2-Amino-4-methyl­pyridinium trifluoro­acetate

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

doi:10.1107/S1600536810008202

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages o781-o782

doi:10.1107/S1600536810008202

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2-Amino-4-methylpyridinium trifluoroacetate

Madhukar Hemamalini ^a and Hoong-Kun Fun ^a ^*‡

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

(Received 19 February 2010; accepted 3 March 2010; online 10 March 2010)

The asymmetric unit of the title compound, C₆H₉N₂⁺·C₂F₃O₂⁻, contains two independent 2-amino-4-methylpyridinium cations and two independent trifluoroacetate anions. The F atoms of both anions are disordered over two sets of sites, with site occupancies of 0.50 (3) and 0.50 (3) in one of the anions, and 0.756 (9) and 0.244 (9) in the other. In the crystal, the cations and anions are linked into chains along the b axis by N—H⋯O hydrogen bonds and these chains are cross-linked by C—H⋯O hydrogen bonds, forming a two-dimensional network lying parallel to (101). The crystal structure is further stabilized by π–π interactions between the pyridinium rings [centroid–centroid distances = 3.5842 (13) and 3.5665 (16) Å].

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ); Katritzky et al. (1996 ). For related structures, see: Kvick & Noordik (1977 ); Shen et al. (2008 ); Hemamalini & Fun (2010 ). For trifluoroacetic acid, see: Rodrigues et al. (2001 ). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ); Jeffrey (1997 ); Scheiner (1997 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₉N₂⁺·C₂F₃O₂⁻
M_r = 222.17
Triclinic, $[P \overline 1]$
a = 8.5229 (2) Å
b = 11.0649 (3) Å
c = 11.6573 (3) Å
α = 81.208 (1)°
β = 72.199 (2)°
γ = 74.647 (1)°
V = 1006.26 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 296 K
0.56 × 0.19 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.925, T_max = 0.989
21533 measured reflections
5803 independent reflections
3405 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.187
S = 1.06
5803 reflections
357 parameters
114 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O2Aⁱ	0.89 (3)	1.85 (3)	2.740 (3)	173 (2)
N2A—H2NA⋯O1Aⁱ	0.85 (2)	2.02 (2)	2.871 (3)	176 (2)
N2A—H3NA⋯O2Bⁱⁱ	0.85 (2)	2.04 (2)	2.835 (3)	156 (2)
N1B—H1NB⋯O2Bⁱⁱ	0.87 (3)	1.86 (3)	2.734 (3)	175 (2)
N2B—H2NB⋯O1Bⁱⁱ	0.85 (2)	2.01 (2)	2.858 (3)	176 (3)
N2B—H3NB⋯O2Aⁱⁱⁱ	0.83 (3)	2.04 (2)	2.848 (3)	164 (3)
C4A—H4AA⋯O1B^iv	0.93	2.57	3.423 (3)	153
C6B—H6BA⋯O1A^v	0.96	2.57	3.518 (5)	169
Symmetry codes: (i) x-1, y+1, z; (ii) x, y, z-1; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1; (v) -x+1, -y, -z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008202/ci5038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008202/ci5038Isup2.hkl

checkCIF report

Comment top

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). They are often involved in hydrogen-bond interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). Trifluoroacetic acid (TFA) is a very strong carboxylic acid, easily volatile, and used for protein purifications. Several trifluoroacetate salts and their crystal structures have been reported (Rodrigues et al., 2001). The crystal structures of 2-amino-4-methylpyridine (Kvick & Noordik, 1977), 2-amino-4-methylpyridinium 4-aminobenzoate (Shen et al., 2008) have also been reported. We have recently reported the crystal structure of 2-amino-4-methylpyridinium 4-nitrobenzoate (Hemamalini & Fun, 2010). In continuation of our studies of pyridinium derivatives, the crystal structure determination of the title compound has been undertaken.

The asymmetric unit of the title compound consists of two crystallographically independent 2-amino-4-methylpyridinium cations (A and B) and two trifluoroacetate anions (A and B) (Fig. 1). Each 2-amino-4-methylpyridinium cation is planar, with a maximum deviation of 0.007 (3) Å for atom C6A in cation A and 0.011 (5) Å for atom C6B in cation B. The protonation of atoms N1A and N1B lead to a slight increase in C1A—N1A—C5A [122.3 (2)°] and C1B—N1B—C5B [121.7 (2)°] angles.

