Bis(adeninium) bis­(hydrogensulfate) sulfate

Guenifa, F.; Bendjeddou, L.; Cherouana, A.; Dahaoui, S.; Lecomte, C.

doi:10.1107/S1600536812044728

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages o3266-o3267

doi:10.1107/S1600536812044728

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Bis(adeninium) bis(hydrogensulfate) sulfate

Fatiha Guenifa,^a Lamia Bendjeddou,^a ^* Aouatef Cherouana,^a Slimane Dahaoui ^b and Claude Lecomte ^b

^aUnité de Recherche Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Faculté des Sciences Exactes, Campus Chaabet Ersas, Université Mentouri de Constantine, 25000 Constantine, Algeria, and ^bCristallographie, Résonance Magnétique et Modélisation (CRM2), Université Henri Poincaré, Nancy 1, Faculté des Sciences, BP 70239, 54506 Vandoeuvre lès Nancy CEDEX, France
^*Correspondence e-mail: Lamiabendjeddou@yahoo.fr

(Received 16 October 2012; accepted 29 October 2012; online 3 November 2012)

The title compound, 2C₅H₇N₅²⁺·2HSO₄⁻·SO₄²⁻, was synthesized from adenine and sulfuric acid. The asymmetric unit contains two diprotonated adeninium cations, two bisulfate anions and one sulfate anion. The crystal structure is stabilized by classical N—H⋯O and O—H⋯O hydrogen bonds, and weak C—H⋯O and C—H⋯N hydrogen bonds, generating a three-dimensional network.

Related literature

For background to the title compound, see: Biradha et al. (2010 ); Guenifa et al. (2009 ); Zeghouan et al. (2012 ). For related structures, see: Bendjeddou et al. (2003 ); Fun et al. (2011 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

2C₅H₇N₅⁺·2HSO₄⁻·SO₄²⁻
M_r = 564.54
Monoclinic, C 2/c
a = 26.370 (5) Å
b = 8.970 (2) Å
c = 20.350 (4) Å
β = 126.184 (10)°
V = 3885.2 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 120 K
0.3 × 0.3 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer
5681 measured reflections
5681 independent reflections
3989 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.131
S = 1.07
5681 reflections
352 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.09 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O4ⁱ	0.84 (2)	1.74 (2)	2.580 (2)	174 (3)
O11—H11⋯O1ⁱⁱ	0.91 (3)	1.56 (2)	2.457 (2)	166 (4)
N1A—H1A⋯O2ⁱⁱ	0.912 (18)	1.92 (2)	2.760 (3)	151 (3)
N1B—H1B⋯O7	0.880 (18)	2.28 (2)	3.027 (3)	142 (2)
N1B—H1B⋯O10	0.880 (18)	2.18 (2)	2.870 (3)	136 (2)
N2A—H21A⋯O3ⁱⁱⁱ	0.89 (2)	1.96 (2)	2.796 (3)	156 (2)
N2A—H22A⋯O2ⁱⁱ	0.911 (18)	2.17 (2)	2.884 (3)	135 (2)
N2A—H22A⋯O9ⁱⁱⁱ	0.911 (18)	2.22 (2)	2.814 (3)	122 (2)
N2B—H21B⋯O10	0.885 (18)	2.01 (3)	2.760 (3)	142 (3)
N2B—H22B⋯O12^iv	0.91 (2)	1.94 (2)	2.817 (3)	162 (2)
N7A—H7A⋯O3ⁱⁱⁱ	0.888 (17)	1.96 (2)	2.757 (2)	149 (2)
N7B—H7B⋯O1^v	0.916 (17)	2.28 (2)	2.858 (3)	121 (2)
N7B—H7B⋯O12^iv	0.916 (17)	1.97 (2)	2.763 (3)	145 (2)
N9A—H9A⋯O8^vi	0.89 (2)	1.95 (2)	2.767 (3)	152.3 (18)
N9B—H9B⋯O7^vii	0.87 (2)	1.920 (19)	2.775 (3)	166 (2)
C2A—H2A⋯O6^viii	0.93	2.21	2.913 (3)	131
C2A—H2A⋯N3B^vi	0.93	2.49	3.189 (3)	132
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z; (v) -x, -y+2, -z; (vi) $[x, -y+1, z-{\script{1\over 2}}]$ ; (vii) x, y+1, z; (viii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: KappaCCD Reference Manual (Nonius, 1998 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ), PARST97 (Nardelli, 1995 ), Mercury (Macrae et al., 2006 ) and POVRay (Persistence of Vision Team, 2004 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812044728/xu5635sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044728/xu5635Isup2.hkl

