2,3-Diamino­pyridinium 3-carb­oxy-4-hy­droxy­benzene­sulfonate monohydrate

Hemamalini, M.; Goh, J.H.; Fun, H.-K.

doi:10.1107/S160053681104445X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3122

doi:10.1107/S160053681104445X

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2,3-Diaminopyridinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate

Madhukar Hemamalini,^a Jia Hao Goh ^a ‡ and Hoong-Kun Fun ^a ^*§

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 19 October 2011; accepted 25 October 2011; online 29 October 2011)

In the title hydrated molecular salt, C₅H₈N₃⁺·C₇H₅O₆S⁻·H₂O, the ion pairs and water molecules are connected by N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, thereby forming a three-dimensional network. There is an intramolecular O—H⋯O hydrogen bond in the 3-carboxy-4-hydroxybenzenesulfonate anion, which generates an S(6) ring motif.

Related literature

For background to 5-sulfosalicylic acid and related compounds, see: Marzotto et al. (2001 ); Onoda et al. (2001 ); Baskar Raj et al. (2003 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₅H₈N₃⁺·C₇H₅O₆S⁻·H₂O
M_r = 345.33
Monoclinic, C c
a = 7.0407 (7) Å
b = 15.5775 (16) Å
c = 13.6244 (12) Å
β = 101.491 (2)°
V = 1464.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.36 × 0.31 × 0.08 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.910, T_max = 0.981
6890 measured reflections
3880 independent reflections
3645 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.087
S = 1.03
3880 reflections
268 parameters
2 restraints
All H-atom parameters refined
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ), 1770 Friedel pairs
Flack parameter: −0.02 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1Wⁱ	0.91 (3)	1.95 (3)	2.806 (3)	158 (3)
N2—H1N2⋯O1ⁱ	0.90 (3)	2.48 (3)	3.222 (2)	140 (2)
N2—H1N2⋯O1Wⁱ	0.90 (3)	2.28 (3)	3.060 (3)	145 (2)
N2—H2N2⋯O2ⁱⁱ	0.86 (3)	2.10 (3)	2.963 (2)	177 (3)
N3—H1N3⋯O2ⁱⁱ	0.89 (3)	2.10 (3)	2.970 (3)	168 (3)
N3—H2N3⋯O4ⁱⁱⁱ	0.92 (3)	2.08 (3)	2.980 (3)	167 (3)
O1—H1O1⋯O6	1.03 (3)	1.75 (3)	2.625 (2)	141 (2)
O5—H1O5⋯O3^iv	0.84 (3)	1.87 (3)	2.655 (2)	155 (3)
O1W—H1W1⋯O3^v	0.89 (3)	1.94 (3)	2.757 (3)	151 (2)
O1W—H2W1⋯O4ⁱⁱⁱ	0.98 (6)	1.89 (6)	2.838 (3)	162 (4)
C7—H7⋯O3^vi	0.95 (3)	2.56 (3)	3.477 (2)	163 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681104445X/hb6457sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104445X/hb6457Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681104445X/hb6457Isup3.cml

checkCIF report

Comment top

5-sulfosalicylic acid, (5-SSA), has been known for a long time to possess anti-inflammatory activity. When it forms complexes with metals, its biological activity is greatly enhanced (Marzotto et al., 2001). Hydrogen-bonding patterns involving sulfonate groups in biological systems and metal complexes are of current interest (Onoda et al., 2001). Such interactions can be utilized for designing supramolecular architectures (Baskar Raj et al., 2003). With the aim of gaining more insight into hydrogen-bonding interactions involving 5-SSA and pyridine derivatives, we report here the molecular and supramolecular structure of the title compound.

The asymmetric unit of (I) contains a 2,3-diaminopyridinium cation, a sulfosalicylate anion and a water molecule (Fig. 1). The 2,3-di aminopyridinium cation is planar, with a maximum deviation of 0.015 (2) Å for atom C1. The dihedral angle between the pyridine (N1/C–C5) and the benzene (C6–C11) ring is 6.09 (9)°. The protonated N1 atom has lead to a slight increase in the C1—N1—C5 angle to 124. 4(2)°. The bond lengths (Allen et al., 1987) and angles are within normal ranges. There is an intramolecular O—H···O hydrogen bond in the 3-carboxy-4-hydroxy benzenesulfonate anion, which generates an S(6) (Bernstein et al., 1995) ring motif.

In the crystal (Fig. 2), the ion-pairs and water molecules are connected via N—H···O, O—H···O and C—H···O hydrogen bonds (Table 1), forming a three-dimensional network.