In the crystal packing (Fig. 2), the A (and B)-type 2-amino-4-methylpyridinium cations interact with the carboxylate groups of A (and B)-type trifluoroacetate anions through a pair of N—H···O hydrogen bonds, forming an R₂²(8) motif (Bernstein et al., 1995). The cation-anion pairs are linked into a chain along the b axis by N—H···O hydrogen bonds. The crystal structure is further stabilized by C—H···O (Table 1) hydrogen bonds and π–π interactions involving the N1A/C1A–C5A and N1A/C1A–C5A pyridine rings [centoid-to-centroid separation = 3.5842 (13) Å], and N1B/C1B–C5B and N1B/C1B–C5B rings [centoid-to-centroid separation = 3.5665 (16) Å].

Related literature top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For related structures, see: Kvick & Noordik (1977); Shen et al. (2008); Hemamalini & Fun (2010). For trifluoroacetic acid, see: Rodrigues et al. (2001). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

To a hot methanol solution (20 ml) of 2-amino-4-methylpyridine (27 mg, Aldrich) was added a few drops of trifluoroacetic acid. The solution was warmed over a water bath for a few minutes. The resulting solution was allowed to cool slowly to room temperature. Crystals of the title compound appeared after a few days.

Computing details top

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

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. All disorder components are shown.
	Fig. 2. The crystal packing of the title compound, showing the hydrogen-bonded (dashed lines) network.

2-Amino-4-methylpyridinium trifluoroacetate top

Crystal data top

C₆H₉N₂⁺·C₂F₃O₂⁻	Z = 4
M_r = 222.17	F(000) = 456
Triclinic, P1	D_x = 1.467 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5229 (2) Å	Cell parameters from 4908 reflections
b = 11.0649 (3) Å	θ = 2.6–30.0°
c = 11.6573 (3) Å	µ = 0.14 mm⁻¹
α = 81.208 (1)°	T = 296 K
β = 72.199 (2)°	Plate, colourless
γ = 74.647 (1)°	0.56 × 0.19 × 0.08 mm
V = 1006.26 (4) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5803 independent reflections
Radiation source: fine-focus sealed tube	3405 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.925, T_max = 0.989	k = −15→15
21533 measured reflections	l = −16→16