checkCIF report

Comment top

Adenine is a purine derivative nucleobase. It is one of the most widely-used nucleobase in biochemistry (Biradha et al., 2010). It is an integral part of DNA, RNA and ATP. As a nucleobase, adenine exhibits a tendency to self associate with the help of Watson-Crick and Hoogsteen hydrogen bonds. We present in this paper the molecular structure of compound (I) which was isolated during our investigations on D—H···A hydrogen bonds in organic-inorganic hybrid systems, including amino acids and nitrogenous bases with various inorganic acids (Guenifa et al., 2009; Zeghouan et al., 2012).

The asymmetric unit of the title compound is formed by two diprotonated adeninium cations, two bisulfate and one sulfate anions (Fig. 1). Recently, similar structures containing adeninium cations have been reported. Among examples, can be named the following ones: Adeninium diperchlorate monohydrate (Bendjeddou et al., 2003), and Adeninium perchlorate (Fun et al., 2011). In the structure of (I), the ions are held together with intermolecular N—H···O, O—H···O, C—H···O and C—H···N hydrogen bonds, forming three-dimensional hydrogen-bonded network.

In the sulfate anion, S1 atom is linked to four equivalents short bonds, which confirm the absence of proton in this anion. The presence of H atom in O5 and O11 atoms of the bisulfate anions is confirmed from the asymmetric S—O bond distances. This ascertain the bisulfate nature of the anion and generate two strong independent O—H···O hydrogen bonds which form a D²₂(7) finite chains (Bernstein et al., 1995), in three-dimensional network (Fig. 2).

In the crystal packing, the adeninium cations are linked by pairs of C—H···N hydrogen bond involving the H2A and N3B atoms of cations into inversion dimers, generating a characteristic D(3) motif (Fig. 2).

Moreover, adeninium cations and bisulfate and sulfate anions are linked by moderates N—H···O and weaks C—H···O hydrogen-bonds forming an alternating noncentrosymmetric rings in two-dimensional network which can be described by the graph-set motif R¹₂(5), R⁴₄(16) and R¹₂(7) which run parallel to the [010] direction (Fig. 3).

The combination of the four types of intermolecular N—H···O, O—H···O, C—H···O and C—H···N hydrogen bonds gives rise to different graph-set motifs and generates a complicated three-dimensional network.

Related literature top

For background to the title compound, see: Biradha et al. (2010); Guenifa et al. (2009); Zeghouan et al. (2012). For related structures, see: Bendjeddou et al. (2003); Fun et al. (2011). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound is prepared by reaction of an aqueous solution containing the adenine and the sulfuric acid. The solution was maintained in 293 K under agitation during twenty minutes. Colourless crystals were appeared by evaporation of the solution at room temperature over the course of a few weeks.

Computing details top

Data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995), Mercury (Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Figures top

	Fig. 1. The asymmetric unit of (I), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure, showing the formation of D(3) and D²₂(7) hydrogen-bonding motifs. [Symmetry codes: (@) x - 1/2, y + 1/2, z - 1; (β) x - 1/2, y + 3/2, z - 1; (α) x - 1/2, -y + 3/2, z - 3/2].
	Fig. 3. Part of the crystal structure, showing the aggregation of R¹₂(5), R⁴₄(16) and R¹₂(7) hydrogen-bonding motifs. [Symmetry codes: (#) x - 1/2, y - 1/2, z; (°) x - 1/2, y + 1/2, z; (^) -x + 1, y, -z + 3/2].

