6-Amino-9H-purine-1,7-diium bis­(4-methyl­benzene­sulfonate) monohydrate

Xiong, Z.-Q.; Ai, Y.-L.; Wen, H.-L.

doi:10.1107/S1600536810000413

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o318

https://doi.org/10.1107/S1600536810000413

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6-Amino-9H-purine-1,7-diium bis(4-methylbenzenesulfonate) monohydrate

Zhi-Qiang Xiong,^a ^* Yun-Long Ai ^a and Hui-Liang Wen ^b

^aCenter of Analysis and Testing, Nanchang Hangkong University, Nanchang 330063, People's Republic of China, and ^bState Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047, People's Republic of China
^*Correspondence e-mail: xiongzq@163.com

(Received 12 November 2009; accepted 5 January 2010; online 9 January 2010)

The asymmetric unit of the title compound, C₅H₇N₅²⁺·2C₇H₇O₃S⁻·H₂O, consists of one diprotonated adeninium cation, two p-toluenesulfonic acid anions and one water molecule. In the crystal, the cations and anions are connected through N—H⋯O hydrogen bonds forming R₂²(8) and R₂²(9) graph-set motifs. The solvent water molecule links cations and anions through O—H⋯O and N—H⋯O hydrogen bonds, generating a two-dimensional layer parallel to (10 $[\overline{1}]$ ).

Related literature

For biological activity of purine and its derivatives, see: Barral et al. (2006 ); Sridhar & Ravikumar (2007 ); Sridhar et al. (2009 ); Xing et al. (2008 ). For hydrogen-bonding motifs, see: Etter (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₅H₇N₅²⁺·2C₇H₇O₃S⁻·H₂O
M_r = 497.54
Monoclinic, P 2₁ /n
a = 16.2462 (11) Å
b = 6.0370 (4) Å
c = 22.7390 (15) Å
β = 90.625 (1)°
V = 2230.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.31 × 0.21 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.915, T_max = 0.942
16652 measured reflections
4153 independent reflections
3452 reflections with I > 2σ(I)
R_int = 0.100

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 1.05
4153 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4	0.86	1.95	2.813 (2)	178
N1—H1B⋯O3	0.86	1.97	2.805 (2)	163
N2—H2A⋯O5	0.86	1.84	2.694 (2)	178
N4—H4⋯O7ⁱ	0.86	1.80	2.653 (2)	170
N5—H5A⋯O1	0.86	2.09	2.884 (3)	152
N5—H5A⋯O3	0.86	2.43	3.149 (3)	141
O7—H1W⋯O6ⁱⁱ	0.84	1.93	2.762 (2)	176
O7—H2W⋯O2	0.83	2.04	2.815 (2)	156
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and CAMERON (Pearce et al., 2000 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000413/dn2513sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000413/dn2513Isup2.hkl

checkCIF report

Comment top

Purin and its derivatives, as one kind of important nucleobase compounds, are essential for understanding many mechanisms of basic importance in the biological process (Xing et al., 2008), and belongs to a group of cytokinin-derived compounds which are indispensable for plant growth. The concept of the acyclic nucleoside phosphonate (ANPs) has been used to design chain terminators for antiviral and therapy proved to be valid (Barral et al., 2006). In C₅H₆N₅⁺.C₈H₇O₂^–.C₈H₈O₂^–.H₂O and C₅H₆N₅⁺.C₄H₃O₄^–.H₂O compounds, the adeninium cations form N-H···O hydrogen bonds with their anion counterparts and adeninium-adeninium self-association base pairs (Sridhar et al., 2007). In C₅H₇N₅²⁺.0.5C₂O₄^2–.2Cl^–compound, adenine is doubly protonated, while in C₅H₆N₅⁺.C₂HO₄^–.0.5C₂H₂O₄.H₂O compound, adenine is monoprotonated (Sridhar et al., 2009).

In the title compound, C₅H₇N₅²⁺.2C₇H₇SO₃^–.H₂O, the asymmetric unit contains one diprotonated adeninium cation, two p-toluenesulfonic acid anions and one water molecule. The two anions are connected to the purin molecule through N-H···O hydrogen bonds building R₂²(8) and R₂²(9) graph set motifs (Table 1, Fig.1) (Etter, 1990; Bernstein et al., 1995) . In the same asymmetric unit, the water molecule is connected through O-H···O hydrogen bond to one of the p-toluenesulfonic acid (Table 1, Fig. 1).