Related literature top

For background to 5-sulfosalicylic acid and related compounds, see: Marzotto et al. (2001); Onoda et al. (2001); Baskar Raj et al. (2003). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

Hot methanol solutions (20 ml) of 2,3-diaminopyridine (52 mg, Aldrich) and 5-sulfosalicylic acid (54. 5 mg, Merck) were mixed and warmed over a heating magnetic stirrer for 5 minutes. The resulting solution was allowed to cool slowly at room temperature. Brown plates of the title compound appeared from the mother liquor after a few days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids. Intramolecular hydrogen bonds shown by dashed lines.
	Fig. 2. The crystal packing of title compound (I).

2,3-Diaminopyridinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate top

Crystal data top

C₅H₈N₃⁺·C₇H₅O₆S⁻·H₂O	F(000) = 720
M_r = 345.33	D_x = 1.566 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3903 reflections
a = 7.0407 (7) Å	θ = 3.0–32.4°
b = 15.5775 (16) Å	µ = 0.26 mm⁻¹
c = 13.6244 (12) Å	T = 100 K
β = 101.491 (2)°	Plate, brown
V = 1464.3 (2) Å³	0.36 × 0.31 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD diffractometer	3880 independent reflections
Radiation source: fine-focus sealed tube	3645 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 30.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.910, T_max = 0.981	k = −20→21
6890 measured reflections	l = −18→19

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)] = 0.033	All H-atom parameters refined
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0525P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3880 reflections	Δρ_max = 0.33 e Å⁻³
268 parameters	Δρ_min = −0.19 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1770 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (5)

Crystal data top

C₅H₈N₃⁺·C₇H₅O₆S⁻·H₂O	V = 1464.3 (2) Å³
M_r = 345.33	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 7.0407 (7) Å	µ = 0.26 mm⁻¹
b = 15.5775 (16) Å	T = 100 K
c = 13.6244 (12) Å	0.36 × 0.31 × 0.08 mm
β = 101.491 (2)°

Data collection top

Bruker APEXII DUO CCD diffractometer	3880 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3645 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.981	R_int = 0.025
6890 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	All H-atom parameters refined
wR(F²) = 0.087	Δρ_max = 0.33 e Å⁻³
S = 1.03	Δρ_min = −0.19 e Å⁻³
3880 reflections	Absolute structure: Flack (1983), 1770 Friedel pairs
268 parameters	Absolute structure parameter: −0.02 (5)
2 restraints

