2-Amino-5-nitro­pyridinium tri­fluoro­acetate

Jovita, J.V.; Sathya, S.; Usha, G.; Vasanthi, R.; Ezhilarasi, K.S.

doi:10.1107/S1600536813011896

2-Amino-5-nitropyridinium trifluoroacetate

J. V. Jovita, S. Sathya, G. Usha, R. Vasanthi and K. S. Ezhilarasi

The title salt, C₅H₆N₃O₂⁺·C₂F₃O₂⁻, crystallizes with two cations and two anions in the asymmetric unit. In the crystal, the acetate and pyridine groups are linked by a pair of N—H

O hydrogen bonds, forming loops described by the graph-set motif R₂²(8). These loops are linked via N—H

O hydrogen bonds, forming chains along [001]. The chains are in turn linked by C—H

O and C—H

F hydrogen bonds, generating a three-dimensional supramolecular network. In both anions, the O and F atoms are disordered over two sites, with occupancy ratios of 0.852 (3):0.148 (3) and 0.851 (3):0.149 (3).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813011896/su2582sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536813011896/su2582Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536813011896/su2582Isup3.cml Supplementary material

CCDC reference: 920486

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
Disorder in main residue
R factor = 0.042
wR factor = 0.118
Data-to-parameter ratio = 11.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.4
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT921_ALERT_1_C R1  in the CIF and FCF Differ by ...............     0.0012
PLAT922_ALERT_1_C wR2 in the CIF and FCF Differ by ...............     0.0036
PLAT923_ALERT_1_C S    values in the CIF and FCF Differ by .......      0.034

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C14 H12 F6 N6 O8
            Atom count from _chemical_formula_moiety:C7 H6 F3 N3 O4
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         29
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined Donor-H Atoms ........          2
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT230_ALERT_2_G Hirshfeld Test Diff for    F6     --  C14     ..        6.0 su
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................         29 %
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2
              C2 F3 O2
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4
              C5 H6 N3 O2
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         25
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         13

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

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

Comment top

Pyridine derivatives are important intermediates in organic synthesis, particularly in the synthesis of biologically active and medicinally important agents, for example, in the synthesis of anticonvulsant agents (Trapani et al., 2003) and antiviral agents (Gueiffier et al.,1998). Compounds containing the imidazo[1,2-a]pyridine ring system have been shown to exhibit antibacterial (Rival et al., 1992) and anti-inflammatory properties (Rupert et al., 2003). The wide spectrum of medicinal applications of this class of compounds prompted us to work in this domain and we report herein on the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound contains two 2-amino-5-nitro-pyridinium cations and two trifluoroacetate anions, Fig. 1. Each cation is planar with a maximum deviation of -0.0379 (2) Å for atom N3 in cation (C1—C5/N1), and 0.0661 (2) Å for atom N6 in cation (C8—C12/N4). The bond distances in the cations are in good agreement with the values reported for the related structure, 2-amino-5-chloropyridinium trifluoroacetate (Hemamalini & Fun, 2010). The sums of the angles around atoms N1 (360°) and N4 (360°) are an indication of their sp³ hybridization.

In the crystal, the acetate group and pyridine moiety are linked by a pair of N—H···O hydrogen bonds bonds, forming a loop described by the graph-set motif R²₂(8) (Bernstein et al., 1995). These loops are linked by N—H···O hydrogen bonds to form chains along the b axis (Table 1 and Fig. 2). The chains are further linked by C—H···O and C—H···F hydrogen bonds, generating a three-dimensional supramolecular network.

