C5B—H5B	121	O4—S1—O1	107.62 (8)
C6B—C5B—H5B	121

O2A—C1A—C2A—C6A	−178.3 (2)	C1B—C2B—C3B—N2B	−179.57 (16)
O1A—C1A—C2A—C6A	1.6 (3)	N2A—C4A—C5A—C6A	1.1 (3)
O2A—C1A—C2A—C3A	1.3 (3)	N2B—C4B—C5B—C6B	−0.1 (3)
O1A—C1A—C2A—C3A	−178.75 (18)	C3A—C2A—C6A—C5A	1.0 (3)
O2B—C1B—C2B—C6B	173.11 (18)	C1A—C2A—C6A—C5A	−179.38 (18)
O1B—C1B—C2B—C6B	−6.9 (2)	C4A—C5A—C6A—C2A	−2.1 (3)
O2B—C1B—C2B—C3B	−6.5 (3)	C3B—C2B—C6B—C5B	−0.1 (3)
O1B—C1B—C2B—C3B	173.45 (16)	C1B—C2B—C6B—C5B	−179.72 (17)
C6A—C2A—C3A—N1A	−179.65 (19)	C4B—C5B—C6B—C2B	−0.2 (3)
C1A—C2A—C3A—N1A	0.7 (3)	C5A—C4A—N2A—C3A	1.0 (3)
C6A—C2A—C3A—N2A	1.1 (3)	N1A—C3A—N2A—C4A	178.57 (18)
C1A—C2A—C3A—N2A	−178.53 (16)	C2A—C3A—N2A—C4A	−2.1 (3)
C6B—C2B—C3B—N1B	179.90 (18)	C5B—C4B—N2B—C3B	0.9 (3)
C1B—C2B—C3B—N1B	−0.5 (3)	N1B—C3B—N2B—C4B	179.60 (18)
C6B—C2B—C3B—N2B	0.8 (3)	C2B—C3B—N2B—C4B	−1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O3Wⁱ	0.84	1.69	2.5152 (18)	167
O1B—H1B···O1W	0.84	1.69	2.5138 (18)	168
O1W—H1W···O2Wⁱⁱ	0.82 (4)	1.93 (3)	2.754 (2)	177 (4)
O3W—H5W···O2W	0.77 (3)	1.98 (3)	2.750 (2)	176 (3)
O1W—H2W···O4	0.75 (4)	2.03 (4)	2.752 (2)	164 (3)
O2W—H3W···O3ⁱⁱⁱ	0.80 (3)	1.92 (3)	2.7151 (19)	169 (3)
O2W—H4W···O4	0.90 (3)	1.87 (3)	2.7675 (19)	175 (3)
O3W—H6W···O2^iv	0.84 (2)	1.88 (2)	2.720 (2)	171 (3)
N2A—H2A···O1	0.88	1.92	2.7681 (18)	163
N2B—H2B···O1^v	0.88	1.88	2.7419 (19)	167
N1A—H11A···O4	0.88	2.05	2.915 (2)	166
N1B—H11B···O2^v	0.88	1.94	2.817 (2)	173
N1A—H12A···O2A	0.88	2.09	2.726 (2)	129
N1A—H12A···O2B	0.88	2.27	2.979 (2)	138
N1B—H12B···O2A	0.88	2.25	2.963 (2)	138
N1B—H12B···O2B	0.88	2.10	2.733 (2)	128
C4A—H4A···O3^vi	0.95	2.46	3.143 (2)	129
C4B—H4B···O3^vii	0.95	2.31	3.169 (2)	150
C6A—H6A···O1A	0.95	2.35	2.697 (2)	101
C6B—H6B···O1B	0.95	2.37	2.709 (2)	100

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

Experimental details

Crystal data
Chemical formula	2C₆H₇N₂O₂⁺·SO₄²⁻·3H₂O
M_r	428.39
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.5372 (5), 12.3141 (10), 23.0274 (19)
V (Å³)	1853.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.58 × 0.13 × 0.04

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.845, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	23588, 4229, 3669
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.06
No. of reflections	4229
No. of parameters	274
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.28
Absolute structure	Flack (1983), 1790 Friedel pairs
Absolute structure parameter	0.45 (6)

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
O1A—H1A···O3Wⁱ	0.84	1.69	2.5152 (18)	167
O1B—H1B···O1W	0.84	1.69	2.5138 (18)	168
O1W—H1W···O2Wⁱⁱ	0.82 (4)	1.93 (3)	2.754 (2)	177 (4)
O3W—H5W···O2W	0.77 (3)	1.98 (3)	2.750 (2)	176 (3)
O1W—H2W···O4	0.75 (4)	2.03 (4)	2.752 (2)	164 (3)
O2W—H3W···O3ⁱⁱⁱ	0.80 (3)	1.92 (3)	2.7151 (19)	169 (3)
O2W—H4W···O4	0.90 (3)	1.87 (3)	2.7675 (19)	175 (3)
O3W—H6W···O2^iv	0.84 (2)	1.88 (2)	2.720 (2)	171 (3)
N2A—H2A···O1	0.88	1.92	2.7681 (18)	163
N2B—H2B···O1^v	0.88	1.88	2.7419 (19)	167
N1A—H11A···O4	0.88	2.05	2.915 (2)	166
N1B—H11B···O2^v	0.88	1.94	2.817 (2)	173
N1A—H12A···O2A	0.88	2.09	2.726 (2)	129
N1A—H12A···O2B	0.88	2.27	2.979 (2)	138
N1B—H12B···O2A	0.88	2.25	2.963 (2)	138
N1B—H12B···O2B	0.88	2.10	2.733 (2)	128
C4A—H4A···O3^vi	0.95	2.46	3.143 (2)	129
C4B—H4B···O3^vii	0.95	2.31	3.169 (2)	150

Footnotes

‡Current address: Département 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.

Acknowledgements

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

References

Athimoolam, S. & Rajaram, R. K. (2005). Acta Cryst. E61, o2764–o2767. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Berrah, F., Lamraoui, H. & Benali-Cherif, N. (2005). Acta Cryst. E61, o210–o212. Web of Science CSD CrossRef IUCr Journals Google Scholar
Berrah, F., Ouakkaf, A., Bouacida, S. & Roisnel, T. (2011a). Acta Cryst. E67, o525–o526. Web of Science CrossRef IUCr Journals Google Scholar
Berrah, F., Ouakkaf, A., Bouacida, S. & Roisnel, T. (2011b). Acta Cryst. E67, o677–o678. Web of Science CrossRef IUCr Journals Google Scholar
Brandenburg, K. & Berndt, M. (2001). DIAMOND. Crystal Impact, Bonn, Germany. Google Scholar
Bruker (2001). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Desiraju, G. R. (2003). Crystal Design: Structure and Function Perspectives in Supramolecular Chemistry, Vol. 7. Chichester: John Wiley & Sons Ltd. Google Scholar
Dobson, A. J. & Gerkin, R. E. (1997). Acta Cryst. C53, 1427–1429. CSD CrossRef CAS IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Giantsidis, J. & Turnbull, M. M. (2000). Acta Cryst. C56, 334–335. CSD CrossRef CAS IUCr Journals Google Scholar
Pawlukojc, A., Starosta, W., Leciejewicz, J., Natkaniec, I. & Nowak, D. (2007). Chem. Phys. Lett. 437, 32–37. CAS Google Scholar
Sheldrick, G. M. (2002). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar