Crystal structure of 2-amino-5-nitro­pyridinium sulfamate

Rajkumar, M.A.; NizamMohideen, M.; Xavier, S.S.J.; Anbarasu, S.; Devarajan, D.P.A.

doi:10.1107/S2056989015000365

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ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages 231-233

doi:10.1107/S2056989015000365

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Crystal structure of 2-amino-5-nitropyridinium sulfamate

M. Ambrose Rajkumar,^a M. NizamMohideen,^b ^* S. Stanly John Xavier,^c S. Anbarasu ^a and Dr. Prem Anand Devarajan ^a ^*

^aPhysics Research Centre, Department of Physics, St. Xavier's College (Autonomous), Palayamkottai 627 002, Tamil Nadu, India, ^bDepartment of Physics, The New College (Autonomous), Chennai 600 014, Tamil Nadu, India, and ^cDepartment of Chemistry, St. Xavier's College (Autonomous), Palayamkottai 627 002, Tamil Nadu, India
^*Correspondence e-mail: mnizam_new@yahoo.in, devarajanpremanand@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 15 December 2014; accepted 8 January 2015; online 31 January 2015)

The title molecular salt, C₅H₆N₃O₂⁺ ·H₂NO₃S⁻, was obtained from the reaction of sulfamic acid with 2-amino-5-nitropyridine. A proton transfer from sulfamic acid to the pyridine N atom occurred, resulting in the formation of a salt. As expected, this protonation leads to the widening of the C—N—C angle of the pyridine ring, to 122.9 (3)°, with the pyridinium ring being essentially planar (r.m.s. deviation = 0.025 Å). In the crystal, the ion pairs are joined by three N—H⋯O and one N—H⋯N hydrogen bonds in which the pyridinium N atom and the amino N atom act as donors, and are hydrogen bonded to the carboxylate O atoms and the N atom of the sulfamate anion, thus generating an R³₃(22) ring motif. These motifs are linked by further N—H⋯O hydrogen bonds enclosing R³₃(8) loops, forming sheets parallel to (100). The sheets are linked via weak C—H⋯O hydrogen bonds, forming a three-dimensional structure. The O atoms of the nitro group are disordered over two sets of sites with a refined occupancy ratio of 0.737 (19):0.263 (19).

Keywords: crystal structure; sulfamic acid; 2-amino-5-nitropyridine; sulfamate; 2-amino-5-pyridinium; molecular salt; hydrogen bonding..

CCDC reference: 1042506

1. Chemical context

Pyridine heterocycles and their derivatives are present in many large molecules having photo-chemical, electro-chemical and catalytic applications. Some pyridine derivatives possess non-linear optical (NLO) properties (Babu et al., 2014a ,b ). Simple organic–inorganic salts containing strong intermolecular hydrogen bonds have attracted attention as materials which display ferroelectric–paraelectric phase transitions (Sethuram, et al., 2013a ,b ; Huq et al., 2013 ; Shihabuddeen Syed et al., 2013 ; Showrilu et al., 2013 ). We have recently reported the crystal structures of 2-amino-6-methylpyridinium 2,2,2-trichloroacetate (Babu et al., 2014a), 2-amino-6-methylpyridinium 4-methylbenzenesulfonate (Babu et al., 2014b) and 2-amino-5-nitropyridinium hydrogen oxalate (Rajkumar et al., 2014 ). In a continuation of our studies of pyridinium salts, we report herein on the crystal structure of the title molecular salt, obtained by the reaction of 2-amino-5-nitropyridine with sulfamic acid.

2. Structural commentary

The asymmetric unit of the title compound, Fig. 1, consists of a 2-amino-5-nitropyridin-1-ium cation and a sulfamate anion. The bond lengths and angles are within normal ranges and comparable with those in closely related structures (Babu et al., 2014a,b; Rajkumar et al., 2014). A proton transfer from the sulfamic acid to the pyridine atom N3 resulted in the formation of a salt. This protonation leads to the widening of the C5—N3—C1 angle of the pyridine ring to 122.9 (3)°, compared with 115.25 (13)° in unprotonated aminopyridine (Anderson et al., 2005 ). This type of protonation is observed in various aminopyridine acid complexes (Babu et al., 2014a,b; Rajkumar et al., 2014). In the sulfamate anion the S—O distances vary from 1.440 (3) to 1.460 (2) Å, and O—S—O angles vary from 111.59 (15) to 114.22 (15) °.