Related literature top

For the biological properties of pyridine derivatives and compounds containing the imidazo[1,2-a]pyridine ring system, see: Trapani et al. (2003); Gueiffier et al. (1998); Rival et al. (1992); Rupert et al. (2003). For the crystal structure of a related compound, see: Hemamalini & Fun (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by the reaction of an equimolar ratio of 2-amino-5-nitropyridine and trifluoroacetic acid. Trifluoroacetic acid was diluted with Millipore water and to this 2-amino-5-nitropyridine was added at room temperature. The mixture was stirred for 6 h to give a homogeneous solution, which was filtered and the filtrate kept for slow evaporation at room temperature. A saturated solution of the solid obtained was prepared by using methanol. It was kept in a constant-temperature water bath at 303 K to stabilize the temperature and avoid the effect of fluctuation in room temperature. After slow evaporation over a period of 15 d large colourless block-like crystals of the title compound were obtained.

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: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling. The displacement ellipsoids are drawn at the 30% probability level. (Only the major components of the disorderd trifluoroacetate anions are shown).
	Fig. 2. A view along the a axis of the crystal packing of the title compound. The various hydrogen bonds are shown as dashed lines (see Table 1 for details).

2-Amino-5-nitropyridinium trifluoroacetate top

Crystal data top

C₅H₆N₃O₂⁺·C₂F₃O₂⁻	F(000) = 1024
M_r = 506.30	D_x = 1.674 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6393 reflections
a = 19.1388 (7) Å	θ = 2.2–25.4°
b = 10.7716 (4) Å	µ = 0.17 mm⁻¹
c = 10.0707 (3) Å	T = 293 K
β = 104.668 (2)°	Block, colourless
V = 2008.47 (12) Å³	0.30 × 0.30 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII Kappa CCD diffractometer	4064 independent reflections
Radiation source: fine-focus sealed tube	3006 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and ϕ scans	θ_max = 26.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −23→23
T_min = 0.950, T_max = 0.958	k = −13→13
18608 measured reflections	l = −12→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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0512P)² + 0.6997P] where P = (F_o² + 2F_c²)/3
4064 reflections	(Δ/σ)_max = 0.001
367 parameters	Δρ_max = 0.28 e Å⁻³
25 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₅H₆N₃O₂⁺·C₂F₃O₂⁻	V = 2008.47 (12) Å³
M_r = 506.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 19.1388 (7) Å	µ = 0.17 mm⁻¹
b = 10.7716 (4) Å	T = 293 K
c = 10.0707 (3) Å	0.30 × 0.30 × 0.25 mm
β = 104.668 (2)°

Data collection top

Bruker APEXII Kappa CCD diffractometer	4064 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3006 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.958	R_int = 0.027
18608 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	25 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.28 e Å⁻³
4064 reflections	Δρ_min = −0.30 e Å⁻³
367 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles.