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.9025 (3)	0.36254 (11)	−0.04106 (15)	0.0419 (4)
N2	0.7986 (3)	0.24446 (13)	−0.14072 (14)	0.0438 (4)
N3	0.7871 (3)	0.14977 (13)	0.03470 (16)	0.0482 (4)
C1	0.8513 (2)	0.27950 (12)	−0.04911 (15)	0.0328 (3)
C2	0.8521 (2)	0.23206 (13)	0.04046 (14)	0.0349 (4)
C3	0.9159 (3)	0.27470 (17)	0.12994 (16)	0.0465 (4)
C4	0.9699 (3)	0.36114 (19)	0.1331 (2)	0.0551 (6)
C5	0.9615 (3)	0.40443 (15)	0.0472 (2)	0.0516 (5)
S1	0.36330 (5)	0.48126 (2)	−0.18842 (3)	0.02841 (9)
O1	0.4248 (2)	0.23706 (10)	0.14554 (10)	0.0430 (3)
O2	0.2649 (2)	0.55517 (9)	−0.15649 (10)	0.0430 (3)
O3	0.5610 (2)	0.50245 (9)	−0.19835 (11)	0.0408 (3)
O4	0.2514 (2)	0.44146 (9)	−0.27754 (10)	0.0402 (3)
O5	0.2302 (2)	0.15275 (9)	−0.14779 (11)	0.0444 (3)
O6	0.2779 (3)	0.11944 (10)	0.01427 (12)	0.0484 (4)
C6	0.4112 (2)	0.28932 (11)	0.06627 (12)	0.0305 (3)
C7	0.4712 (3)	0.37427 (12)	0.08458 (13)	0.0337 (3)
C8	0.4596 (2)	0.43146 (11)	0.00715 (13)	0.0312 (3)
C9	0.3843 (2)	0.40512 (10)	−0.09102 (11)	0.0253 (3)
C10	0.3256 (2)	0.32121 (10)	−0.11074 (12)	0.0258 (3)
C11	0.3407 (2)	0.26183 (10)	−0.03244 (12)	0.0264 (3)
C12	0.2809 (2)	0.17180 (11)	−0.05209 (13)	0.0306 (3)
O1W	0.3732 (3)	0.08650 (11)	0.25895 (15)	0.0533 (4)
H3	0.930 (4)	0.2373 (19)	0.1958 (19)	0.046 (7)*
H4	1.007 (5)	0.389 (2)	0.193 (3)	0.069 (9)*
H5	1.011 (5)	0.463 (2)	0.039 (2)	0.067 (9)*
H7	0.515 (4)	0.3983 (18)	0.149 (2)	0.041 (6)*
H8	0.510 (4)	0.4874 (19)	0.021 (2)	0.043 (7)*
H10	0.271 (3)	0.3039 (15)	−0.1722 (17)	0.025 (5)*
H1N1	0.899 (5)	0.393 (2)	−0.098 (2)	0.057 (8)*
H1N2	0.820 (4)	0.277 (2)	−0.192 (2)	0.053 (8)*
H2N2	0.793 (4)	0.1894 (19)	−0.146 (2)	0.042 (6)*
H1N3	0.763 (4)	0.1187 (19)	−0.021 (2)	0.047 (7)*
H2N3	0.794 (4)	0.1179 (18)	0.092 (2)	0.044 (6)*
H1O1	0.354 (4)	0.181 (2)	0.122 (2)	0.053 (7)*
H1O5	0.203 (5)	0.100 (2)	−0.149 (2)	0.057 (8)*
H1W1	0.265 (5)	0.055 (2)	0.250 (2)	0.053 (8)*
H2W1	0.490 (8)	0.071 (4)	0.234 (4)	0.110 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0392 (8)	0.0377 (9)	0.0515 (10)	0.0004 (6)	0.0154 (7)	0.0051 (7)
N2	0.0607 (10)	0.0399 (10)	0.0340 (8)	0.0010 (7)	0.0169 (7)	0.0017 (7)
N3	0.0721 (12)	0.0387 (9)	0.0373 (9)	−0.0017 (8)	0.0194 (8)	0.0054 (8)
C1	0.0297 (7)	0.0335 (8)	0.0366 (8)	0.0024 (6)	0.0103 (6)	0.0016 (7)
C2	0.0330 (8)	0.0385 (10)	0.0352 (9)	0.0044 (6)	0.0116 (7)	0.0007 (8)
C3	0.0452 (10)	0.0592 (13)	0.0343 (10)	0.0045 (9)	0.0058 (8)	0.0009 (9)
C4	0.0444 (11)	0.0639 (15)	0.0538 (14)	−0.0043 (9)	0.0017 (9)	−0.0239 (12)
C5	0.0415 (9)	0.0405 (11)	0.0723 (15)	−0.0054 (8)	0.0105 (10)	−0.0113 (10)
S1	0.03858 (18)	0.02089 (16)	0.02544 (16)	−0.00344 (14)	0.00561 (12)	−0.00076 (14)
O1	0.0647 (9)	0.0366 (7)	0.0267 (6)	−0.0019 (6)	0.0068 (6)	0.0070 (5)
O2	0.0621 (8)	0.0302 (7)	0.0362 (7)	0.0129 (6)	0.0085 (6)	0.0010 (5)
O3	0.0469 (7)	0.0314 (6)	0.0462 (8)	−0.0108 (5)	0.0141 (6)	0.0010 (5)
O4	0.0577 (8)	0.0349 (7)	0.0264 (6)	−0.0101 (6)	0.0043 (5)	−0.0034 (5)
O5	0.0663 (9)	0.0270 (6)	0.0374 (7)	−0.0146 (6)	0.0043 (6)	−0.0016 (5)
O6	0.0745 (11)	0.0289 (7)	0.0416 (8)	−0.0115 (7)	0.0114 (7)	0.0064 (6)
C6	0.0364 (8)	0.0281 (8)	0.0275 (7)	0.0003 (6)	0.0078 (6)	0.0019 (6)
C7	0.0417 (8)	0.0323 (9)	0.0256 (8)	0.0013 (6)	0.0031 (6)	−0.0057 (6)
C8	0.0349 (7)	0.0246 (7)	0.0323 (8)	−0.0024 (6)	0.0027 (6)	−0.0067 (6)
C9	0.0303 (7)	0.0209 (6)	0.0250 (7)	−0.0012 (5)	0.0060 (5)	0.0000 (5)
C10	0.0310 (7)	0.0208 (6)	0.0257 (7)	−0.0020 (5)	0.0063 (5)	−0.0019 (5)
C11	0.0298 (7)	0.0220 (7)	0.0285 (8)	−0.0008 (5)	0.0083 (6)	0.0001 (5)
C12	0.0337 (7)	0.0245 (7)	0.0342 (8)	−0.0029 (6)	0.0084 (6)	0.0010 (6)
O1W	0.0539 (9)	0.0464 (9)	0.0617 (10)	−0.0046 (7)	0.0169 (8)	−0.0035 (8)