Figure 1
View of the molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the cation, the N2—C1 [1.317 (5) Å] bond is shorter than the N3—C1 [1.357 (4) Å] and N3—C5 [1.340 (5) Å] bonds, and the C1—C2 [1.411 (5) Å] and C3—C4 [1.402 (6) Å] bonds lengths are significantly longer than bonds C2—C3 [1.348 (5) Å] and C4—C5 [1.338 (6) Å], similar to those observed previously for the aminopyridinium cation (Babu et al., 2014a,b; Rajkumar et al., 2014). In contrast, in the solid-state structure of aminopyridinium, the C—N(H₂) bond is clearly longer than that in the ring (Nahringbauer & Kvick, 1977 ). The geometrical features of the aminopyridinium cation (N1/N3/C1–C5) resemble those observed in other 2-aminopyridinium structures (Babu et al., 2014a,b; Rajkumar et al., 2014) that are believed to be involved in amine–imine tautomerism (Ishikawa et al., 2002 ). However, previous studies have shown that a pyridinium cation always possesses an expanded C—N—C angle in comparison with pyridine itself (Jin et al., 2005 ).

In this atomic arrangement, one can distinguish the intercation-to-anion contact C5—H5⋯O3 (H5⋯O5 = 2.41 Å), which induces the aggregation of the independent organic cation 2-amino-5-nitropyridinium. This kind of arrangement is also observed in the related structure of 2-amino-5-nitropyridinium hydrogen selenate (Akriche & Rzaigui, 2009 ). These pairs are located between the anionic layers to link them by various interactions. The geometric features of the organic cation are usual and comparable with values observed for other 2-amino nitropyridinium compounds (Akriche & Rzaigui, 2009). It is worth noticing that the C—NH₂ [1.317 (5) Å] and C—NO₂ [1.449 (6) Å] distances in the cations are, respectively, shortened and lengthened with respect to the same bond lengths [1.337 (4) and 1.429 (4) Å] observed for 2-amino-nitropyridine (Aakeroy et al., 1998 ). All the 2-amino-nitropyridinium cations encapsulated in various anionic sub-networks show the same changes in the C—NH₂ and C—NO₂ distances, revealing a weak increase of π bond character in the bond C—NH₂ and a decrease in the bond C—NO₂.

3. Supramolecular features

In the crystal, the ion pairs are linked by the N—H⋯O and N—H⋯N hydrogen bonds (Table 1 and Fig. 2). The protonated atom (N3) and the 2-amino group (N2) of the cation are hydrogen bonded to the carboxylate oxygen atoms (O5 and O4) and the nitrogen atom (N4) of the sulfamate anion via a pair of N—H⋯O and N—H⋯N (N3—H3A⋯O5, N2—H2B⋯O4 and N2—H2A⋯N4) hydrogen bonds (Table 1), forming an R₃³(22)ring motif. These motifs are further linked by N—H⋯O hydrogen bonds, enclosing R₃³(8) loops, and forming sheets lying parallel to (100). Weak C—H⋯O hydrogen bonds link the sheets, forming a three-dimensional structure (Fig. 2 and Table 1). The identification of such supramolecular patterns will help us design and construct preferred hydrogen-bonding patterns of drug-like molecules.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O4ⁱ	0.88 (2)	1.98 (2)	2.861 (4)	176 (4)
N2—H2A⋯N4ⁱⁱ	0.88 (2)	2.18 (2)	3.044 (4)	169 (4)
N3—H3A⋯O5ⁱⁱⁱ	0.89 (2)	1.91 (2)	2.766 (4)	163 (4)
N4—H4B⋯O4^iv	0.89 (2)	2.20 (2)	3.073 (4)	166 (3)
N4—H4A⋯O5^v	0.89 (2)	2.20 (2)	2.960 (4)	143 (3)
C2—H2⋯O3ⁱ	0.93	2.57	3.469 (4)	163
C3—H3⋯O2^vi	0.93	2.46	3.328 (13)	155
C5—H5⋯O3ⁱⁱⁱ	0.93	2.41	3.187 (4)	141
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+1, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
The crystal packing of the title salt, viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1

for details; only the major components of the disordered nitro O atoms are shown).

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.35, May 2014; Groom & Allen, 2014 ) for the cation 2-amino-5-nitropyridinium gave 42 hits for which there were 36 hits with atomic coordinates present. For these structures, the average C—N—C bond angle is ca 123°, while the average C—N(H₂) and C—N(O₂) bond lengths are ca 1.32 and 1.45 Å, respectively. A search for the anion aminosulfamate gave 23 hits but only 17 contained atomic coordinates. Here the S—O bond lengths vary from ca 1.399 to 1.469 Å, while the N—S bond length varies from ca 1.63 to 1.80 Å. The bond lengths and angles in the title salt are very similar to those reported for the various structures in the CSD.

5. Synthesis and crystallization

The starting material 2-amino-5-nitropyridine was obtained by treating 3-nitropyridine with ammonia in the presence of KMnO₄. Colourless block-like crystals of the title salt were obtained by slow evaporation of a 1:1 equimolar mixture of 2-amino-5-nitropyridine and sulfamic acid in methanol at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N-bound H atoms were located in a difference Fourier map and refined with distance restraints: N—H = 0.89 (2) Å. The C-bound H atoms were positioned geometrically and refined using a riding model: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C). The O atoms of the nitro group are disordered over two sets of sites (O1/O1′ and O2/O2′) with a refined occupancy ratio of 0.737 (19):0.263 (19).

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₆N₃O₂⁺·H₂NO₃S⁻
M_r	236.21
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	28.0866 (10), 9.0052 (3), 7.4023 (2)
V (Å³)	1872.23 (10)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.36
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.887, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	15358, 1653, 1557
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.111, 1.28
No. of reflections	1653
No. of parameters	175
No. of restraints	50
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.45
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1042506

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015000365/su5048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000365/su5048Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015000365/su5048Isup3.cml

checkCIF report

Chemical context top

Pyridine heterocycles and their derivatives are present in many large molecules having photo-chemical, electro-chemical and catalytic applications. Some pyridine derivatives possess non-linear optical (NLO) properties (Babu et al., 2014a,b). Simple organic–inorganic salts containing strong intermolecular hydrogen bonds have attracted attention as materials which display ferroelectric–paraelectric phase transitions (Sethuram, et al., 2013a,b; Huq et al., 2013; Shihabuddeen Syed et al., 2013; Showrilu et al., 2013). We have recently reported the crystal structures of 2-amino-6-methylpyridinium 2,2,2-trichloroacetate (Babu et al., 2014a), 2-amino-6-methylpyridinium 4-methylbenzenesulfonate (Babu et al., 2014b) and 2-amino-5-nitropyridinium hydrogen oxalate (Rajkumar et al., 2014). In a continuation of our studies of pyridinium salts, we report herein on the crystal structure of the title molecular salt, obtained by the reaction of 2-amino-5-nitropyridine with sulfamic acid.

Structural commentary top

The asymmetric unit of the title compound, Fig. 1, consists of a 2-amino-5-nitropyridin-1-ium cation and a sulfamate anion. The bond lengths and angles are within normal ranges and comparable with those in closely related structures (Babu et al., 2014a,b; Rajkumar et al., 2014). A proton transfer from the sulfamic acid to the pyridine atom N3 resulted in the formation of a salt. This protonation leads to the widening of the C5—N3—C1 angle of the pyridine ring to 122.9 (3)°, compared with 115.25 (13)° in unprotonated aminopyridine (Anderson et al., 2005). This type of protonation is observed in various aminopyridine acid complexes (Babu et al., 2014a,b; Rajkumar et al., 2014). In the sulfamate anion the S—O distances vary from 1.440 (3) to 1.460 (2) Å, and O—S—O angles vary from 111.59 (15) to 114.22 (15) °.

In the cation, the N2—C1 [1.317 (5) Å] bond is shorter than the N3—C1 [1.357 (4) Å] and N3—C5 [1.340 (5) Å] bonds, and the C1—C2 [1.411 (5) Å] and C3—C4 [1.402 (6) Å] bonds lengths are significantly longer than bonds C2—C3 [1.348 (5) Å] and C4—C5 [1.338 (6) Å], similar to those observed previously for the aminopyridinium cation (Babu et al., 2014a,b; Rajkumar et al., 2014). In contrast, in the solid-state structure of aminopyridinium, the C—N(H₂) bond is clearly longer than that in the ring (Nahringbauer & Kvick, 1977). The geometrical features of the aminopyridinium cation (N1/N3/C1–C5) resemble those observed in other 2-aminopyridinium structures (Babu et al., 2014a,b; Rajkumar et al., 2014) that are believed to be involved in amine–imine tautomerism (Ishikawa et al., 2002). However, previous studies have shown that a pyridinium cation always possesses an expanded C—N—C angle in comparison with pyridine itself (Jin et al., 2005).

In this atomic arrangement, one can distinguish the intercation-to-anion contact C5—H5···O3 (H5···O5 = 2.41 Å), which induces the aggregation of the independent organic cation 2-amino-5-nitropyridinium. This kind of arrangement is also observed in the related structure of 2-amino-5- nitropyridinium hydrogen selenate (Akriche & Rzaigui, 2009). These pairs are located between the anionic layers to link them by various interactions. The geometric features of the organic cation are usual and comparable with values observed for other 2-amino nitropyridinium compounds (Akriche & Rzaigui, 2009). It is worth noticing that the C—NH₂ [1.317 (5) Å] and C—NO₂ [1.449 (6) Å] distances in the cations are, respectively, shortened and lengthened with respect to the same bond lengths [1.337 (4) and 1.429 (4) Å] observed for 2-amino-nitropyridine (Aakeroy et al., 1998). All the 2-amino-nitropyridinium cations encapsulated in various anionic sub-networks show the same changes in the C—NH₂ and C—NO₂ distances, revealing a weak increase of π bond character in the bond C—NH₂ and a decrease in the bond C—NO₂.

Supramolecular features top

In the crystal, the ion pairs are linked by the N—H···O and N—H···N hydrogen bonds (Table 1 and Fig. 2). The protonated atom (N3) and the 2-amino group (N2) of the cation are hydrogen bonded to the carboxylate oxygen atoms (O5 and O4) and the nitrogen atom (N4) of the sulfamate anion via a pair of N—H···O and N—H···N (N3—H3A···O5, N2—H2B···O4 and N2—H2A···N4) hydrogen bonds (Table 1), forming an R₃³(22)ring motif. These motifs are further linked by N—H···O and N—H···N hydrogen bonds, enclosing R₃³(8) loops, and forming sheets lying parallel to (100). Weak C—H···O hydrogen bonds link the sheets, forming a three-dimensional structure (Fig. 2 and Table 1). The identification of such supramolecular patterns will help us design and construct preferred hydrogen-bonding patterns of drug-like molecules.

Database survey top

A search of the Cambridge Structural Database (CSD, Version 5.35, May 2014; Groom & Allen, 2014) for the cation 2-amino-5-nitropyridinium gave 42 hits for which there were 36 hits with atomic coordinates present. For these structures, the average C—N—C bond angle is ca 123°, while the average C—N(H₂) and C—N(O₂) bond lengths are ca 1.32 and 1.45 Å, respectively. A search for the anion aminosulfamate gave 23 hits but only 17 contained atomic coordinates. Here the S—O bond lengths vary from ca 1.399 to 1.469 Å, while the N—S bond length varies from ca 1.63 to 1.80 Å. The bond lengths and angles in the title salt are very similar to those reported for the various structures in the CSD.

Synthesis and crystallization top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The N-bound H atoms were located in a difference Fourier map and refined with distance restraints: N—H = 0.89 (2) Å. The C-bound H atoms were positioned geometrically and refined using a riding model: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C). The O atoms of the nitro group are disordered over two sets of sites (O1/O1' and O2/O2') with a refined occupancy ratio of 0.737 (19):0.263 (19).

Related literature top

For related literature, see: Aakeroy et al. (1998); Akriche & Rzaigui (2009); Anderson et al. (2005); Babu et al. (2014a, 2014b); Groom & Allen (2014); Huq et al. (2013); Ishikawa et al. (2002); Jin et al. (2005); Nahringbauer & Kvick (1977); Rajkumar et al. (2014); Sethuram et al. (2013a, 2013b); Shihabuddeen Syed, Rajarajan & NizamMohideen (2013); Showrilu et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title salt, viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details; only the major components of the disordered nitro O atoms are shown).

2-Amino-5-nitropyridinium sulfamate top

Crystal data top

C₅H₆N₃O₂⁺·H₂NO₃S⁻	F(000) = 976
M_r = 236.21	D_x = 1.676 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1653 reflections
a = 28.0866 (10) Å	θ = 2.4–31.1°
b = 9.0052 (3) Å	µ = 0.36 mm⁻¹
c = 7.4023 (2) Å	T = 293 K
V = 1872.23 (10) Å³	Block, colourless
Z = 8	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1653 independent reflections
Radiation source: fine-focus sealed tube	1557 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −33→33
T_min = 0.887, T_max = 0.917	k = −10→10
15358 measured reflections	l = −8→8

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	w = 1/[σ²(F_o²) + (0.0116P)² + 5.4481P] where P = (F_o² + 2F_c²)/3
1653 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.27 e Å⁻³
50 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₅H₆N₃O₂⁺·H₂NO₃S⁻	V = 1872.23 (10) Å³
M_r = 236.21	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 28.0866 (10) Å	µ = 0.36 mm⁻¹
b = 9.0052 (3) Å	T = 293 K
c = 7.4023 (2) Å	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1653 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1557 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.917	R_int = 0.024
15358 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	50 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	Δρ_max = 0.27 e Å⁻³
1653 reflections	Δρ_min = −0.45 e Å⁻³
175 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	Occ. (<1)
C1	0.38918 (12)	0.1439 (4)	0.6248 (5)	0.0269 (8)
C2	0.35730 (13)	0.0484 (4)	0.5342 (5)	0.0292 (8)
H2	0.3602	−0.0538	0.5477	0.035*
C3	0.32268 (13)	0.1047 (4)	0.4283 (5)	0.0373 (9)
H3	0.3014	0.0421	0.3693	0.045*
C4	0.31924 (13)	0.2591 (4)	0.4085 (6)	0.0371 (9)
C5	0.34829 (13)	0.3498 (4)	0.4998 (5)	0.0345 (9)
H5	0.3453	0.4522	0.4880	0.041*
N1	0.28526 (15)	0.3204 (5)	0.2816 (7)	0.0721 (15)
N2	0.42542 (12)	0.0961 (4)	0.7215 (4)	0.0343 (8)
N3	0.38170 (11)	0.2922 (3)	0.6083 (4)	0.0298 (7)
N4	0.47684 (11)	0.3034 (3)	−0.0187 (4)	0.0267 (7)
O1	0.2679 (4)	0.2322 (7)	0.1676 (14)	0.105 (4)	0.737 (19)
O2	0.2783 (4)	0.4550 (6)	0.280 (2)	0.078 (4)	0.737 (19)
O1'	0.2456 (5)	0.258 (2)	0.279 (4)	0.089 (7)	0.263 (19)
O2'	0.2901 (9)	0.4556 (11)	0.254 (6)	0.050 (6)	0.263 (19)
O3	0.39040 (9)	0.3227 (3)	0.0338 (4)	0.0330 (6)
O4	0.44135 (9)	0.2156 (3)	0.2645 (3)	0.0325 (6)
O5	0.44161 (9)	0.4796 (3)	0.2125 (3)	0.0336 (6)
S1	0.43441 (3)	0.33299 (9)	0.13275 (11)	0.0231 (2)
H4B	0.5038 (10)	0.282 (4)	0.038 (5)	0.040 (12)*
H4A	0.4797 (12)	0.384 (3)	−0.087 (4)	0.040 (12)*
H3A	0.4008 (12)	0.356 (4)	0.663 (5)	0.043 (12)*
H2B	0.4319 (13)	0.001 (2)	0.732 (6)	0.046 (12)*
H2A	0.4435 (13)	0.154 (3)	0.787 (5)	0.051 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0336 (18)	0.0247 (18)	0.0225 (17)	−0.0018 (15)	0.0077 (16)	−0.0052 (15)
C2	0.038 (2)	0.0201 (17)	0.0297 (19)	−0.0061 (15)	0.0054 (17)	−0.0005 (16)
C3	0.034 (2)	0.039 (2)	0.039 (2)	−0.0128 (17)	−0.0037 (18)	0.0011 (19)
C4	0.0303 (19)	0.039 (2)	0.042 (2)	−0.0001 (17)	0.0015 (17)	0.0127 (19)
C5	0.038 (2)	0.0248 (18)	0.040 (2)	0.0018 (16)	0.0134 (18)	0.0053 (17)
N1	0.046 (2)	0.070 (3)	0.100 (4)	−0.007 (2)	−0.023 (3)	0.039 (3)
N2	0.0415 (19)	0.0261 (17)	0.0353 (19)	−0.0004 (15)	−0.0064 (15)	−0.0048 (15)
N3	0.0382 (18)	0.0210 (15)	0.0303 (17)	−0.0046 (13)	0.0038 (14)	−0.0074 (14)
N4	0.0323 (17)	0.0268 (16)	0.0211 (15)	0.0009 (13)	−0.0010 (13)	0.0003 (13)
O1	0.097 (7)	0.089 (5)	0.129 (7)	−0.034 (4)	−0.080 (6)	0.036 (4)
O2	0.055 (6)	0.073 (5)	0.105 (8)	0.032 (3)	0.014 (5)	0.029 (4)
O1'	0.062 (10)	0.099 (11)	0.106 (14)	0.002 (9)	−0.043 (9)	0.003 (11)
O2'	0.032 (10)	0.050 (10)	0.068 (11)	0.023 (6)	0.008 (10)	0.026 (7)
O3	0.0326 (13)	0.0323 (14)	0.0340 (14)	−0.0008 (11)	−0.0074 (12)	−0.0047 (12)
O4	0.0407 (15)	0.0289 (13)	0.0277 (13)	−0.0039 (12)	0.0010 (12)	0.0047 (11)
O5	0.0415 (14)	0.0245 (13)	0.0349 (14)	0.0030 (12)	−0.0083 (12)	−0.0085 (11)
S1	0.0293 (4)	0.0191 (4)	0.0210 (4)	−0.0007 (3)	−0.0026 (4)	−0.0015 (3)

