research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 231-233

Crystal structure of 2-amino-5-nitro­pyridinium sulfamate

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).

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[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391-o392.],b[Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600-o601.]). Simple organic–inorganic salts containing strong inter­molecular hydrogen bonds have attracted attention as materials which display ferroelectric–paraelectric phase transitions (Sethuram, et al., 2013a[Sethuram, M., Bhargavi, G., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013a). Acta Cryst. E69, o1301-o1302.],b[Sethuram, M., Rajasekharan, M. V., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013b). Acta Cryst. E69, o957-o958.]; Huq et al., 2013[Huq, C. A. M. A., Fouzia, S. & NizamMohideen, M. (2013). Acta Cryst. E69, o1766-o1767.]; Shihabuddeen Syed et al., 2013[Shihabuddeen Syed, A., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, i33.]; Showrilu et al., 2013[Showrilu, K., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, m469-m470.]). We have recently reported the crystal structures of 2-amino-6-methyl­pyridinium 2,2,2-tri­chloro­acetate (Babu et al., 2014a[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391-o392.]), 2-amino-6-methyl­pyridinium 4-methyl­benzene­sulfonate (Babu et al., 2014b[Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600-o601.]) and 2-amino-5-nitro­pyridinium hydrogen oxalate (Rajkumar et al., 2014[Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.]). 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.

[Scheme 1]

2. Structural commentary

The asymmetric unit of the title compound, Fig. 1[link], 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[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391-o392.],b[Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600-o601.]; Rajkumar et al., 2014[Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.]). 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[Anderson, F. P., Gallagher, J. F., Kenny, P. T. M. & Lough, A. J. (2005). Acta Cryst. E61, o1350-o1353.]). This type of protonation is observed in various amino­pyridine acid complexes (Babu et al., 2014a[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391-o392.],b[Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600-o601.]; Rajkumar et al., 2014[Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.]). 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]
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[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391-o392.],b[Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600-o601.]; Rajkumar et al., 2014[Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.]). 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[Nahringbauer, I. & Kvick, Å. (1977). Acta Cryst. B33, 2902-2905.]). The geometrical features of the amino­pyridinium cation (N1/N3/C1–C5) resemble those observed in other 2-amino­pyridinium structures (Babu et al., 2014a[Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391-o392.],b[Babu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600-o601.]; Rajkumar et al., 2014[Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473-o474.]) that are believed to be involved in amine–imine tautomerism (Ishikawa et al., 2002[Ishikawa, H., Iwata, K. & Hamaguchi, H. (2002). J. Phys. Chem. A, 106, 2305-2312.]). 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[Jin, Z.-M., Shun, N., Lü, Y.-P., Hu, M.-L. & Shen, L. (2005). Acta Cryst. C61, m43-m45.]).

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[Akriche, S. & Rzaigui, M. (2009). Acta Cryst. E65, o1648.]). 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[Akriche, S. & Rzaigui, M. (2009). Acta Cryst. E65, o1648.]). 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[Aakeroy, C. B., Beatty, A. M., Nieuwenhuyzen, M. & Zou, M. (1998). J. Mater. Chem. pp. 1385-1389.]). 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[link] and Fig. 2[link]). 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[link]), 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[link] and Table 1[link]). 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 DA 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⋯O4iv 0.89 (2) 2.20 (2) 3.073 (4) 166 (3)
N4—H4A⋯O5v 0.89 (2) 2.20 (2) 2.960 (4) 143 (3)
C2—H2⋯O3i 0.93 2.57 3.469 (4) 163
C3—H3⋯O2vi 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]
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[link] 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[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) 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[link]. 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 Uiso(H) = 1.2Ueq(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
Mr 236.21
Crystal system, space group Orthorhombic, Pbcn
Temperature (K) 293
a, b, c (Å) 28.0866 (10), 9.0052 (3), 7.4023 (2)
V3) 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[Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.887, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections 15358, 1653, 1557
Rint 0.024
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.27, −0.45
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004[Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), ORTEP-3 for Windows and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), Mercury (Macrae et al., 2008[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.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


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

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.