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0642P)² + 0.3844P] where P = (F_o² + 2F_c²)/3
5803 reflections	(Δ/σ)_max = 0.001
357 parameters	Δρ_max = 0.25 e Å⁻³
114 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₆H₉N₂⁺·C₂F₃O₂⁻	γ = 74.647 (1)°
M_r = 222.17	V = 1006.26 (4) Å³
Triclinic, P1	Z = 4
a = 8.5229 (2) Å	Mo Kα radiation
b = 11.0649 (3) Å	µ = 0.14 mm⁻¹
c = 11.6573 (3) Å	T = 296 K
α = 81.208 (1)°	0.56 × 0.19 × 0.08 mm
β = 72.199 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5803 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3405 reflections with I > 2σ(I)
T_min = 0.925, T_max = 0.989	R_int = 0.028
21533 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	114 restraints
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.25 e Å⁻³
5803 reflections	Δρ_min = −0.26 e Å⁻³
357 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1A	0.3581 (3)	0.99313 (18)	0.21338 (18)	0.0510 (5)
N2A	0.2610 (3)	0.8369 (2)	0.1674 (2)	0.0672 (6)
C1A	0.4811 (3)	1.0518 (2)	0.2081 (2)	0.0589 (6)
H1AA	0.4538	1.1237	0.2490	0.071*
C2A	0.6422 (3)	1.0074 (3)	0.1447 (2)	0.0605 (6)
H2AA	0.7258	1.0485	0.1412	0.073*
C3A	0.6831 (3)	0.8980 (2)	0.0835 (2)	0.0553 (6)
C4A	0.5572 (3)	0.8401 (2)	0.0901 (2)	0.0548 (6)
H4AA	0.5829	0.7678	0.0500	0.066*
C5A	0.3900 (3)	0.8882 (2)	0.1564 (2)	0.0500 (6)
C6A	0.8627 (4)	0.8466 (3)	0.0138 (3)	0.0779 (8)
H6AA	0.8721	0.7662	−0.0125	0.117*
H6AB	0.9358	0.8373	0.0645	0.117*
H6AC	0.8951	0.9033	−0.0554	0.117*
N1B	0.2268 (3)	0.49192 (19)	0.32553 (19)	0.0529 (5)
N2B	0.1215 (4)	0.3395 (2)	0.2805 (2)	0.0708 (7)
C1B	0.2776 (3)	0.5451 (3)	0.4013 (2)	0.0600 (7)
H1BB	0.309 (4)	0.622 (3)	0.367 (3)	0.072 (8)*
C2B	0.2732 (3)	0.4938 (3)	0.5135 (3)	0.0634 (7)
H2BA	0.3074	0.5315	0.5648	0.076*
C3B	0.2162 (3)	0.3817 (3)	0.5533 (2)	0.0612 (6)
C4B	0.1643 (3)	0.3302 (2)	0.4769 (2)	0.0581 (6)
H4BA	0.1248	0.2572	0.5027	0.070*
C5B	0.1695 (3)	0.3855 (2)	0.3598 (2)	0.0508 (6)
C6B	0.2136 (6)	0.3216 (4)	0.6779 (3)	0.0997 (12)
H6BA	0.1825	0.2426	0.6877	0.149*
H6BB	0.1326	0.3759	0.7365	0.149*
H6BC	0.3240	0.3079	0.6894	0.149*
F1A	0.7612 (16)	0.1532 (10)	0.5327 (7)	0.084 (2)	0.50 (3)
F2A	0.6477 (14)	0.1650 (13)	0.3757 (10)	0.102 (3)	0.50 (3)
F3A	0.6788 (15)	0.0165 (9)	0.5069 (8)	0.093 (3)	0.50 (3)
F1C	0.7539 (17)	0.1841 (16)	0.5129 (13)	0.110 (4)	0.50 (3)
F2C	0.6745 (18)	0.2046 (15)	0.3790 (11)	0.122 (4)	0.50 (3)
F3C	0.6439 (18)	0.0349 (13)	0.4851 (15)	0.117 (4)	0.50 (3)
O1A	0.9324 (3)	−0.0511 (2)	0.3165 (2)	0.0937 (7)
O2A	1.0382 (2)	0.10073 (17)	0.34606 (19)	0.0712 (6)
C7A	0.9242 (3)	0.0450 (2)	0.3593 (2)	0.0562 (6)
C8A	0.7515 (3)	0.1063 (3)	0.4389 (2)	0.0636 (7)
F1B	0.4287 (6)	0.6567 (4)	0.8679 (3)	0.0917 (13)	0.756 (9)
F2B	0.1802 (5)	0.6740 (7)	0.8575 (4)	0.136 (2)	0.756 (9)
F3B	0.3737 (6)	0.5082 (4)	0.8111 (4)	0.1062 (14)	0.756 (9)
F1D	0.310 (2)	0.7120 (8)	0.8858 (9)	0.101 (4)	0.244 (9)
F2D	0.1842 (14)	0.6008 (13)	0.8405 (11)	0.094 (4)	0.244 (9)
F3D	0.4324 (15)	0.5237 (15)	0.8247 (14)	0.122 (5)	0.244 (9)
O1B	0.2191 (3)	0.4371 (2)	1.03426 (19)	0.0899 (7)
O2B	0.2503 (3)	0.60549 (17)	1.09745 (16)	0.0786 (6)