Bis(adeninium) bis(hydrogensulfate) sulfate top

Crystal data top

2C₅H₇N₅⁺·2HSO₄⁻·SO₄²⁻	F(000) = 2320
M_r = 564.54	D_x = 1.93 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5681 reflections
a = 26.370 (5) Å	θ = 3–30.0°
b = 8.970 (2) Å	µ = 0.48 mm⁻¹
c = 20.350 (4) Å	T = 120 K
β = 126.184 (10)°	Needle, colourless
V = 3885.2 (15) Å³	0.3 × 0.3 × 0.2 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	3989 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 30.0°, θ_min = 3.0°
ω scans	h = 0→37
5681 measured reflections	k = 0→12
5681 independent reflections	l = −28→23

Refinement top

Refinement on F²	12 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0749P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.131	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 1.09 e Å⁻³
5681 reflections	Δρ_min = −0.60 e Å⁻³
352 parameters

Crystal data top

2C₅H₇N₅⁺·2HSO₄⁻·SO₄²⁻	V = 3885.2 (15) Å³
M_r = 564.54	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 26.370 (5) Å	µ = 0.48 mm⁻¹
b = 8.970 (2) Å	T = 120 K
c = 20.350 (4) Å	0.3 × 0.3 × 0.2 mm
β = 126.184 (10)°

Data collection top

Nonius KappaCCD diffractometer	3989 reflections with I > 2σ(I)
5681 measured reflections	R_int = 0.000
5681 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	12 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.09 e Å⁻³
5681 reflections	Δρ_min = −0.60 e Å⁻³
352 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
N1A	0.20719 (9)	0.0944 (2)	0.05345 (11)	0.0164 (5)
N2A	0.27322 (9)	0.0677 (2)	0.19479 (12)	0.0196 (6)
N3A	0.18368 (9)	0.3217 (2)	−0.01909 (11)	0.0177 (5)
N7A	0.28666 (9)	0.4136 (2)	0.19011 (11)	0.0161 (5)
N9A	0.23914 (9)	0.5305 (2)	0.07420 (11)	0.0171 (5)
C2A	0.17772 (10)	0.1776 (3)	−0.01588 (13)	0.0177 (6)
C4A	0.22262 (10)	0.3823 (2)	0.05632 (13)	0.0145 (6)
C5A	0.25287 (10)	0.3085 (2)	0.12903 (13)	0.0149 (6)
C6A	0.24601 (10)	0.1527 (2)	0.12997 (13)	0.0153 (6)
C8A	0.27706 (10)	0.5455 (2)	0.15458 (14)	0.0172 (6)
N1B	0.05771 (9)	0.5676 (2)	0.20961 (12)	0.0179 (5)
N2B	−0.01182 (9)	0.5628 (2)	0.06749 (12)	0.0172 (5)
N3B	0.08777 (9)	0.7852 (2)	0.29107 (12)	0.0206 (6)
N7B	−0.02158 (9)	0.9017 (2)	0.08688 (12)	0.0168 (5)
N9B	0.03572 (9)	1.0065 (2)	0.20639 (12)	0.0196 (6)
C2B	0.09047 (11)	0.6417 (3)	0.28198 (14)	0.0203 (7)
C4B	0.04770 (10)	0.8566 (3)	0.21910 (13)	0.0164 (6)
C5B	0.01143 (10)	0.7901 (2)	0.14346 (13)	0.0154 (6)
C6B	0.01706 (10)	0.6360 (2)	0.13545 (13)	0.0154 (6)
C8B	−0.00578 (10)	1.0302 (3)	0.12637 (13)	0.0179 (6)
S2	0.12525 (3)	0.26071 (6)	0.38069 (3)	0.0165 (2)
O5	0.08129 (8)	0.35729 (19)	0.39253 (10)	0.0234 (5)
O6	0.12578 (9)	0.1108 (2)	0.40732 (12)	0.0339 (6)
O7	0.09306 (9)	0.2668 (2)	0.29303 (11)	0.0294 (6)
O8	0.18679 (8)	0.3294 (2)	0.42607 (11)	0.0332 (6)
S3	0.11514 (3)	0.24895 (6)	0.13708 (3)	0.0156 (2)
O9	0.17374 (8)	0.3204 (2)	0.20016 (10)	0.0253 (5)
O10	0.05962 (7)	0.30655 (18)	0.12953 (10)	0.0202 (5)
O11	0.12193 (8)	0.08329 (18)	0.16194 (10)	0.0213 (5)
O12	0.10420 (8)	0.24888 (17)	0.05736 (9)	0.0179 (4)
S1	0.13614 (3)	0.77672 (6)	0.08987 (3)	0.0152 (2)
O1	0.09098 (8)	0.90674 (18)	0.05182 (10)	0.0216 (5)
O2	0.19547 (7)	0.81613 (18)	0.10101 (10)	0.0204 (5)
O3	0.14779 (8)	0.74736 (17)	0.16871 (9)	0.0191 (5)
O4	0.10611 (7)	0.64802 (18)	0.03559 (9)	0.0201 (5)
H1A	0.2012 (12)	−0.0058 (19)	0.0530 (15)	0.0240*
H2A	0.15110	0.12780	−0.06510	0.0210*
H7A	0.3078 (11)	0.393 (3)	0.2428 (10)	0.0240*
H8A	0.29440	0.63500	0.18200	0.0210*
H9A	0.2268 (12)	0.602 (2)	0.0373 (13)	0.0240*
H21A	0.2959 (11)	0.105 (3)	0.2450 (11)	0.0240*
H22A	0.2669 (12)	−0.0326 (19)	0.1924 (15)	0.0240*
H1B	0.0625 (12)	0.4704 (19)	0.2105 (16)	0.0240*
H2B	0.11700	0.58560	0.32890	0.0240*
H7B	−0.0488 (10)	0.891 (3)	0.0315 (10)	0.0240*
H8B	−0.02120	1.12300	0.10210	0.0210*
H9B	0.0541 (11)	1.081 (2)	0.2402 (13)	0.0240*
H21B	−0.0057 (12)	0.4657 (19)	0.0680 (16)	0.0240*
H22B	−0.0407 (10)	0.611 (3)	0.0202 (12)	0.0240*
H5	0.0918 (12)	0.357 (3)	0.4403 (11)	0.0300*
H11	0.1146 (13)	0.026 (3)	0.1202 (13)	0.0300*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0185 (9)	0.0135 (9)	0.0155 (9)	−0.0025 (7)	0.0091 (8)	−0.0015 (7)
N2A	0.0237 (10)	0.0134 (9)	0.0181 (10)	−0.0018 (8)	0.0103 (9)	0.0027 (8)
N3A	0.0184 (9)	0.0176 (9)	0.0161 (9)	−0.0003 (8)	0.0096 (8)	0.0000 (7)
N7A	0.0170 (9)	0.0137 (9)	0.0151 (9)	−0.0006 (7)	0.0081 (8)	−0.0010 (7)
N9A	0.0192 (9)	0.0114 (9)	0.0176 (9)	0.0011 (7)	0.0092 (8)	0.0022 (7)
C2A	0.0167 (10)	0.0194 (11)	0.0158 (11)	−0.0008 (9)	0.0089 (9)	−0.0038 (8)
C4A	0.0153 (10)	0.0132 (10)	0.0150 (10)	0.0004 (8)	0.0090 (9)	0.0019 (8)
C5A	0.0155 (10)	0.0135 (10)	0.0140 (10)	−0.0015 (8)	0.0078 (9)	−0.0014 (8)
C6A	0.0157 (10)	0.0135 (10)	0.0169 (11)	−0.0006 (8)	0.0098 (9)	−0.0011 (8)
C8A	0.0169 (10)	0.0131 (10)	0.0206 (11)	0.0006 (8)	0.0106 (10)	−0.0011 (8)
N1B	0.0173 (9)	0.0137 (9)	0.0185 (10)	0.0014 (7)	0.0083 (8)	0.0004 (7)
N2B	0.0200 (9)	0.0117 (9)	0.0166 (9)	0.0004 (7)	0.0090 (8)	−0.0016 (7)
N3B	0.0204 (10)	0.0216 (10)	0.0159 (9)	0.0004 (8)	0.0085 (8)	−0.0001 (8)
N7B	0.0160 (9)	0.0132 (9)	0.0178 (10)	0.0007 (7)	0.0081 (8)	0.0006 (7)
N9B	0.0195 (10)	0.0148 (9)	0.0217 (10)	−0.0024 (8)	0.0106 (9)	−0.0054 (8)
C2B	0.0183 (11)	0.0223 (12)	0.0175 (11)	0.0008 (9)	0.0090 (10)	0.0019 (9)
C4B	0.0160 (10)	0.0168 (11)	0.0172 (11)	−0.0009 (8)	0.0102 (9)	−0.0033 (8)
C5B	0.0142 (10)	0.0140 (10)	0.0173 (10)	−0.0011 (8)	0.0090 (9)	0.0002 (8)
C6B	0.0155 (10)	0.0143 (10)	0.0182 (11)	−0.0002 (8)	0.0110 (9)	0.0021 (8)
C8B	0.0168 (10)	0.0170 (11)	0.0210 (11)	−0.0003 (9)	0.0118 (10)	−0.0005 (9)
S2	0.0199 (3)	0.0132 (3)	0.0163 (3)	0.0007 (2)	0.0107 (2)	−0.0011 (2)
O5	0.0289 (9)	0.0221 (9)	0.0216 (9)	0.0104 (7)	0.0162 (8)	0.0040 (7)
O6	0.0460 (12)	0.0167 (9)	0.0509 (12)	0.0040 (8)	0.0351 (11)	0.0044 (8)
O7	0.0392 (11)	0.0308 (10)	0.0184 (9)	0.0032 (8)	0.0171 (8)	−0.0005 (7)
O8	0.0261 (9)	0.0396 (11)	0.0318 (10)	−0.0102 (8)	0.0160 (9)	−0.0156 (9)
S3	0.0160 (3)	0.0147 (3)	0.0138 (3)	0.0010 (2)	0.0076 (2)	−0.0010 (2)
O9	0.0218 (8)	0.0263 (9)	0.0206 (9)	−0.0052 (7)	0.0086 (7)	−0.0057 (7)
O10	0.0217 (8)	0.0174 (8)	0.0230 (8)	0.0054 (7)	0.0141 (7)	0.0024 (7)
O11	0.0288 (9)	0.0144 (8)	0.0202 (9)	0.0053 (7)	0.0142 (8)	0.0019 (6)
O12	0.0215 (8)	0.0173 (8)	0.0137 (7)	−0.0002 (6)	0.0098 (7)	−0.0006 (6)
S1	0.0166 (3)	0.0123 (2)	0.0142 (3)	−0.0005 (2)	0.0078 (2)	−0.0011 (2)
O1	0.0240 (8)	0.0167 (8)	0.0180 (8)	0.0063 (7)	0.0091 (7)	0.0021 (6)
O2	0.0212 (8)	0.0141 (8)	0.0258 (9)	−0.0035 (6)	0.0139 (7)	−0.0023 (7)
O3	0.0252 (8)	0.0175 (8)	0.0132 (8)	0.0008 (6)	0.0105 (7)	0.0007 (6)
O4	0.0246 (8)	0.0145 (8)	0.0208 (8)	−0.0061 (7)	0.0132 (7)	−0.0058 (6)