Geometric parameters (Å, º) top

N1—C1	1.342 (3)	S1—C9	1.7640 (16)
N1—C5	1.358 (3)	O1—C6	1.341 (2)
N1—H1N1	0.91 (3)	O1—H1O1	1.02 (3)
N2—C1	1.345 (3)	O5—C12	1.315 (2)
N2—H1N2	0.90 (3)	O5—H1O5	0.84 (4)
N2—H2N2	0.86 (3)	O6—C12	1.221 (2)
N3—C2	1.358 (3)	C6—C7	1.396 (3)
N3—H1N3	0.88 (3)	C6—C11	1.404 (2)
N3—H2N3	0.92 (3)	C7—C8	1.371 (3)
C1—C2	1.426 (3)	C7—H7	0.95 (3)
C2—C3	1.382 (3)	C8—C9	1.398 (2)
C3—C4	1.397 (4)	C8—H8	0.95 (3)
C3—H3	1.06 (3)	C9—C10	1.381 (2)
C4—C5	1.342 (4)	C10—C11	1.400 (2)
C4—H4	0.91 (4)	C10—H10	0.89 (2)
C5—H5	0.99 (4)	C11—C12	1.473 (2)
S1—O4	1.4484 (14)	O1W—H1W1	0.90 (3)
S1—O2	1.4542 (14)	O1W—H2W1	0.98 (5)
S1—O3	1.4631 (14)

C1—N1—C5	124.4 (2)	O4—S1—C9	107.04 (8)
C1—N1—H1N1	118 (2)	O2—S1—C9	106.31 (8)
C5—N1—H1N1	117 (2)	O3—S1—C9	106.41 (8)
C1—N2—H1N2	115.9 (19)	C6—O1—H1O1	108.2 (16)
C1—N2—H2N2	118.6 (18)	C12—O5—H1O5	105 (2)
H1N2—N2—H2N2	120 (3)	O1—C6—C7	117.46 (16)
C2—N3—H1N3	124.8 (18)	O1—C6—C11	122.76 (16)
C2—N3—H2N3	120.1 (18)	C7—C6—C11	119.78 (15)
H1N3—N3—H2N3	113 (3)	C8—C7—C6	120.59 (15)
N1—C1—N2	119.15 (19)	C8—C7—H7	114.7 (16)
N1—C1—C2	118.33 (18)	C6—C7—H7	124.6 (16)
N2—C1—C2	122.50 (18)	C7—C8—C9	119.90 (15)
N3—C2—C3	123.45 (19)	C7—C8—H8	119.0 (17)
N3—C2—C1	119.73 (18)	C9—C8—H8	121.1 (17)
C3—C2—C1	116.80 (19)	C10—C9—C8	120.37 (15)
C2—C3—C4	121.9 (2)	C10—C9—S1	120.87 (12)
C2—C3—H3	116.2 (16)	C8—C9—S1	118.76 (12)
C4—C3—H3	121.7 (16)	C9—C10—C11	120.19 (14)
C5—C4—C3	119.5 (2)	C9—C10—H10	121.7 (15)
C5—C4—H4	120 (2)	C11—C10—H10	118.0 (15)
C3—C4—H4	120 (2)	C10—C11—C6	119.14 (14)
C4—C5—N1	118.9 (2)	C10—C11—C12	120.99 (15)
C4—C5—H5	127.2 (19)	C6—C11—C12	119.87 (14)
N1—C5—H5	113.4 (19)	O6—C12—O5	122.81 (16)
O4—S1—O2	112.20 (9)	O6—C12—C11	123.21 (16)
O4—S1—O3	112.80 (9)	O5—C12—C11	113.97 (15)
O2—S1—O3	111.58 (9)	H1W1—O1W—H2W1	124 (4)