Geometric parameters (Å, º) top

C1—N2	1.317 (5)	N1—O2'	1.243 (8)
C1—N3	1.357 (4)	N1—O1'	1.246 (8)
C1—C2	1.411 (5)	N1—O1	1.257 (6)
C2—C3	1.348 (5)	N2—H2B	0.884 (18)
C2—H2	0.9300	N2—H2A	0.877 (18)
C3—C4	1.402 (6)	N3—H3A	0.886 (19)
C3—H3	0.9300	N4—S1	1.657 (3)
C4—C5	1.338 (6)	N4—H4B	0.889 (18)
C4—N1	1.449 (6)	N4—H4A	0.890 (18)
C5—N3	1.340 (5)	O3—S1	1.440 (3)
C5—H5	0.9300	O4—S1	1.451 (3)
N1—O2	1.228 (6)	O5—S1	1.460 (2)

N2—C1—N3	119.3 (3)	O1'—N1—O1	50.3 (11)
N2—C1—C2	123.4 (3)	O2—N1—C4	119.1 (8)
N3—C1—C2	117.3 (3)	O2'—N1—C4	114.0 (14)
C3—C2—C1	120.3 (3)	O1'—N1—C4	115.3 (10)
C3—C2—H2	119.8	O1—N1—C4	116.7 (5)
C1—C2—H2	119.8	C1—N2—H2B	122 (2)
C2—C3—C4	118.9 (4)	C1—N2—H2A	124 (3)
C2—C3—H3	120.5	H2B—N2—H2A	114 (3)
C4—C3—H3	120.5	C5—N3—C1	122.9 (3)
C5—C4—C3	120.7 (4)	C5—N3—H3A	116 (3)
C5—C4—N1	119.8 (4)	C1—N3—H3A	120 (3)
C3—C4—N1	119.4 (4)	S1—N4—H4B	109 (3)
C4—C5—N3	119.6 (3)	S1—N4—H4A	108 (2)
C4—C5—H5	120.2	H4B—N4—H4A	112 (3)
N3—C5—H5	120.2	O3—S1—O4	114.22 (15)
O2—N1—O2'	17.8 (19)	O3—S1—O5	112.50 (15)
O2—N1—O1'	107.6 (12)	O4—S1—O5	111.59 (15)
O2'—N1—O1'	122.5 (12)	O3—S1—N4	105.26 (16)
O2—N1—O1	123.8 (8)	O4—S1—N4	103.93 (15)
O2'—N1—O1	123.5 (19)	O5—S1—N4	108.63 (15)