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 Uiso(H) = 1.2Ueq(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
[Figure 1] Fig. 1. View of the molecular structure of the title molecular salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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+·H2NO3SF(000) = 976
Mr = 236.21Dx = 1.676 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 1653 reflections
a = 28.0866 (10) Åθ = 2.4–31.1°
b = 9.0052 (3) ŵ = 0.36 mm1
c = 7.4023 (2) ÅT = 293 K
V = 1872.23 (10) Å3Block, colourless
Z = 80.35 × 0.30 × 0.25 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1653 independent reflections
Radiation source: fine-focus sealed tube1557 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω and ϕ scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 3333
Tmin = 0.887, Tmax = 0.917k = 1010
15358 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.28 w = 1/[σ2(Fo2) + (0.0116P)2 + 5.4481P]
where P = (Fo2 + 2Fc2)/3
1653 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 0.27 e Å3
50 restraintsΔρmin = 0.45 e Å3
Crystal data top
C5H6N3O2+·H2NO3SV = 1872.23 (10) Å3
Mr = 236.21Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 28.0866 (10) ŵ = 0.36 mm1
b = 9.0052 (3) ÅT = 293 K
c = 7.4023 (2) Å0.35 × 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)
Tmin = 0.887, Tmax = 0.917Rint = 0.024
15358 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05550 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.28Δρmax = 0.27 e Å3
1653 reflectionsΔρmin = 0.45 e Å3
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
xyzUiso*/UeqOcc. (<1)
C10.38918 (12)0.1439 (4)0.6248 (5)0.0269 (8)
C20.35730 (13)0.0484 (4)0.5342 (5)0.0292 (8)
H20.36020.05380.54770.035*
C30.32268 (13)0.1047 (4)0.4283 (5)0.0373 (9)
H30.30140.04210.36930.045*
C40.31924 (13)0.2591 (4)0.4085 (6)0.0371 (9)
C50.34829 (13)0.3498 (4)0.4998 (5)0.0345 (9)
H50.34530.45220.48800.041*
N10.28526 (15)0.3204 (5)0.2816 (7)0.0721 (15)
N20.42542 (12)0.0961 (4)0.7215 (4)0.0343 (8)
N30.38170 (11)0.2922 (3)0.6083 (4)0.0298 (7)
N40.47684 (11)0.3034 (3)0.0187 (4)0.0267 (7)
O10.2679 (4)0.2322 (7)0.1676 (14)0.105 (4)0.737 (19)
O20.2783 (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)
O30.39040 (9)0.3227 (3)0.0338 (4)0.0330 (6)
O40.44135 (9)0.2156 (3)0.2645 (3)0.0325 (6)
O50.44161 (9)0.4796 (3)0.2125 (3)0.0336 (6)
S10.43441 (3)0.33299 (9)0.13275 (11)0.0231 (2)
H4B0.5038 (10)0.282 (4)0.038 (5)0.040 (12)*
H4A0.4797 (12)0.384 (3)0.087 (4)0.040 (12)*
H3A0.4008 (12)0.356 (4)0.663 (5)0.043 (12)*
H2B0.4319 (13)0.001 (2)0.732 (6)0.046 (12)*
H2A0.4435 (13)0.154 (3)0.787 (5)0.051 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0336 (18)0.0247 (18)0.0225 (17)0.0018 (15)0.0077 (16)0.0052 (15)
C20.038 (2)0.0201 (17)0.0297 (19)0.0061 (15)0.0054 (17)0.0005 (16)
C30.034 (2)0.039 (2)0.039 (2)0.0128 (17)0.0037 (18)0.0011 (19)
C40.0303 (19)0.039 (2)0.042 (2)0.0001 (17)0.0015 (17)0.0127 (19)
C50.038 (2)0.0248 (18)0.040 (2)0.0018 (16)0.0134 (18)0.0053 (17)
N10.046 (2)0.070 (3)0.100 (4)0.007 (2)0.023 (3)0.039 (3)
N20.0415 (19)0.0261 (17)0.0353 (19)0.0004 (15)0.0064 (15)0.0048 (15)
N30.0382 (18)0.0210 (15)0.0303 (17)0.0046 (13)0.0038 (14)0.0074 (14)
N40.0323 (17)0.0268 (16)0.0211 (15)0.0009 (13)0.0010 (13)0.0003 (13)
O10.097 (7)0.089 (5)0.129 (7)0.034 (4)0.080 (6)0.036 (4)