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 > 2sigma(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)
F1'	0.6216 (3)	0.0649 (2)	0.6851 (3)	0.0814 (9)	0.852 (3)
F2'	0.56447 (14)	0.2115 (4)	0.5636 (3)	0.1083 (15)	0.852 (3)
F3'	0.63061 (13)	0.2483 (2)	0.7641 (2)	0.0768 (9)	0.852 (3)
O3'	0.70962 (17)	0.31733 (18)	0.5942 (3)	0.0575 (10)	0.852 (3)
O4'	0.7170 (6)	0.1168 (5)	0.5457 (14)	0.0457 (12)	0.852 (3)
C6	0.69027 (10)	0.20703 (17)	0.58967 (18)	0.0399 (6)
C7	0.62582 (11)	0.1822 (2)	0.6500 (2)	0.0512 (7)
F1	0.624 (2)	0.0769 (12)	0.717 (2)	0.0814 (9)	0.148 (3)
F2	0.5709 (9)	0.171 (3)	0.5411 (17)	0.1083 (15)	0.148 (3)
F3	0.6058 (9)	0.2704 (12)	0.7193 (13)	0.0768 (9)	0.148 (3)
O3	0.6905 (13)	0.3188 (9)	0.558 (2)	0.0575 (10)	0.148 (3)
O4	0.725 (4)	0.122 (3)	0.555 (9)	0.0457 (12)	0.148 (3)
F4	1.09841 (15)	0.2673 (2)	0.9010 (3)	0.1233 (10)	0.851 (3)
F5	1.15881 (12)	0.1049 (2)	0.8967 (2)	0.1058 (9)	0.851 (3)
F6	1.08797 (13)	0.1125 (3)	1.0222 (3)	0.1281 (12)	0.851 (3)
O7	1.2114 (4)	0.3372 (2)	1.0927 (10)	0.0567 (16)	0.851 (3)
O8	1.2245 (3)	0.1454 (6)	1.1793 (7)	0.0529 (13)	0.851 (3)
C13	1.19568 (11)	0.22682 (19)	1.0956 (2)	0.0450 (7)
C14	1.13362 (13)	0.1801 (2)	0.9792 (2)	0.0613 (8)
F4'	1.1391 (8)	0.2274 (13)	0.8650 (10)	0.1233 (10)	0.149 (3)
F5'	1.1264 (8)	0.0609 (8)	0.9603 (13)	0.1058 (9)	0.149 (3)
F6'	1.0714 (5)	0.2141 (16)	0.9973 (18)	0.1281 (12)	0.149 (3)
O7'	1.195 (2)	0.3400 (9)	1.109 (6)	0.054 (9)	0.149 (3)
O8'	1.2391 (18)	0.150 (3)	1.163 (4)	0.045 (6)	0.149 (3)
O1	0.96571 (10)	0.58183 (17)	0.87250 (19)	0.0753 (7)
O2	1.00888 (11)	0.4598 (2)	0.7436 (3)	0.0991 (9)
N1	0.82378 (8)	0.31869 (13)	0.91912 (15)	0.0381 (5)
N2	0.78170 (10)	0.11850 (16)	0.8954 (2)	0.0517 (6)
N3	0.96796 (10)	0.4827 (2)	0.8153 (2)	0.0606 (7)
C1	0.86882 (10)	0.40934 (17)	0.90128 (18)	0.0408 (6)
C2	0.91883 (10)	0.38461 (18)	0.83148 (19)	0.0437 (6)
C3	0.92425 (11)	0.2660 (2)	0.7785 (2)	0.0500 (7)
C4	0.87916 (10)	0.1762 (2)	0.7980 (2)	0.0490 (7)
C5	0.82704 (9)	0.20153 (17)	0.87184 (18)	0.0385 (5)
O5	1.44036 (10)	0.50593 (17)	1.1714 (2)	0.0860 (7)
O6	1.48351 (9)	0.36088 (19)	1.31572 (16)	0.0756 (6)
N4	1.32454 (8)	0.25957 (13)	0.90524 (15)	0.0403 (5)
N5	1.30568 (10)	0.06118 (17)	0.82079 (19)	0.0533 (6)
N6	1.44654 (9)	0.3977 (2)	1.20577 (19)	0.0564 (7)
C8	1.35833 (10)	0.34404 (17)	0.99745 (19)	0.0417 (6)
C9	1.40837 (10)	0.30535 (18)	1.10970 (19)	0.0425 (6)
C10	1.42431 (10)	0.17906 (19)	1.1319 (2)	0.0477 (6)
C11	1.39007 (11)	0.09627 (18)	1.0385 (2)	0.0459 (6)
C12	1.33876 (10)	0.13646 (16)	0.91913 (19)	0.0394 (6)
H1	0.86560	0.48830	0.93670	0.0490*
H1A	0.79150	0.33570	0.96230	0.0460*
H2A	0.7521 (11)	0.135 (2)	0.953 (2)	0.065 (7)*
H2B	0.7837 (13)	0.0419 (17)	0.862 (2)	0.068 (7)*
H3	0.95870	0.24950	0.73020	0.0600*
H4	0.88220	0.09710	0.76280	0.0590*
H4A	1.29250	0.28480	0.83420	0.0480*
H5A	1.2713 (10)	0.092 (2)	0.7491 (18)	0.065 (7)*
H5B	1.3104 (13)	−0.018 (2)	0.840 (2)	0.066 (7)*
H8	1.34740	0.42800	0.98410	0.0500*
H10	1.45820	0.15290	1.21030	0.0570*
H11	1.40010	0.01210	1.05240	0.0550*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1'	0.1041 (13)	0.0575 (10)	0.108 (2)	−0.0127 (10)	0.074 (2)	0.0002 (11)