N2—C1—C2—C3	−175.9 (4)	C5—C4—N1—O2'	8 (2)
N3—C1—C2—C3	3.6 (5)	C3—C4—N1—O2'	−169 (2)
C1—C2—C3—C4	0.6 (6)	C5—C4—N1—O1'	−141.5 (16)
C2—C3—C4—C5	−3.2 (6)	C3—C4—N1—O1'	41.3 (16)
C2—C3—C4—N1	174.0 (4)	C5—C4—N1—O1	162.1 (8)
C3—C4—C5—N3	1.4 (6)	C3—C4—N1—O1	−15.1 (9)
N1—C4—C5—N3	−175.7 (4)	C4—C5—N3—C1	3.1 (6)
C5—C4—N1—O2	−11.3 (11)	N2—C1—N3—C5	174.0 (3)
C3—C4—N1—O2	171.4 (9)	C2—C1—N3—C5	−5.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4ⁱ	0.88 (2)	1.98 (2)	2.861 (4)	176 (4)
N2—H2A···N4ⁱⁱ	0.88 (2)	2.18 (2)	3.044 (4)	169 (4)
N3—H3A···O5ⁱⁱⁱ	0.89 (2)	1.91 (2)	2.766 (4)	163 (4)
N4—H4B···O4^iv	0.89 (2)	2.20 (2)	3.073 (4)	166 (3)
N4—H4A···O5^v	0.89 (2)	2.20 (2)	2.960 (4)	143 (3)
C2—H2···O3ⁱ	0.93	2.57	3.469 (4)	163
C3—H3···O2^vi	0.93	2.46	3.328 (13)	155
C5—H5···O3ⁱⁱⁱ	0.93	2.41	3.187 (4)	141

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4ⁱ	0.884 (18)	1.979 (19)	2.861 (4)	176 (4)
N2—H2A···N4ⁱⁱ	0.877 (18)	2.18 (2)	3.044 (4)	169 (4)
N3—H3A···O5ⁱⁱⁱ	0.886 (19)	1.91 (2)	2.766 (4)	163 (4)
N4—H4B···O4^iv	0.889 (18)	2.204 (19)	3.073 (4)	166 (3)
N4—H4A···O5^v	0.890 (18)	2.20 (2)	2.960 (4)	143 (3)
C2—H2···O3ⁱ	0.93	2.57	3.469 (4)	163
C3—H3···O2^vi	0.93	2.46	3.328 (13)	155
C5—H5···O3ⁱⁱⁱ	0.93	2.41	3.187 (4)	141

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

Experimental details

Crystal data
Chemical formula	C₅H₆N₃O₂⁺·H₂NO₃S⁻
M_r	236.21
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	28.0866 (10), 9.0052 (3), 7.4023 (2)
V (Å³)	1872.23 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.887, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	15358, 1653, 1557
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.111, 1.28
No. of reflections	1653
No. of parameters	175
No. of restraints	50
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.45

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Acknowledgements

MAR, PAD and SSJX would like to thank the Board of Research in the Nuclear Sciences Department of Atomic Energy (BRNS–DAE) (File No. 2012/34/63/BRNS/2865; date: 01 March 2013) for funding this major research project.

References

Aakeroy, C. B., Beatty, A. M., Nieuwenhuyzen, M. & Zou, M. (1998). J. Mater. Chem. pp. 1385–1389. Google Scholar
Akriche, S. & Rzaigui, M. (2009). Acta Cryst. E65, o1648. Web of Science CSD CrossRef IUCr Journals Google Scholar
Anderson, F. P., Gallagher, J. F., Kenny, P. T. M. & Lough, A. J. (2005). Acta Cryst. E61, o1350–o1353. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600–o601. Google Scholar
Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391–o392. Google Scholar
Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS Google Scholar
Huq, C. A. M. A., Fouzia, S. & NizamMohideen, M. (2013). Acta Cryst. E69, o1766–o1767. CSD CrossRef CAS IUCr Journals Google Scholar
Ishikawa, H., Iwata, K. & Hamaguchi, H. (2002). J. Phys. Chem. A, 106, 2305–2312. Web of Science CrossRef CAS Google Scholar
Jin, Z.-M., Shun, N., Lü, Y.-P., Hu, M.-L. & Shen, L. (2005). Acta Cryst. C61, m43–m45. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nahringbauer, I. & Kvick, Å. (1977). Acta Cryst. B33, 2902–2905. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473–o474. CSD CrossRef CAS IUCr Journals Google Scholar
Sethuram, M., Bhargavi, G., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013a). Acta Cryst. E69, o1301–o1302. CSD CrossRef CAS IUCr Journals Google Scholar
Sethuram, M., Rajasekharan, M. V., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013b). Acta Cryst. E69, o957–o958. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shihabuddeen Syed, A., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, i33. CrossRef IUCr Journals Google Scholar
Showrilu, K., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, m469–m470. CSD CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 2| February 2015| Pages 231-233

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