Crystal structure of 2-amino-5-nitro­pyridinium sulfamate

The title mol­ecular salt, obtained by the reaction of sulfamic acid with 2-amino-5-nitro­pyridine, is the result of a proton transfer from sulfamic acid to the N atom of the pyridine ring. In the crystal, the cations and anions are linked by a number of N—H...O and N—H...N hydrogen bonds, forming sheets lying parallel to (100).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.055
• wR factor = 0.111
• Data-to-parameter ratio = 9.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.45 Note
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0050 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.473 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.065 Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         13 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          4 Report
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       5.45 Why ?
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         13 Note
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         16 Check
              O2   -N1   -O2'     1.555   1.555   1.555             17.80 Deg.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         50 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          90 %
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  13 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. 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.

S2. 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) °.

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.

S3. 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 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.

S4. 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.

S5. 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.

S6. 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).

Related literature

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

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

	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

Crystal data

C5H6N3O2^+·H2NO3S^−	F(000) = 976
Mr = 236.21	Dx = 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) Å^3	Block, colourless
Z = 8	0.35 × 0.30 × 0.25 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	w = 1/[σ^2(Fo^2) + (0.0116P)^2 + 5.4481P] where P = (Fo^2 + 2Fc^2)/3
1653 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.27 e Å^−3
50 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4^i	0.88 (2)	1.98 (2)	2.861 (4)	176 (4)
N2—H2A···N4^ii	0.88 (2)	2.18 (2)	3.044 (4)	169 (4)
N3—H3A···O5^iii	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···O3^i	0.93	2.57	3.469 (4)	163
C3—H3···O2^vi	0.93	2.46	3.328 (13)	155
C5—H5···O3^iii	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.