C7B	0.2531 (3)	0.5397 (2)	1.0201 (2)	0.0566 (6)
C8B	0.3048 (3)	0.5954 (3)	0.8898 (2)	0.0649 (7)
H1NA	0.252 (4)	1.022 (2)	0.257 (2)	0.057 (7)*
H2NA	0.161 (3)	0.869 (2)	0.209 (2)	0.062 (8)*
H3NA	0.276 (4)	0.775 (2)	0.127 (2)	0.077 (9)*
H1NB	0.238 (3)	0.524 (2)	0.251 (3)	0.058 (7)*
H2NB	0.146 (4)	0.368 (3)	0.2065 (19)	0.079 (10)*
H3NB	0.078 (3)	0.278 (2)	0.301 (3)	0.070 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0562 (13)	0.0494 (11)	0.0466 (11)	−0.0169 (9)	−0.0063 (10)	−0.0099 (8)
N2A	0.0761 (17)	0.0585 (14)	0.0704 (15)	−0.0299 (13)	−0.0057 (13)	−0.0204 (12)
C1A	0.0699 (17)	0.0555 (14)	0.0587 (15)	−0.0232 (13)	−0.0167 (13)	−0.0136 (11)
C2A	0.0599 (16)	0.0667 (16)	0.0606 (15)	−0.0210 (13)	−0.0189 (13)	−0.0064 (12)
C3A	0.0599 (15)	0.0566 (14)	0.0451 (13)	−0.0056 (12)	−0.0168 (11)	−0.0005 (10)
C4A	0.0710 (16)	0.0439 (12)	0.0463 (13)	−0.0077 (11)	−0.0160 (12)	−0.0049 (10)
C5A	0.0684 (16)	0.0418 (11)	0.0407 (11)	−0.0174 (11)	−0.0143 (11)	0.0007 (9)
C6A	0.0636 (18)	0.084 (2)	0.076 (2)	−0.0031 (15)	−0.0145 (15)	−0.0103 (16)
N1B	0.0631 (13)	0.0487 (11)	0.0455 (11)	−0.0230 (10)	−0.0047 (10)	−0.0029 (9)
N2B	0.0989 (19)	0.0645 (15)	0.0620 (15)	−0.0456 (14)	−0.0189 (14)	−0.0039 (12)
C1B	0.0676 (17)	0.0579 (15)	0.0575 (15)	−0.0305 (13)	−0.0076 (12)	−0.0056 (12)
C2B	0.0653 (16)	0.0714 (17)	0.0621 (16)	−0.0281 (14)	−0.0186 (13)	−0.0066 (13)
C3B	0.0603 (15)	0.0629 (15)	0.0607 (15)	−0.0179 (12)	−0.0191 (12)	0.0055 (12)
C4B	0.0627 (15)	0.0490 (13)	0.0619 (15)	−0.0228 (12)	−0.0122 (12)	0.0048 (11)
C5B	0.0505 (13)	0.0451 (12)	0.0545 (14)	−0.0159 (10)	−0.0054 (10)	−0.0068 (10)
C6B	0.140 (3)	0.101 (3)	0.079 (2)	−0.054 (2)	−0.058 (2)	0.0303 (19)
F1A	0.096 (4)	0.091 (4)	0.054 (3)	−0.014 (3)	−0.010 (2)	−0.012 (3)
F2A	0.083 (4)	0.122 (5)	0.092 (4)	0.007 (4)	−0.037 (3)	−0.012 (4)
F3A	0.076 (4)	0.117 (4)	0.073 (4)	−0.038 (3)	0.000 (3)	0.015 (3)
F1C	0.101 (5)	0.114 (6)	0.127 (6)	−0.038 (4)	−0.010 (4)	−0.068 (5)
F2C	0.100 (5)	0.125 (6)	0.103 (5)	0.013 (4)	−0.025 (3)	0.023 (4)
F3C	0.080 (4)	0.131 (6)	0.146 (7)	−0.068 (4)	0.001 (4)	−0.024 (4)
O1A	0.0789 (14)	0.0947 (16)	0.1201 (19)	−0.0387 (12)	−0.0099 (13)	−0.0498 (14)
O2A	0.0621 (11)	0.0612 (11)	0.0907 (14)	−0.0314 (9)	−0.0031 (10)	−0.0147 (10)
C7A	0.0600 (15)	0.0598 (14)	0.0554 (14)	−0.0271 (12)	−0.0143 (12)	−0.0044 (11)
C8A	0.0613 (16)	0.0771 (19)	0.0573 (16)	−0.0277 (14)	−0.0137 (13)	−0.0049 (13)
F1B	0.098 (3)	0.100 (2)	0.0800 (17)	−0.053 (2)	−0.0076 (16)	0.0035 (15)
F2B	0.086 (2)	0.174 (4)	0.093 (2)	0.023 (3)	−0.0136 (18)	0.040 (3)
F3B	0.119 (3)	0.130 (3)	0.0665 (18)	−0.051 (2)	0.0142 (19)	−0.0440 (16)
F1D	0.146 (8)	0.084 (5)	0.079 (5)	−0.052 (5)	−0.025 (5)	0.008 (4)
F2D	0.105 (6)	0.113 (7)	0.084 (5)	−0.030 (5)	−0.062 (5)	0.012 (5)
F3D	0.078 (6)	0.148 (8)	0.112 (7)	−0.006 (5)	−0.002 (5)	−0.010 (6)
O1B	0.140 (2)	0.0703 (13)	0.0708 (13)	−0.0528 (14)	−0.0189 (13)	−0.0111 (10)
O2B	0.1372 (19)	0.0565 (11)	0.0532 (11)	−0.0412 (12)	−0.0259 (11)	−0.0054 (8)
C7B	0.0670 (16)	0.0506 (13)	0.0537 (14)	−0.0165 (12)	−0.0137 (12)	−0.0094 (11)
C8B	0.0657 (18)	0.0713 (18)	0.0547 (15)	−0.0147 (15)	−0.0106 (13)	−0.0108 (13)