Futhermore The water links cation and anion through O-H···O and N-H···O hydrogen bonds forming a R66(20) graph set motif and buiding a two dimensional layer parallel to the (1 0 -1) plane (Fig. 2, Table 1).

In the 9H-purin-6-amine molecule, all atoms are coplanar, the dihedral angles between the plane of the 9H-purin-6-amine and the benzene rings of the p-toluenesulfonate anions are 87.78 (5)° and 87.15 (5)°, respectively, indicating that the 9H-purin-6-amine is almost perpendicular to the two benzene rings.

Related literature top

For biological activity of purin and its derivatives, see: Barral et al. (2006); Sridhar & Ravikumar (2007); Sridhar et al. (2009); Xing et al. (2008). For hydrogen-bonding motifs, see: Etter (1990); Bernstein et al. (1995).

Experimental top

A mixture of purin-6-amine (10.0 mmol) and toluene sulfonic acid (20.0 mmol) was dissolved in ethanol (40 ml) in batches over a period of 2 h under reflux, heating was continued for 1 h. The mixture was cooled to room temperature and separated, the solvent of the organic phase was removed and the residue recrystallized with ethyl acetate. Yellow crystals of the title compound suitable for X-ray diffraction analysis were obtained after several days. Yield 77.3%.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Pearce et al., 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. : Partial packing view of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines.

6-Amino-9H-purine-1,7-diium bis(4-methylbenzenesulfonate) monohydrate top

Crystal data top

C₅H₇N₅²⁺·2C₇H₇O₃S⁻·H₂O	F(000) = 1040
M_r = 497.54	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7679 reflections
a = 16.2462 (11) Å	θ = 2.5–28.1°
b = 6.0370 (4) Å	µ = 0.29 mm⁻¹
c = 22.7390 (15) Å	T = 296 K
β = 90.625 (1)°	Block, yellow
V = 2230.1 (3) Å³	0.31 × 0.21 × 0.21 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	4153 independent reflections
Radiation source: fine-focus sealed tube	3452 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.100
φ and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −19→19
T_min = 0.915, T_max = 0.942	k = −7→7
16652 measured reflections	l = −27→26