F2'	0.0443 (10)	0.182 (4)	0.0999 (15)	0.0261 (13)	0.0206 (10)	0.0242 (15)
F3'	0.0902 (18)	0.0800 (13)	0.0738 (14)	0.0095 (10)	0.0457 (12)	−0.0166 (11)
O3'	0.076 (2)	0.0308 (8)	0.076 (2)	−0.0038 (9)	0.0383 (15)	−0.0069 (8)
O4'	0.048 (3)	0.0320 (9)	0.064 (2)	0.0004 (12)	0.027 (3)	−0.0028 (9)
C6	0.0466 (10)	0.0315 (10)	0.0434 (10)	0.0018 (8)	0.0145 (8)	0.0004 (8)
C7	0.0504 (12)	0.0497 (12)	0.0588 (12)	0.0055 (10)	0.0237 (10)	0.0010 (10)
F1	0.1041 (13)	0.0575 (10)	0.108 (2)	−0.0127 (10)	0.074 (2)	0.0002 (11)
F2	0.0443 (10)	0.182 (4)	0.0999 (15)	0.0261 (13)	0.0206 (10)	0.0242 (15)
F3	0.0902 (18)	0.0800 (13)	0.0738 (14)	0.0095 (10)	0.0457 (12)	−0.0166 (11)
O3	0.076 (2)	0.0308 (8)	0.076 (2)	−0.0038 (9)	0.0383 (15)	−0.0069 (8)
O4	0.048 (3)	0.0320 (9)	0.064 (2)	0.0004 (12)	0.027 (3)	−0.0028 (9)
F4	0.109 (2)	0.0852 (15)	0.1244 (18)	0.0264 (13)	−0.0654 (16)	0.0034 (13)
F5	0.0952 (16)	0.1350 (19)	0.0739 (13)	0.0144 (14)	−0.0033 (10)	−0.0568 (13)
F6	0.0820 (14)	0.178 (3)	0.1117 (17)	−0.0743 (18)	0.0010 (13)	−0.0013 (19)
O7	0.056 (4)	0.0419 (17)	0.0666 (17)	0.0009 (13)	0.005 (2)	0.0002 (15)
O8	0.056 (3)	0.0368 (15)	0.055 (2)	0.0024 (17)	−0.006 (2)	−0.0057 (13)
C13	0.0423 (11)	0.0408 (12)	0.0486 (11)	0.0064 (9)	0.0052 (8)	−0.0068 (9)
C14	0.0556 (13)	0.0542 (14)	0.0627 (14)	0.0072 (11)	−0.0061 (11)	−0.0064 (11)
F4'	0.109 (2)	0.0852 (15)	0.1244 (18)	0.0264 (13)	−0.0654 (16)	0.0034 (13)
F5'	0.0952 (16)	0.1350 (19)	0.0739 (13)	0.0144 (14)	−0.0033 (10)	−0.0568 (13)
F6'	0.0820 (14)	0.178 (3)	0.1117 (17)	−0.0743 (18)	0.0010 (13)	−0.0013 (19)
O7'	0.043 (14)	0.026 (8)	0.08 (2)	0.013 (6)	−0.006 (12)	−0.014 (8)
O8'	0.034 (9)	0.044 (10)	0.059 (10)	0.005 (7)	0.015 (7)	−0.007 (6)
O1	0.0771 (12)	0.0604 (11)	0.0829 (12)	−0.0246 (9)	0.0099 (9)	0.0145 (9)
O2	0.0768 (13)	0.0950 (15)	0.1466 (19)	0.0023 (11)	0.0674 (14)	0.0403 (13)
N1	0.0381 (8)	0.0327 (8)	0.0460 (8)	0.0026 (6)	0.0153 (6)	−0.0017 (6)
N2	0.0548 (11)	0.0353 (10)	0.0711 (12)	−0.0039 (8)	0.0271 (9)	−0.0098 (8)
N3	0.0436 (10)	0.0655 (14)	0.0702 (12)	−0.0022 (9)	0.0098 (9)	0.0302 (11)
C1	0.0414 (10)	0.0332 (9)	0.0453 (10)	0.0011 (8)	0.0062 (8)	0.0046 (8)
C2	0.0334 (9)	0.0471 (11)	0.0488 (10)	0.0008 (8)	0.0069 (8)	0.0134 (9)
C3	0.0377 (10)	0.0625 (14)	0.0528 (11)	0.0094 (9)	0.0169 (9)	0.0043 (10)
C4	0.0451 (11)	0.0465 (12)	0.0564 (11)	0.0077 (9)	0.0147 (9)	−0.0095 (9)
C5	0.0369 (9)	0.0337 (9)	0.0440 (9)	0.0035 (8)	0.0085 (8)	−0.0022 (8)
O5	0.0863 (13)	0.0543 (11)	0.1018 (14)	−0.0114 (10)	−0.0050 (11)	−0.0169 (10)
O6	0.0656 (10)	0.1026 (14)	0.0505 (9)	0.0010 (10)	−0.0002 (8)	−0.0128 (9)
N4	0.0404 (8)	0.0309 (8)	0.0449 (8)	0.0026 (6)	0.0024 (7)	0.0069 (7)
N5	0.0614 (11)	0.0309 (9)	0.0612 (11)	−0.0006 (8)	0.0036 (9)	0.0047 (8)
N6	0.0433 (10)	0.0675 (13)	0.0565 (11)	−0.0012 (9)	0.0093 (8)	−0.0115 (9)
C8	0.0407 (10)	0.0317 (9)	0.0524 (10)	0.0002 (8)	0.0115 (8)	0.0022 (8)
C9	0.0368 (10)	0.0452 (11)	0.0456 (10)	0.0002 (8)	0.0107 (8)	−0.0004 (8)
C10	0.0424 (10)	0.0550 (13)	0.0444 (10)	0.0077 (9)	0.0087 (8)	0.0127 (9)
C11	0.0501 (11)	0.0354 (10)	0.0522 (11)	0.0088 (9)	0.0129 (9)	0.0142 (9)
C12	0.0398 (10)	0.0305 (9)	0.0489 (10)	0.0007 (8)	0.0131 (8)	0.0075 (8)