Geometric parameters (Å, º) top

N1A—C5A	1.350 (3)	C2B—H2BA	0.93
N1A—C1A	1.354 (3)	C3B—C4B	1.356 (4)
N1A—H1NA	0.89 (3)	C3B—C6B	1.499 (4)
N2A—C5A	1.330 (3)	C4B—C5B	1.401 (3)
N2A—H2NA	0.855 (18)	C4B—H4BA	0.93
N2A—H3NA	0.850 (19)	C6B—H6BA	0.96
C1A—C2A	1.344 (4)	C6B—H6BB	0.96
C1A—H1AA	0.93	C6B—H6BC	0.96
C2A—C3A	1.408 (4)	F1A—C8A	1.314 (6)
C2A—H2AA	0.93	F2A—C8A	1.301 (6)
C3A—C4A	1.366 (3)	F3A—C8A	1.336 (6)
C3A—C6A	1.499 (4)	F1C—C8A	1.316 (6)
C4A—C5A	1.401 (3)	F2C—C8A	1.331 (6)
C4A—H4AA	0.93	F3C—C8A	1.306 (6)
C6A—H6AA	0.96	O1A—C7A	1.219 (3)
C6A—H6AB	0.96	O2A—C7A	1.243 (3)
C6A—H6AC	0.96	C7A—C8A	1.522 (4)
N1B—C5B	1.351 (3)	F1B—C8B	1.343 (4)
N1B—C1B	1.356 (3)	F2B—C8B	1.296 (4)
N1B—H1NB	0.88 (3)	F3B—C8B	1.326 (4)
N2B—C5B	1.329 (3)	F1D—C8B	1.297 (6)
N2B—H2NB	0.854 (19)	F2D—C8B	1.307 (7)
N2B—H3NB	0.830 (19)	F3D—C8B	1.269 (8)
C1B—C2B	1.338 (4)	O1B—C7B	1.220 (3)
C1B—H1BB	0.95 (3)	O2B—C7B	1.233 (3)
C2B—C3B	1.412 (4)	C7B—C8B	1.526 (4)