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.059P)² + 0.6101P] where P = (F_o² + 2F_c²)/3
4153 reflections	(Δ/σ)_max < 0.001
300 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₅H₇N₅²⁺·2C₇H₇O₃S⁻·H₂O	V = 2230.1 (3) Å³
M_r = 497.54	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 16.2462 (11) Å	µ = 0.29 mm⁻¹
b = 6.0370 (4) Å	T = 296 K
c = 22.7390 (15) Å	0.31 × 0.21 × 0.21 mm
β = 90.625 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4153 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	3452 reflections with I > 2σ(I)
T_min = 0.915, T_max = 0.942	R_int = 0.100
16652 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.46 e Å⁻³
4153 reflections	Δρ_min = −0.31 e Å⁻³
300 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.58230 (11)	0.6806 (3)	0.70038 (8)	0.0345 (4)
C2	0.68007 (12)	0.9106 (3)	0.75121 (9)	0.0424 (5)
H2	0.7096	0.9311	0.7860	0.051*
C3	0.64254 (11)	1.0129 (3)	0.66210 (8)	0.0342 (4)
C4	0.58820 (11)	0.8401 (3)	0.65534 (8)	0.0342 (4)
C5	0.58704 (13)	1.0362 (3)	0.57478 (9)	0.0439 (5)
H5	0.5744	1.0860	0.5371	0.053*
C6	0.12147 (18)	0.2967 (6)	0.73440 (13)	0.0827 (9)
H6A	0.1439	0.2918	0.7736	0.124*
H6B	0.0967	0.1566	0.7250	0.124*
H6C	0.0806	0.4113	0.7319	0.124*
C7	0.18958 (15)	0.3450 (4)	0.69138 (11)	0.0578 (6)
C8	0.19569 (15)	0.5466 (4)	0.66313 (11)	0.0605 (6)
H8	0.1573	0.6566	0.6709	0.073*
C9	0.25782 (14)	0.5885 (4)	0.62340 (10)	0.0523 (5)
H9	0.2609	0.7254	0.6048	0.063*
C10	0.31520 (12)	0.4262 (3)	0.61154 (9)	0.0410 (5)
C11	0.30975 (16)	0.2236 (4)	0.63958 (11)	0.0577 (6)
H11	0.3479	0.1129	0.6318	0.069*
C12	0.24765 (16)	0.1866 (4)	0.67901 (12)	0.0653 (7)
H12	0.2449	0.0501	0.6979	0.078*
C13	0.30034 (16)	0.4904 (5)	1.01182 (12)	0.0714 (8)
H13A	0.2502	0.4442	0.9928	0.107*
H13B	0.2984	0.6471	1.0189	0.107*
H13C	0.3066	0.4135	1.0485	0.107*
C14	0.37220 (13)	0.4378 (4)	0.97288 (9)	0.0470 (5)
C15	0.40420 (16)	0.5906 (4)	0.93554 (12)	0.0622 (7)
H15	0.3813	0.7317	0.9344	0.075*
C16	0.46944 (16)	0.5434 (4)	0.89932 (11)	0.0595 (6)
H16	0.4907	0.6524	0.8749	0.071*
C17	0.50300 (12)	0.3336 (3)	0.89954 (8)	0.0374 (4)
C18	0.47223 (15)	0.1783 (4)	0.93719 (10)	0.0558 (6)
H18	0.4949	0.0369	0.9382	0.067*
C19	0.40759 (15)	0.2304 (4)	0.97374 (11)	0.0599 (6)
H19	0.3876	0.1236	0.9994	0.072*
N1	0.53750 (11)	0.5001 (3)	0.69920 (7)	0.0431 (4)
H1A	0.5384	0.4109	0.7287	0.052*
H1B	0.5072	0.4708	0.6689	0.052*
N2	0.63051 (10)	0.7299 (3)	0.74765 (7)	0.0397 (4)
H2A	0.6296	0.6412	0.7772	0.048*
N3	0.68966 (10)	1.0571 (3)	0.71004 (7)	0.0398 (4)
N4	0.64043 (10)	1.1311 (3)	0.61096 (7)	0.0394 (4)
H4	0.6690	1.2476	0.6036	0.047*
N5	0.55420 (10)	0.8603 (3)	0.59990 (7)	0.0416 (4)
H5A	0.5180	0.7738	0.5844	0.050*
O1	0.40025 (13)	0.7072 (3)	0.55042 (8)	0.0729 (5)
O2	0.37421 (11)	0.3460 (3)	0.50891 (7)	0.0669 (5)
O3	0.46938 (10)	0.3929 (4)	0.58895 (7)	0.0720 (5)