Geometric parameters (Å, º) top

F1—C7	1.325 (16)	N3—C2	1.451 (3)
F1'—C7	1.320 (3)	N1—H1A	0.8600
F2—C7	1.319 (17)	N2—H2B	0.896 (19)
F2'—C7	1.311 (4)	N2—H2A	0.93 (2)
F3—C7	1.293 (14)	N4—C12	1.354 (2)
F3'—C7	1.335 (3)	N4—C8	1.343 (2)
F4—C14	1.299 (3)	N5—C12	1.312 (3)
F4'—C14	1.286 (11)	N6—C9	1.450 (3)
F5—C14	1.335 (3)	N4—H4A	0.8600
F5'—C14	1.300 (9)	N5—H5A	0.908 (19)
F6—C14	1.293 (4)	N5—H5B	0.87 (2)
F6'—C14	1.302 (12)	C6—C7	1.530 (3)
O3—C6	1.246 (11)	C13—C14	1.527 (3)
O3'—C6	1.242 (3)	C1—C2	1.350 (3)
O4—C6	1.23 (6)	C2—C3	1.399 (3)
O4'—C6	1.232 (9)	C3—C4	1.343 (3)
O7—C13	1.229 (4)	C4—C5	1.414 (3)
O7'—C13	1.227 (12)	C1—H1	0.9300
O8—C13	1.244 (7)	C3—H3	0.9300
O8'—C13	1.25 (4)	C4—H4	0.9300
O1—N3	1.219 (3)	C8—C9	1.349 (3)
O2—N3	1.217 (3)	C9—C10	1.400 (3)
O5—N6	1.213 (3)	C10—C11	1.341 (3)
O6—N6	1.220 (2)	C11—C12	1.414 (3)
N1—C1	1.344 (2)	C8—H8	0.9300
N1—C5	1.356 (2)	C10—H10	0.9300
N2—C5	1.309 (3)	C11—H11	0.9300