C5A—N1A—C1A	122.3 (2)	C4B—C3B—C2B	118.8 (2)
C5A—N1A—H1NA	116.6 (16)	C4B—C3B—C6B	121.1 (3)
C1A—N1A—H1NA	121.0 (16)	C2B—C3B—C6B	120.0 (3)
C5A—N2A—H2NA	121.2 (18)	C3B—C4B—C5B	120.9 (2)
C5A—N2A—H3NA	119 (2)	C3B—C4B—H4BA	119.5
H2NA—N2A—H3NA	119 (3)	C5B—C4B—H4BA	119.5
C2A—C1A—N1A	120.9 (2)	N2B—C5B—N1B	118.1 (2)
C2A—C1A—H1AA	119.5	N2B—C5B—C4B	123.9 (2)
N1A—C1A—H1AA	119.5	N1B—C5B—C4B	118.0 (2)
C1A—C2A—C3A	119.3 (2)	C3B—C6B—H6BA	109.5
C1A—C2A—H2AA	120.3	C3B—C6B—H6BB	109.5
C3A—C2A—H2AA	120.3	H6BA—C6B—H6BB	109.5
C4A—C3A—C2A	118.9 (2)	C3B—C6B—H6BC	109.5
C4A—C3A—C6A	121.2 (2)	H6BA—C6B—H6BC	109.5
C2A—C3A—C6A	119.9 (3)	H6BB—C6B—H6BC	109.5
C3A—C4A—C5A	120.8 (2)	O1A—C7A—O2A	128.6 (3)
C3A—C4A—H4AA	119.6	O1A—C7A—C8A	116.2 (2)
C5A—C4A—H4AA	119.6	O2A—C7A—C8A	115.2 (2)
N2A—C5A—N1A	117.9 (2)	F2A—C8A—F1A	122.3 (9)
N2A—C5A—C4A	124.3 (2)	F3C—C8A—F1C	114.7 (11)
N1A—C5A—C4A	117.7 (2)	F3C—C8A—F2C	106.7 (7)
C3A—C6A—H6AA	109.5	F1C—C8A—F2C	88.3 (16)
C3A—C6A—H6AB	109.5	F2A—C8A—F3A	104.7 (7)
H6AA—C6A—H6AB	109.5	F1A—C8A—F3A	93.2 (7)
C3A—C6A—H6AC	109.5	F2A—C8A—C7A	112.1 (6)
H6AA—C6A—H6AC	109.5	F1A—C8A—C7A	112.8 (6)
H6AB—C6A—H6AC	109.5	F3A—C8A—C7A	108.9 (5)
C5B—N1B—C1B	121.7 (2)	O1B—C7B—O2B	128.6 (3)
C5B—N1B—H1NB	118.8 (17)	O1B—C7B—C8B	116.2 (2)
C1B—N1B—H1NB	119.3 (16)	O2B—C7B—C8B	115.2 (2)
C5B—N2B—H2NB	120 (2)	F3D—C8B—F1D	116.9 (9)
C5B—N2B—H3NB	120 (2)	F3D—C8B—F2D	103.4 (9)
H2NB—N2B—H3NB	120 (3)	F1D—C8B—F2D	103.7 (7)
C2B—C1B—N1B	121.1 (2)	F2B—C8B—F3B	108.5 (4)
C2B—C1B—H1BB	125.9 (17)	F2B—C8B—F1B	106.5 (4)
N1B—C1B—H1BB	112.9 (17)	F3B—C8B—F1B	101.8 (3)
C1B—C2B—C3B	119.4 (2)	F2B—C8B—C7B	113.0 (3)
C1B—C2B—H2BA	120.3	F3B—C8B—C7B	112.8 (3)
C3B—C2B—H2BA	120.3	F1B—C8B—C7B	113.5 (2)