O4	0.53719 (10)	0.2035 (3)	0.79461 (6)	0.0519 (4)
O5	0.63123 (10)	0.4573 (3)	0.84146 (6)	0.0547 (4)
O6	0.62452 (10)	0.0766 (3)	0.87476 (7)	0.0567 (4)
O7	0.28741 (10)	0.4810 (2)	0.40726 (7)	0.0553 (4)
H1W	0.2375	0.4616	0.3992	0.083*
H2W	0.2988	0.4323	0.4403	0.083*
S1	0.57997 (3)	0.26166 (8)	0.84914 (2)	0.04219 (17)
S2	0.39453 (3)	0.47017 (9)	0.56027 (2)	0.04297 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0338 (9)	0.0381 (10)	0.0317 (9)	0.0065 (8)	0.0063 (8)	0.0004 (7)
C2	0.0416 (11)	0.0517 (12)	0.0336 (10)	0.0055 (9)	−0.0047 (8)	−0.0050 (9)
C3	0.0328 (9)	0.0382 (9)	0.0316 (9)	0.0051 (7)	0.0052 (7)	−0.0012 (7)
C4	0.0346 (9)	0.0406 (10)	0.0275 (9)	0.0017 (8)	0.0024 (7)	0.0000 (7)
C5	0.0521 (12)	0.0470 (11)	0.0326 (10)	−0.0033 (9)	−0.0002 (9)	0.0057 (8)
C6	0.0648 (17)	0.112 (2)	0.0718 (19)	−0.0161 (16)	0.0225 (15)	0.0054 (17)
C7	0.0492 (13)	0.0741 (16)	0.0503 (13)	−0.0088 (12)	0.0086 (10)	0.0015 (12)
C8	0.0550 (14)	0.0653 (15)	0.0614 (15)	0.0093 (12)	0.0104 (12)	−0.0015 (12)
C9	0.0560 (13)	0.0478 (12)	0.0531 (13)	0.0019 (10)	0.0022 (11)	0.0063 (10)
C10	0.0415 (11)	0.0442 (11)	0.0372 (10)	−0.0045 (9)	−0.0008 (8)	0.0013 (8)
C11	0.0584 (14)	0.0510 (13)	0.0639 (15)	0.0063 (11)	0.0151 (12)	0.0119 (11)
C12	0.0716 (17)	0.0554 (14)	0.0692 (16)	−0.0057 (12)	0.0161 (13)	0.0190 (12)
C13	0.0567 (15)	0.096 (2)	0.0615 (16)	0.0150 (14)	0.0110 (13)	−0.0165 (14)
C14	0.0411 (11)	0.0591 (13)	0.0408 (11)	0.0044 (10)	0.0006 (9)	−0.0061 (10)
C15	0.0678 (16)	0.0438 (12)	0.0752 (17)	0.0182 (11)	0.0124 (13)	0.0016 (11)
C16	0.0696 (16)	0.0404 (11)	0.0687 (16)	0.0089 (11)	0.0183 (13)	0.0168 (11)
C17	0.0373 (10)	0.0396 (10)	0.0354 (10)	0.0028 (8)	0.0009 (8)	0.0067 (8)
C18	0.0631 (14)	0.0431 (11)	0.0616 (14)	0.0145 (11)	0.0203 (12)	0.0172 (10)
C19	0.0622 (15)	0.0613 (15)	0.0568 (14)	0.0064 (11)	0.0233 (12)	0.0174 (11)
N1	0.0495 (10)	0.0433 (9)	0.0364 (9)	−0.0034 (8)	0.0008 (7)	0.0074 (7)
N2	0.0455 (9)	0.0448 (9)	0.0286 (8)	0.0059 (7)	0.0007 (7)	0.0048 (7)
N3	0.0354 (9)	0.0472 (9)	0.0368 (9)	0.0007 (7)	−0.0010 (7)	−0.0037 (7)
N4	0.0404 (9)	0.0411 (9)	0.0367 (9)	−0.0048 (7)	0.0047 (7)	0.0043 (7)
N5	0.0485 (10)	0.0443 (9)	0.0319 (8)	−0.0097 (8)	−0.0050 (7)	0.0037 (7)
O1	0.0845 (13)	0.0551 (10)	0.0795 (13)	−0.0160 (9)	0.0234 (10)	0.0090 (9)
O2	0.0717 (11)	0.0869 (12)	0.0421 (9)	−0.0227 (10)	0.0037 (8)	−0.0136 (8)
O3	0.0437 (9)	0.1191 (16)	0.0532 (10)	0.0023 (10)	−0.0032 (8)	−0.0017 (10)
O4	0.0592 (9)	0.0593 (9)	0.0374 (8)	−0.0005 (7)	0.0032 (7)	0.0043 (7)
O5	0.0508 (9)	0.0690 (10)	0.0443 (9)	−0.0112 (7)	0.0028 (7)	0.0169 (7)
O6	0.0532 (9)	0.0628 (10)	0.0543 (9)	0.0222 (8)	0.0087 (7)	0.0125 (7)
O7	0.0526 (9)	0.0561 (9)	0.0571 (9)	−0.0114 (7)	0.0004 (8)	0.0093 (7)
S1	0.0414 (3)	0.0495 (3)	0.0358 (3)	0.0052 (2)	0.0047 (2)	0.0099 (2)
S2	0.0426 (3)	0.0509 (3)	0.0354 (3)	−0.0092 (2)	0.0005 (2)	0.0004 (2)