O20.055 (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)
O30.0326 (13)0.0323 (14)0.0340 (14)0.0008 (11)0.0074 (12)0.0047 (12)
O40.0407 (15)0.0289 (13)0.0277 (13)0.0039 (12)0.0010 (12)0.0047 (11)
O50.0415 (14)0.0245 (13)0.0349 (14)0.0030 (12)0.0083 (12)0.0085 (11)
S10.0293 (4)0.0191 (4)0.0210 (4)0.0007 (3)0.0026 (4)0.0015 (3)
Geometric parameters (Å, º) top
C1—N21.317 (5)N1—O2'1.243 (8)
C1—N31.357 (4)N1—O1'1.246 (8)
C1—C21.411 (5)N1—O11.257 (6)
C2—C31.348 (5)N2—H2B0.884 (18)
C2—H20.9300N2—H2A0.877 (18)
C3—C41.402 (6)N3—H3A0.886 (19)
C3—H30.9300N4—S11.657 (3)
C4—C51.338 (6)N4—H4B0.889 (18)
C4—N11.449 (6)N4—H4A0.890 (18)
C5—N31.340 (5)O3—S11.440 (3)
C5—H50.9300O4—S11.451 (3)
N1—O21.228 (6)O5—S11.460 (2)
N2—C1—N3119.3 (3)O1'—N1—O150.3 (11)
N2—C1—C2123.4 (3)O2—N1—C4119.1 (8)
N3—C1—C2117.3 (3)O2'—N1—C4114.0 (14)
C3—C2—C1120.3 (3)O1'—N1—C4115.3 (10)
C3—C2—H2119.8O1—N1—C4116.7 (5)
C1—C2—H2119.8C1—N2—H2B122 (2)
C2—C3—C4118.9 (4)C1—N2—H2A124 (3)
C2—C3—H3120.5H2B—N2—H2A114 (3)
C4—C3—H3120.5C5—N3—C1122.9 (3)
C5—C4—C3120.7 (4)C5—N3—H3A116 (3)
C5—C4—N1119.8 (4)C1—N3—H3A120 (3)
C3—C4—N1119.4 (4)S1—N4—H4B109 (3)
C4—C5—N3119.6 (3)S1—N4—H4A108 (2)
C4—C5—H5120.2H4B—N4—H4A112 (3)
N3—C5—H5120.2O3—S1—O4114.22 (15)
O2—N1—O2'17.8 (19)O3—S1—O5112.50 (15)
O2—N1—O1'107.6 (12)O4—S1—O5111.59 (15)
O2'—N1—O1'122.5 (12)O3—S1—N4105.26 (16)
O2—N1—O1123.8 (8)O4—S1—N4103.93 (15)
O2'—N1—O1123.5 (19)O5—S1—N4108.63 (15)
N2—C1—C2—C3175.9 (4)C5—C4—N1—O2'8 (2)
N3—C1—C2—C33.6 (5)C3—C4—N1—O2'169 (2)
C1—C2—C3—C40.6 (6)C5—C4—N1—O1'141.5 (16)
C2—C3—C4—C53.2 (6)C3—C4—N1—O1'41.3 (16)
C2—C3—C4—N1174.0 (4)C5—C4—N1—O1162.1 (8)
C3—C4—C5—N31.4 (6)C3—C4—N1—O115.1 (9)
N1—C4—C5—N3175.7 (4)C4—C5—N3—C13.1 (6)
C5—C4—N1—O211.3 (11)N2—C1—N3—C5174.0 (3)
C3—C4—N1—O2171.4 (9)C2—C1—N3—C55.5 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O4i0.88 (2)1.98 (2)2.861 (4)176 (4)
N2—H2A···N4ii0.88 (2)2.18 (2)3.044 (4)169 (4)
N3—H3A···O5iii0.89 (2)1.91 (2)2.766 (4)163 (4)
N4—H4B···O4iv0.89 (2)2.20 (2)3.073 (4)166 (3)
N4—H4A···O5v0.89 (2)2.20 (2)2.960 (4)143 (3)
C2—H2···O3i0.932.573.469 (4)163
C3—H3···O2vi0.932.463.328 (13)155
C5—H5···O3iii0.932.413.187 (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, z1/2; (vi) x+1/2, y1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O4i0.884 (18)1.979 (19)2.861 (4)176 (4)
N2—H2A···N4ii0.877 (18)2.18 (2)3.044 (4)169 (4)
N3—H3A···O5iii0.886 (19)1.91 (2)2.766 (4)163 (4)
N4—H4B···O4iv0.889 (18)2.204 (19)3.073 (4)166 (3)
N4—H4A···O5v0.890 (18)2.20 (2)2.960 (4)143 (3)
C2—H2···O3i0.932.573.469 (4)163
C3—H3···O2vi0.932.463.328 (13)155
C5—H5···O3iii0.932.413.187 (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, z1/2; (vi) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC5H6N3O2+·H2NO3S
Mr236.21
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)293
a, b, c (Å)28.0866 (10), 9.0052 (3), 7.4023 (2)
V3)1872.23 (10)
Z8
Radiation typeMo Kα
µ (mm1)0.36
Crystal size (mm)0.35 × 0.30 × 0.25
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.887, 0.917
No. of measured, independent and
observed [I > 2σ(I)] reflections
15358, 1653, 1557
Rint0.024
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.111, 1.28
No. of reflections1653
No. of parameters175
No. of restraints50
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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