Geometric parameters (Å, º) top

S2—O7	1.4553 (19)	N2A—H22A	0.911 (18)
S2—O8	1.448 (2)	N7A—H7A	0.888 (17)
S2—O5	1.576 (2)	N9A—H9A	0.89 (2)
S2—O6	1.447 (2)	N1B—C6B	1.376 (3)
S3—O10	1.473 (2)	N1B—C2B	1.362 (3)
S3—O9	1.451 (2)	N2B—C6B	1.296 (3)
S3—O12	1.4705 (18)	N3B—C2B	1.308 (3)
S3—O11	1.5457 (17)	N3B—C4B	1.358 (3)
S1—O3	1.4683 (18)	N7B—C5B	1.379 (3)
S1—O2	1.485 (2)	N7B—C8B	1.324 (3)
S1—O1	1.513 (2)	N9B—C8B	1.338 (3)
S1—O4	1.4653 (17)	N9B—C4B	1.371 (3)
O5—H5	0.84 (2)	N1B—H1B	0.880 (18)
O11—H11	0.91 (3)	N2B—H22B	0.91 (2)
N1A—C2A	1.363 (3)	N2B—H21B	0.885 (18)
N1A—C6A	1.365 (3)	N7B—H7B	0.916 (17)
N2A—C6A	1.311 (3)	N9B—H9B	0.87 (2)
N3A—C4A	1.358 (3)	C4A—C5A	1.368 (3)
N3A—C2A	1.308 (3)	C5A—C6A	1.411 (3)
N7A—C8A	1.331 (3)	C2A—H2A	0.9300
N7A—C5A	1.386 (3)	C8A—H8A	0.9300
N9A—C4A	1.379 (3)	C4B—C5B	1.379 (3)
N9A—C8A	1.328 (3)	C5B—C6B	1.410 (3)
N1A—H1A	0.912 (18)	C2B—H2B	0.9300
N2A—H21A	0.89 (2)	C8B—H8B	0.9300