Geometric parameters (Å, º) top

C1—N1	1.311 (2)	C13—C14	1.507 (3)
C1—N2	1.356 (2)	C13—H13A	0.9600
C1—C4	1.410 (3)	C13—H13B	0.9600
C2—N3	1.299 (3)	C13—H13C	0.9600
C2—N2	1.357 (3)	C14—C15	1.361 (3)
C2—H2	0.9300	C14—C19	1.377 (3)
C3—N3	1.352 (2)	C15—C16	1.379 (3)
C3—N4	1.365 (2)	C15—H15	0.9300
C3—C4	1.374 (3)	C16—C17	1.379 (3)
C4—N5	1.376 (2)	C16—H16	0.9300
C5—N4	1.320 (3)	C17—C18	1.368 (3)
C5—N5	1.321 (3)	C17—S1	1.760 (2)
C5—H5	0.9300	C18—C19	1.382 (3)
C6—C7	1.513 (3)	C18—H18	0.9300
C6—H6A	0.9600	C19—H19	0.9300
C6—H6B	0.9600	N1—H1A	0.8602
C6—H6C	0.9600	N1—H1B	0.8608
C7—C12	1.374 (4)	N2—H2A	0.8595
C7—C8	1.380 (4)	N4—H4	0.8601
C8—C9	1.385 (3)	N5—H5A	0.8592
C8—H8	0.9300	O1—S2	1.4513 (18)
C9—C10	1.381 (3)	O2—S2	1.4237 (16)
C9—H9	0.9300	O3—S2	1.4506 (17)
C10—C11	1.383 (3)	O4—S1	1.4576 (16)
C10—S2	1.767 (2)	O5—S1	1.4569 (16)
C11—C12	1.375 (3)	O6—S1	1.4498 (15)
C11—H11	0.9300	O7—H1W	0.8376
C12—H12	0.9300	O7—H2W	0.8259

N1—C1—N2	120.98 (17)	C15—C14—C19	117.6 (2)
N1—C1—C4	126.53 (17)	C15—C14—C13	121.8 (2)
N2—C1—C4	112.49 (17)	C19—C14—C13	120.6 (2)
N3—C2—N2	125.47 (18)	C14—C15—C16	122.3 (2)
N3—C2—H2	117.3	C14—C15—H15	118.9
N2—C2—H2	117.3	C16—C15—H15	118.9
N3—C3—N4	126.33 (17)	C17—C16—C15	119.6 (2)
N3—C3—C4	126.72 (17)	C17—C16—H16	120.2
N4—C3—C4	106.96 (16)	C15—C16—H16	120.2
C3—C4—N5	106.63 (16)	C18—C17—C16	119.0 (2)
C3—C4—C1	119.08 (17)	C18—C17—S1	120.36 (16)
N5—C4—C1	134.12 (18)	C16—C17—S1	120.54 (16)
N4—C5—N5	110.20 (17)	C17—C18—C19	120.4 (2)
N4—C5—H5	124.9	C17—C18—H18	119.8
N5—C5—H5	124.9	C19—C18—H18	119.8
C7—C6—H6A	109.5	C14—C19—C18	121.2 (2)
C7—C6—H6B	109.5	C14—C19—H19	119.4
H6A—C6—H6B	109.5	C18—C19—H19	119.4
C7—C6—H6C	109.5	C1—N1—H1A	120.0
H6A—C6—H6C	109.5	C1—N1—H1B	120.0
H6B—C6—H6C	109.5	H1A—N1—H1B	120.0
C12—C7—C8	117.7 (2)	C1—N2—C2	124.11 (16)
C12—C7—C6	120.5 (2)	C1—N2—H2A	117.9
C8—C7—C6	121.8 (2)	C2—N2—H2A	118.0
C7—C8—C9	121.4 (2)	C2—N3—C3	112.03 (17)
C7—C8—H8	119.3	C5—N4—C3	108.31 (16)
C9—C8—H8	119.3	C5—N4—H4	125.9
C10—C9—C8	119.7 (2)	C3—N4—H4	125.8
C10—C9—H9	120.1	C5—N5—C4	107.90 (16)
C8—C9—H9	120.1	C5—N5—H5A	126.1
C9—C10—C11	119.4 (2)	C4—N5—H5A	126.0
C9—C10—S2	121.40 (16)	H1W—O7—H2W	110.9
C11—C10—S2	119.21 (17)	O6—S1—O5	112.91 (10)
C12—C11—C10	119.7 (2)	O6—S1—O4	112.80 (10)
C12—C11—H11	120.1	O5—S1—O4	111.18 (9)
C10—C11—H11	120.1	O6—S1—C17	106.48 (9)
C7—C12—C11	122.0 (2)	O5—S1—C17	106.79 (10)
C7—C12—H12	119.0	O4—S1—C17	106.13 (9)
C11—C12—H12	119.0	O2—S2—O3	112.64 (12)
C14—C13—H13A	109.5	O2—S2—O1	114.04 (12)
C14—C13—H13B	109.5	O3—S2—O1	109.38 (13)
H13A—C13—H13B	109.5	O2—S2—C10	107.32 (10)
C14—C13—H13C	109.5	O3—S2—C10	105.60 (10)
H13A—C13—H13C	109.5	O1—S2—C10	107.35 (10)
H13B—C13—H13C	109.5