C5—N1—C1—N2	−178.76 (19)	O2—S1—C9—C10	129.29 (13)
C5—N1—C1—C2	2.2 (3)	O3—S1—C9—C10	−111.65 (13)
N1—C1—C2—N3	175.05 (18)	O4—S1—C9—C8	−170.06 (13)
N2—C1—C2—N3	−3.9 (3)	O2—S1—C9—C8	−49.97 (14)
N1—C1—C2—C3	−3.3 (2)	O3—S1—C9—C8	69.09 (14)
N2—C1—C2—C3	177.74 (19)	C8—C9—C10—C11	0.1 (2)
N3—C2—C3—C4	−175.7 (2)	S1—C9—C10—C11	−179.10 (11)
C1—C2—C3—C4	2.5 (3)	C9—C10—C11—C6	1.7 (2)
C2—C3—C4—C5	−0.6 (4)	C9—C10—C11—C12	−179.31 (14)
C3—C4—C5—N1	−0.7 (4)	O1—C6—C11—C10	178.04 (16)
C1—N1—C5—C4	−0.2 (3)	C7—C6—C11—C10	−2.2 (2)
O1—C6—C7—C8	−179.37 (17)	O1—C6—C11—C12	−1.0 (2)
C11—C6—C7—C8	0.8 (3)	C7—C6—C11—C12	178.81 (15)
C6—C7—C8—C9	1.0 (3)	C10—C11—C12—O6	−174.36 (18)
C7—C8—C9—C10	−1.5 (2)	C6—C11—C12—O6	4.6 (3)
C7—C8—C9—S1	177.74 (14)	C10—C11—C12—O5	5.4 (2)
O4—S1—C9—C10	9.19 (15)	C6—C11—C12—O5	−175.63 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1Wⁱ	0.91 (3)	1.95 (3)	2.806 (3)	158 (3)
N2—H1N2···O1ⁱ	0.90 (3)	2.48 (3)	3.222 (2)	140 (2)
N2—H1N2···O1Wⁱ	0.90 (3)	2.28 (3)	3.060 (3)	145 (2)
N2—H2N2···O2ⁱⁱ	0.86 (3)	2.10 (3)	2.963 (2)	177 (3)
N3—H1N3···O2ⁱⁱ	0.89 (3)	2.10 (3)	2.970 (3)	168 (3)
N3—H2N3···O4ⁱⁱⁱ	0.92 (3)	2.08 (3)	2.980 (3)	167 (3)
O1—H1O1···O6	1.03 (3)	1.75 (3)	2.625 (2)	141 (2)
O5—H1O5···O3^iv	0.84 (3)	1.87 (3)	2.655 (2)	155 (3)
O1W—H1W1···O3^v	0.89 (3)	1.94 (3)	2.757 (3)	151 (2)
O1W—H2W1···O4ⁱⁱⁱ	0.98 (6)	1.89 (6)	2.838 (3)	162 (4)
C7—H7···O3^vi	0.95 (3)	2.56 (3)	3.477 (2)	163 (2)

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

Experimental details

Crystal data
Chemical formula	C₅H₈N₃⁺·C₇H₅O₆S⁻·H₂O
M_r	345.33
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	7.0407 (7), 15.5775 (16), 13.6244 (12)
β (°)	101.491 (2)
V (Å³)	1464.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.36 × 0.31 × 0.08

Data collection
Diffractometer	Bruker APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.910, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	6890, 3880, 3645
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.087, 1.03
No. of reflections	3880
No. of parameters	268
No. of restraints	2
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.19
Absolute structure	Flack (1983), 1770 Friedel pairs
Absolute structure parameter	−0.02 (5)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1Wⁱ	0.91 (3)	1.95 (3)	2.806 (3)	158 (3)
N2—H1N2···O1ⁱ	0.90 (3)	2.48 (3)	3.222 (2)	140 (2)
N2—H1N2···O1Wⁱ	0.90 (3)	2.28 (3)	3.060 (3)	145 (2)
N2—H2N2···O2ⁱⁱ	0.86 (3)	2.10 (3)	2.963 (2)	177 (3)
N3—H1N3···O2ⁱⁱ	0.89 (3)	2.10 (3)	2.970 (3)	168 (3)
N3—H2N3···O4ⁱⁱⁱ	0.92 (3)	2.08 (3)	2.980 (3)	167 (3)
O1—H1O1···O6	1.03 (3)	1.75 (3)	2.625 (2)	141 (2)
O5—H1O5···O3^iv	0.84 (3)	1.87 (3)	2.655 (2)	155 (3)
O1W—H1W1···O3^v	0.89 (3)	1.94 (3)	2.757 (3)	151 (2)
O1W—H2W1···O4ⁱⁱⁱ	0.98 (6)	1.89 (6)	2.838 (3)	162 (4)
C7—H7···O3^vi	0.95 (3)	2.56 (3)	3.477 (2)	163 (2)

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

Footnotes

‡Thomson Reuters ResearcherID: C-7576-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

MH, JHG and HKF thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

References

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