O7—S2—O8	112.88 (14)	C2B—N1B—H1B	118.0 (17)
O5—S2—O7	102.56 (12)	H21B—N2B—H22B	121 (2)
O5—S2—O8	108.50 (11)	C6B—N2B—H21B	119.9 (17)
O5—S2—O6	107.40 (14)	C6B—N2B—H22B	119.1 (16)
O6—S2—O8	113.41 (13)	C8B—N7B—H7B	125.1 (17)
O6—S2—O7	111.33 (11)	C5B—N7B—H7B	126.9 (17)
O9—S3—O12	112.90 (13)	C8B—N9B—H9B	120.8 (13)
O9—S3—O11	106.15 (11)	C4B—N9B—H9B	130.1 (14)
O9—S3—O10	114.29 (11)	N1A—C2A—N3A	125.5 (2)
O11—S3—O12	105.67 (10)	N3A—C4A—C5A	126.71 (18)
O10—S3—O11	106.70 (12)	N9A—C4A—C5A	106.83 (18)
O10—S3—O12	110.47 (11)	N3A—C4A—N9A	126.46 (19)
O1—S1—O4	108.04 (10)	C4A—C5A—C6A	119.78 (19)
O3—S1—O4	110.72 (10)	N7A—C5A—C6A	132.96 (19)
O1—S1—O2	109.55 (11)	N7A—C5A—C4A	107.26 (16)
O1—S1—O3	106.93 (12)	N1A—C6A—C5A	112.32 (18)
O2—S1—O4	110.76 (12)	N1A—C6A—N2A	121.42 (18)
O2—S1—O3	110.73 (11)	N2A—C6A—C5A	126.3 (2)
S2—O5—H5	114 (2)	N7A—C8A—N9A	110.04 (18)
S3—O11—H11	108.5 (17)	N3A—C2A—H2A	117.00
C2A—N1A—C6A	123.81 (19)	N1A—C2A—H2A	117.00
C2A—N3A—C4A	111.84 (18)	N7A—C8A—H8A	125.00
C5A—N7A—C8A	107.59 (18)	N9A—C8A—H8A	125.00
C4A—N9A—C8A	108.28 (17)	N1B—C2B—N3B	125.5 (2)
C6A—N1A—H1A	113.5 (16)	N9B—C4B—C5B	106.44 (19)
C2A—N1A—H1A	122.7 (16)	N3B—C4B—C5B	125.8 (2)
H21A—N2A—H22A	114 (2)	N3B—C4B—N9B	127.7 (2)
C6A—N2A—H22A	123.1 (16)	C4B—C5B—C6B	120.1 (2)
C6A—N2A—H21A	122.3 (17)	N7B—C5B—C4B	107.33 (18)
C5A—N7A—H7A	123.7 (17)	N7B—C5B—C6B	132.3 (2)
C8A—N7A—H7A	128.6 (17)	N1B—C6B—N2B	122.07 (18)
C4A—N9A—H9A	124.8 (13)	N2B—C6B—C5B	125.8 (2)
C8A—N9A—H9A	126.9 (13)	N1B—C6B—C5B	112.17 (18)
C2B—N1B—C6B	123.68 (19)	N7B—C8B—N9B	109.8 (2)
C2B—N3B—C4B	112.6 (2)	N3B—C2B—H2B	117.00
C5B—N7B—C8B	107.93 (19)	N1B—C2B—H2B	117.00
C4B—N9B—C8B	108.5 (2)	N9B—C8B—H8B	125.00
C6B—N1B—H1B	118.3 (17)	N7B—C8B—H8B	125.00