C5A—N1A—C1A—C2A	0.2 (4)	O1A—C7A—C8A—F3C	20.8 (11)
N1A—C1A—C2A—C3A	−0.3 (4)	O2A—C7A—C8A—F3C	−159.7 (11)
C1A—C2A—C3A—C4A	0.2 (4)	O1A—C7A—C8A—F1A	141.7 (6)
C1A—C2A—C3A—C6A	−179.2 (3)	O2A—C7A—C8A—F1A	−38.8 (6)
C2A—C3A—C4A—C5A	0.0 (4)	O1A—C7A—C8A—F1C	159.8 (10)
C6A—C3A—C4A—C5A	179.4 (2)	O2A—C7A—C8A—F1C	−20.6 (10)
C1A—N1A—C5A—N2A	179.6 (2)	O1A—C7A—C8A—F2C	−101.8 (11)
C1A—N1A—C5A—C4A	0.0 (3)	O2A—C7A—C8A—F2C	77.7 (11)
C3A—C4A—C5A—N2A	−179.7 (2)	O1A—C7A—C8A—F3A	39.7 (6)
C3A—C4A—C5A—N1A	−0.1 (3)	O2A—C7A—C8A—F3A	−140.8 (6)
C5B—N1B—C1B—C2B	0.1 (4)	O1B—C7B—C8B—F3D	−57.7 (10)
N1B—C1B—C2B—C3B	0.6 (4)	O2B—C7B—C8B—F3D	122.7 (10)
C1B—C2B—C3B—C4B	−1.2 (4)	O1B—C7B—C8B—F2B	96.6 (5)
C1B—C2B—C3B—C6B	178.8 (3)	O2B—C7B—C8B—F2B	−83.0 (5)
C2B—C3B—C4B—C5B	1.1 (4)	O1B—C7B—C8B—F1D	169.3 (10)
C6B—C3B—C4B—C5B	−179.0 (3)	O2B—C7B—C8B—F1D	−10.3 (10)
C1B—N1B—C5B—N2B	179.7 (3)	O1B—C7B—C8B—F2D	55.9 (8)
C1B—N1B—C5B—C4B	−0.3 (4)	O2B—C7B—C8B—F2D	−123.7 (7)
C3B—C4B—C5B—N2B	179.6 (3)	O1B—C7B—C8B—F3B	−26.9 (4)
C3B—C4B—C5B—N1B	−0.3 (4)	O2B—C7B—C8B—F3B	153.5 (3)
O1A—C7A—C8A—F2A	−75.6 (8)	O1B—C7B—C8B—F1B	−142.0 (3)
O2A—C7A—C8A—F2A	103.9 (8)	O2B—C7B—C8B—F1B	38.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O2Aⁱ	0.89 (3)	1.85 (3)	2.740 (3)	173 (2)
N2A—H2NA···O1Aⁱ	0.85 (2)	2.02 (2)	2.871 (3)	176 (2)
N2A—H3NA···O2Bⁱⁱ	0.85 (2)	2.04 (2)	2.835 (3)	156 (2)
N1B—H1NB···O2Bⁱⁱ	0.87 (3)	1.86 (3)	2.734 (3)	175 (2)
N2B—H2NB···O1Bⁱⁱ	0.85 (2)	2.01 (2)	2.858 (3)	176 (3)
N2B—H3NB···O2Aⁱⁱⁱ	0.83 (3)	2.04 (2)	2.848 (3)	164 (3)
C4A—H4AA···O1B^iv	0.93	2.57	3.423 (3)	153
C6B—H6BA···O1A^v	0.96	2.57	3.518 (5)	169

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₂F₃O₂⁻
M_r	222.17
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.5229 (2), 11.0649 (3), 11.6573 (3)
α, β, γ (°)	81.208 (1), 72.199 (2), 74.647 (1)
V (Å³)	1006.26 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.56 × 0.19 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.925, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	21533, 5803, 3405
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.187, 1.06
No. of reflections	5803
No. of parameters	357
No. of restraints	114
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.26

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O2Aⁱ	0.89 (3)	1.85 (3)	2.740 (3)	173 (2)
N2A—H2NA···O1Aⁱ	0.85 (2)	2.02 (2)	2.871 (3)	176 (2)
N2A—H3NA···O2Bⁱⁱ	0.85 (2)	2.04 (2)	2.835 (3)	156 (2)
N1B—H1NB···O2Bⁱⁱ	0.87 (3)	1.86 (3)	2.734 (3)	175 (2)
N2B—H2NB···O1Bⁱⁱ	0.85 (2)	2.01 (2)	2.858 (3)	176 (3)
N2B—H3NB···O2Aⁱⁱⁱ	0.83 (3)	2.04 (2)	2.848 (3)	164 (3)
C4A—H4AA···O1B^iv	0.93	2.57	3.423 (3)	153
C6B—H6BA···O1A^v	0.96	2.57	3.518 (5)	169

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

MH and HKF thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research University Golden Goose grant No. 1001/PFIZIK/811012. MH thanks USM for a post-doctoral research fellowship.

References

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