First citationAakeroy, C. B., Beatty, A. M., Nieuwenhuyzen, M. & Zou, M. (1998). J. Mater. Chem. pp. 1385–1389.  Google Scholar
First citationAkriche, S. & Rzaigui, M. (2009). Acta Cryst. E65, o1648.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationAnderson, 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
First citationBabu, K. S. S., Dhavamurthy, M., NizamMohideen, M., Peramaiyan, G. & Mohan, R. (2014b). Acta Cryst. E70, o600–o601.  Google Scholar
First citationBabu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014a). Acta Cryst. E70, o391–o392.  Google Scholar
First citationBruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CrossRef CAS Google Scholar
First citationHuq, C. A. M. A., Fouzia, S. & NizamMohideen, M. (2013). Acta Cryst. E69, o1766–o1767.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationIshikawa, H., Iwata, K. & Hamaguchi, H. (2002). J. Phys. Chem. A, 106, 2305–2312.  Web of Science CrossRef CAS Google Scholar
First citationJin, 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
First citationMacrae, 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
First citationNahringbauer, I. & Kvick, Å. (1977). Acta Cryst. B33, 2902–2905.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationRajkumar, 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
First citationSethuram, M., Bhargavi, G., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013a). Acta Cryst. E69, o1301–o1302.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationSethuram, M., Rajasekharan, M. V., Dhandapani, M., Amirthaganesan, G. & NizamMohideen, M. (2013b). Acta Cryst. E69, o957–o958.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShihabuddeen Syed, A., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, i33.  CrossRef IUCr Journals Google Scholar
First citationShowrilu, K., Rajarajan, K. & NizamMohideen, M. (2013). Acta Cryst. E69, m469–m470.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationSpek, 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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