N3—C3—C4—N5	−179.98 (17)	C13—C14—C19—C18	178.4 (2)
N4—C3—C4—N5	−0.4 (2)	C17—C18—C19—C14	0.6 (4)
N3—C3—C4—C1	−4.1 (3)	N1—C1—N2—C2	178.16 (18)
N4—C3—C4—C1	175.47 (16)	C4—C1—N2—C2	−1.0 (3)
N1—C1—C4—C3	−175.61 (18)	N3—C2—N2—C1	−1.6 (3)
N2—C1—C4—C3	3.5 (2)	N2—C2—N3—C3	1.3 (3)
N1—C1—C4—N5	−1.2 (3)	N4—C3—N3—C2	−177.93 (18)
N2—C1—C4—N5	177.89 (19)	C4—C3—N3—C2	1.6 (3)
C12—C7—C8—C9	0.3 (4)	N5—C5—N4—C3	−0.2 (2)
C6—C7—C8—C9	−179.4 (2)	N3—C3—N4—C5	179.97 (18)
C7—C8—C9—C10	0.0 (4)	C4—C3—N4—C5	0.4 (2)
C8—C9—C10—C11	0.0 (3)	N4—C5—N5—C4	0.0 (2)
C8—C9—C10—S2	178.90 (18)	C3—C4—N5—C5	0.3 (2)
C9—C10—C11—C12	−0.3 (4)	C1—C4—N5—C5	−174.7 (2)
S2—C10—C11—C12	−179.2 (2)	C18—C17—S1—O6	−26.8 (2)
C8—C7—C12—C11	−0.6 (4)	C16—C17—S1—O6	157.08 (19)
C6—C7—C12—C11	179.1 (3)	C18—C17—S1—O5	−147.66 (19)
C10—C11—C12—C7	0.6 (4)	C16—C17—S1—O5	36.2 (2)
C19—C14—C15—C16	0.2 (4)	C18—C17—S1—O4	93.6 (2)
C13—C14—C15—C16	−179.4 (2)	C16—C17—S1—O4	−82.5 (2)
C14—C15—C16—C17	1.4 (4)	C9—C10—S2—O2	−106.24 (19)
C15—C16—C17—C18	−2.0 (4)	C11—C10—S2—O2	72.7 (2)
C15—C16—C17—S1	174.2 (2)	C9—C10—S2—O3	133.38 (19)
C16—C17—C18—C19	1.0 (4)	C11—C10—S2—O3	−47.7 (2)
S1—C17—C18—C19	−175.2 (2)	C9—C10—S2—O1	16.7 (2)
C15—C14—C19—C18	−1.2 (4)	C11—C10—S2—O1	−164.35 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.86	1.95	2.813 (2)	178
N1—H1B···O3	0.86	1.97	2.805 (2)	163
N2—H2A···O5	0.86	1.84	2.694 (2)	178
N4—H4···O7ⁱ	0.86	1.80	2.653 (2)	170
N5—H5A···O1	0.86	2.09	2.884 (3)	152
N5—H5A···O3	0.86	2.43	3.149 (3)	141
O7—H1W···O6ⁱⁱ	0.84	1.93	2.762 (2)	176
O7—H2W···O2	0.83	2.04	2.815 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₅H₇N₅²⁺·2C₇H₇O₃S⁻·H₂O
M_r	497.54
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	16.2462 (11), 6.0370 (4), 22.7390 (15)
β (°)	90.625 (1)
V (Å³)	2230.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.31 × 0.21 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.915, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	16652, 4153, 3452
R_int	0.100
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 1.05
No. of reflections	4153
No. of parameters	300
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Pearce et al., 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.86	1.95	2.813 (2)	178.1
N1—H1B···O3	0.86	1.97	2.805 (2)	163.3
N2—H2A···O5	0.86	1.84	2.694 (2)	177.8
N4—H4···O7ⁱ	0.86	1.80	2.653 (2)	169.5
N5—H5A···O1	0.86	2.09	2.884 (3)	152.4
N5—H5A···O3	0.86	2.43	3.149 (3)	141.1
O7—H1W···O6ⁱⁱ	0.84	1.93	2.762 (2)	175.7
O7—H2W···O2	0.83	2.04	2.815 (2)	156.00

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (20662007).

References

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