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4ⁱ	0.84 (2)	1.74 (2)	2.580 (2)	174 (3)
O11—H11···O1ⁱⁱ	0.91 (3)	1.56 (2)	2.457 (2)	166 (4)
N1A—H1A···O2ⁱⁱ	0.912 (18)	1.92 (2)	2.760 (3)	151 (3)
N1A—H1A···O6ⁱⁱⁱ	0.912 (18)	2.58 (2)	3.050 (3)	112.5 (18)
N1B—H1B···O7	0.880 (18)	2.28 (2)	3.027 (3)	142 (2)
N1B—H1B···O10	0.880 (18)	2.18 (2)	2.870 (3)	136 (2)
N2A—H21A···O3^iv	0.89 (2)	1.96 (2)	2.796 (3)	156 (2)
N2A—H22A···O2ⁱⁱ	0.911 (18)	2.17 (2)	2.884 (3)	135 (2)
N2A—H22A···O9^iv	0.911 (18)	2.22 (2)	2.814 (3)	122 (2)
N2B—H21B···O10	0.885 (18)	2.01 (3)	2.760 (3)	142 (3)
N2B—H21B···O4^v	0.885 (18)	2.43 (3)	2.829 (3)	108 (2)
N2B—H22B···O12^v	0.91 (2)	1.94 (2)	2.817 (3)	162 (2)
N7A—H7A···O3^iv	0.888 (17)	1.96 (2)	2.757 (2)	149 (2)
N7A—H7A···O11^vi	0.888 (17)	2.42 (2)	2.937 (3)	117 (2)
N7B—H7B···O1^vii	0.916 (17)	2.28 (2)	2.858 (3)	121 (2)
N7B—H7B···O12^v	0.916 (17)	1.97 (2)	2.763 (3)	145 (2)
N9A—H9A···O8^viii	0.89 (2)	1.95 (2)	2.767 (3)	152.3 (18)
N9B—H9B···O7^ix	0.87 (2)	1.920 (19)	2.775 (3)	166 (2)
C2A—H2A···O6ⁱⁱⁱ	0.93	2.21	2.913 (3)	131
C2A—H2A···N3B^viii	0.93	2.49	3.189 (3)	132
C8B—H8B···O10^ix	0.93	2.48	2.999 (3)	115
C8B—H8B···O1^vii	0.93	2.54	2.983 (3)	109

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

Experimental details

Crystal data
Chemical formula	2C₅H₇N₅⁺·2HSO₄⁻·SO₄²⁻
M_r	564.54
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	26.370 (5), 8.970 (2), 20.350 (4)
β (°)	126.184 (10)
V (Å³)	3885.2 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.3 × 0.3 × 0.2

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5681, 5681, 3989
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.131, 1.07
No. of reflections	5681
No. of parameters	352
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.09, −0.60

Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995), Mercury (Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4ⁱ	0.84 (2)	1.74 (2)	2.580 (2)	174 (3)
O11—H11···O1ⁱⁱ	0.91 (3)	1.56 (2)	2.457 (2)	166 (4)
N1A—H1A···O2ⁱⁱ	0.912 (18)	1.92 (2)	2.760 (3)	151 (3)
N1B—H1B···O7	0.880 (18)	2.28 (2)	3.027 (3)	142 (2)
N1B—H1B···O10	0.880 (18)	2.18 (2)	2.870 (3)	136 (2)
N2A—H21A···O3ⁱⁱⁱ	0.89 (2)	1.96 (2)	2.796 (3)	156 (2)
N2A—H22A···O2ⁱⁱ	0.911 (18)	2.17 (2)	2.884 (3)	135 (2)
N2A—H22A···O9ⁱⁱⁱ	0.911 (18)	2.22 (2)	2.814 (3)	122 (2)
N2B—H21B···O10	0.885 (18)	2.01 (3)	2.760 (3)	142 (3)
N2B—H22B···O12^iv	0.91 (2)	1.94 (2)	2.817 (3)	162 (2)
N7A—H7A···O3ⁱⁱⁱ	0.888 (17)	1.96 (2)	2.757 (2)	149 (2)
N7B—H7B···O1^v	0.916 (17)	2.28 (2)	2.858 (3)	121 (2)
N7B—H7B···O12^iv	0.916 (17)	1.97 (2)	2.763 (3)	145 (2)
N9A—H9A···O8^vi	0.89 (2)	1.95 (2)	2.767 (3)	152.3 (18)
N9B—H9B···O7^vii	0.87 (2)	1.920 (19)	2.775 (3)	166 (2)
C2A—H2A···O6^viii	0.93	2.21	2.913 (3)	131
C2A—H2A···N3B^vi	0.93	2.49	3.189 (3)	132

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

Acknowledgements

Technical support (X-ray measurements at SCDRX) from Université Henry Poincaré, Nancy 1, is gratefully acknowledged.

References

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