C1—N1—C5	122.76 (16)	F4—C14—C13	114.2 (2)
O1—N3—C2	118.91 (19)	F5'—C14—C13	118.1 (6)
O2—N3—C2	116.9 (2)	F6'—C14—C13	111.2 (8)
O1—N3—O2	124.2 (2)	F4'—C14—F5'	106.9 (8)
C5—N1—H1A	119.00	F5—C14—C13	110.2 (2)
C1—N1—H1A	119.00	F4'—C14—C13	109.4 (6)
H2A—N2—H2B	120 (2)	F5—C14—F6	104.4 (2)
C5—N2—H2B	117.9 (16)	F4—C14—F6	108.6 (3)
C5—N2—H2A	121.5 (13)	F5'—C14—F6'	103.4 (10)
C8—N4—C12	122.89 (16)	F6—C14—C13	112.9 (2)
O5—N6—C9	118.21 (18)	F4'—C14—F6'	107.4 (10)
O6—N6—C9	117.5 (2)	F4—C14—F5	106.0 (2)
O5—N6—O6	124.3 (2)	N1—C1—C2	119.31 (17)
C12—N4—H4A	119.00	N3—C2—C3	120.64 (18)
C8—N4—H4A	119.00	C1—C2—C3	120.66 (18)
C12—N5—H5B	115.7 (14)	N3—C2—C1	118.69 (18)
C12—N5—H5A	119.2 (13)	C2—C3—C4	119.31 (19)
H5A—N5—H5B	123 (2)	C3—C4—C5	120.19 (19)
O3'—C6—C7	114.6 (2)	N2—C5—C4	123.50 (18)
O4—C6—C7	122 (3)	N1—C5—N2	118.73 (17)
O4'—C6—C7	117.1 (5)	N1—C5—C4	117.76 (17)
O3—C6—C7	109.0 (11)	C2—C1—H1	120.00
O3'—C6—O4'	128.4 (5)	N1—C1—H1	120.00
O3—C6—O4	128 (3)	C2—C3—H3	120.00
F2'—C7—F3'	107.3 (2)	C4—C3—H3	120.00
F2—C7—F3	103.5 (14)	C5—C4—H4	120.00
F1'—C7—F3'	106.0 (2)	C3—C4—H4	120.00
F1'—C7—C6	112.6 (3)	N4—C8—C9	119.03 (17)
F3'—C7—C6	111.22 (19)	N6—C9—C8	118.56 (18)
F3—C7—C6	117.7 (7)	C8—C9—C10	120.92 (18)
F2'—C7—C6	111.8 (2)	N6—C9—C10	120.51 (17)
F1—C7—F3	107.7 (12)	C9—C10—C11	119.10 (18)
F2—C7—C6	103.8 (8)	C10—C11—C12	120.25 (18)
F1—C7—F2	103.1 (18)	N4—C12—C11	117.77 (16)
F1'—C7—F2'	107.6 (3)	N5—C12—C11	123.44 (17)
F1—C7—C6	118.7 (16)	N4—C12—N5	118.78 (17)
O8'—C13—C14	118.8 (16)	N4—C8—H8	120.00
O7—C13—O8	129.0 (5)	C9—C8—H8	120.00
O7—C13—C14	116.6 (5)	C9—C10—H10	120.00
O7'—C13—O8'	129 (3)	C11—C10—H10	120.00
O7'—C13—C14	113 (2)	C10—C11—H11	120.00
O8—C13—C14	114.4 (3)	C12—C11—H11	120.00

C1—N1—C5—C4	−1.6 (3)	O8—C13—C14—F6	47.9 (4)
C1—N1—C5—N2	179.07 (18)	O7—C13—C14—F4	−9.0 (5)
C5—N1—C1—C2	1.2 (3)	O8—C13—C14—F4	172.6 (4)
O2—N3—C2—C1	−174.9 (2)	O8—C13—C14—F5	−68.3 (4)
O1—N3—C2—C1	4.7 (3)	O7—C13—C14—F5	110.1 (5)
O2—N3—C2—C3	6.5 (3)	O7—C13—C14—F6	−133.7 (5)
O1—N3—C2—C3	−173.9 (2)	N1—C1—C2—N3	−178.84 (17)
C12—N4—C8—C9	−0.5 (3)	N1—C1—C2—C3	−0.3 (3)
C8—N4—C12—C11	1.9 (3)	C1—C2—C3—C4	−0.2 (3)
C8—N4—C12—N5	−176.76 (19)	N3—C2—C3—C4	178.37 (19)
O5—N6—C9—C10	167.4 (2)	C2—C3—C4—C5	−0.3 (3)
O5—N6—C9—C8	−11.3 (3)	C3—C4—C5—N1	1.1 (3)
O6—N6—C9—C10	−11.8 (3)	C3—C4—C5—N2	−179.6 (2)
O6—N6—C9—C8	169.47 (19)	N4—C8—C9—C10	−1.1 (3)
O4'—C6—C7—F3'	138.5 (7)	N4—C8—C9—N6	177.59 (17)
O4'—C6—C7—F1'	19.7 (7)	C8—C9—C10—C11	1.2 (3)
O3'—C6—C7—F2'	79.7 (3)	N6—C9—C10—C11	−177.44 (19)
O4'—C6—C7—F2'	−101.6 (7)	C9—C10—C11—C12	0.2 (3)
O3'—C6—C7—F1'	−159.0 (3)	C10—C11—C12—N5	176.9 (2)
O3'—C6—C7—F3'	−40.3 (3)	C10—C11—C12—N4	−1.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4′ⁱ	0.86	1.90	2.758 (12)	175
N2—H2A···O3′ⁱ	0.93 (2)	1.88 (2)	2.791 (4)	168 (2)
N2—H2B···O8ⁱⁱ	0.90 (2)	2.06 (2)	2.935 (7)	166 (2)
N4—H4A···O8ⁱⁱⁱ	0.86	1.91	2.772 (7)	175
N5—H5A···O7ⁱⁱⁱ	0.91 (2)	1.86 (2)	2.763 (9)	172 (2)
N5—H5B···O3′^iv	0.87 (2)	1.97 (2)	2.801 (3)	160 (2)
C1—H1···O7^v	0.93	2.36	3.140 (5)	141
C4—H4···O2^iv	0.93	2.57	3.264 (3)	132
C8—H8···F1′^vi	0.93	2.44	3.089 (3)	127
C8—H8···O4′^vi	0.93	2.36	3.253 (7)	161

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y, −z+2; (iii) x, −y+1/2, z−1/2; (iv) −x+2, y−1/2, −z+3/2; (v) −x+2, −y+1, −z+2; (vi) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₅H₆N₃O₂⁺·C₂F₃O₂⁻
M_r	506.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	19.1388 (7), 10.7716 (4), 10.0707 (3)
β (°)	104.668 (2)
V (Å³)	2008.47 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Bruker APEXII Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.950, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	18608, 4064, 3006
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.118, 1.06
No. of reflections	4064
No. of parameters	367
No. of restraints	25
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.30

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).