2-Amino-5-chloro­pyridinium trifluoro­acetate

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

doi:10.1107/S1600536810008196

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages o783-o784

doi:10.1107/S1600536810008196

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2-Amino-5-chloropyridinium 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 22 February 2010; accepted 3 March 2010; online 10 March 2010)

The asymmetric unit of the title salt, C₅H₆ClN₂⁺·C₂F₃O₂⁻, contains two independent 2-amino-5-chloropyridinium cations and two independent trifluoroacetate anions. The F atoms of both anions are disordered over two sets of positions, with occupancy ratios of 0.672 (12):0.328 (12) and 0.587 (15):0.413 (15). In the crystal, the cations and anions are linked via N—H⋯O and C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (001).

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ); Katritzky et al. (1996 ). For related structures, see: Pourayoubi et al. (2007 ); Hemamalini & Fun (2010a ,b ,c ). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ); Jeffrey (1997 ); Scheiner (1997 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₅H₆ClN₂⁺·C₂F₃O₂⁻
M_r = 242.59
Monoclinic, P c
a = 5.0377 (1) Å
b = 11.2923 (2) Å
c = 17.5386 (3) Å
β = 90.001 (1)°
V = 997.72 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 296 K
0.43 × 0.26 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.842, T_max = 0.945
17652 measured reflections
4388 independent reflections
3191 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.03
4388 reflections
375 parameters
110 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 2096 Friedel pairs
Flack parameter: 0.01 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1Aⁱ	0.94 (3)	1.79 (3)	2.727 (3)	173 (3)
N2A—H2NA⋯O2Aⁱ	0.90 (3)	1.95 (3)	2.840 (4)	175 (3)
N2A—H3NA⋯O1Bⁱⁱ	0.87 (3)	2.00 (2)	2.863 (3)	171 (4)
N1B—H1NB⋯O1Bⁱⁱⁱ	0.87 (3)	1.87 (3)	2.734 (3)	175 (3)
N2B—H2NB⋯O2Bⁱⁱⁱ	0.90 (2)	1.94 (2)	2.838 (4)	170 (2)
N2B—H3NB⋯O1A	0.87 (3)	1.99 (2)	2.861 (3)	175 (4)
C5A—H5AA⋯O2Bⁱ	0.97 (3)	2.29 (3)	3.210 (4)	158 (3)
C5B—H5BA⋯O2A^iv	0.96 (3)	2.31 (3)	3.208 (3)	157 (3)
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+2, z-{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) x, y+1, z.

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/S1600536810008196/ci5043sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008196/ci5043Isup2.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). We have recently reported the crystal structures of 2-amino-5-chloropyridinium 4-hydroxybenzoate (Hemamalini & Fun, 2010a), 2-amino-5-chloropyridine benzoic acid (Hemamalini & Fun, 2010b) and 2-amino-5-chloropyridinium hydrogen succinate. (Hemamalini & Fun, 2010c). 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-5-chloropyridinium cations (A and B) and two trifluoroacetate anions (A and B) (Fig. 1). Each 2-amino-5-chloropyridinium cation is planar, with a maximum deviation of 0.017 (3) Å for atom C3A in cation A and 0.026 (1) Å for atom C1B in cation B. In the cations, protonation at atoms N1A and N1B lead to a slight increase in the C1A–N1A–C5A [122.7 (3)°] and C1B—N1B—C5B [123.2 (3)°] angles compared to those observed in an unprotonated structure (Pourayoubi et al., 2007). Bond lengths and angles are normal (Allen et al., 1987).

In the crystal packing (Fig. 2), the A/B type 2-amino-5-chloropyridinium cations interact with the carboxylate groups of the A/B type trifluoroacetate anions through a pair of N—H···O hydrogen bonds, forming an R₂²(8) (Bernstein et al., 1995) ring motif. The packing is further stabilized by weak C5A—H5AA···O2B and C5B—H5BA···O2A (Table 1) hydrogen bonds.

Related literature top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For related structures, see: Pourayoubi et al. (2007); Hemamalini & Fun (2010a,b,c). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987).

Experimental top

To a hot methanol solution (20 ml) of 2-amino-5-chloropyridine (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 50% probability level. All disorder components are shown.
	Fig. 2. The crystal packing of the title compound, showing the hydrogen-bonded (dashed lines) networks.

2-Amino-5-chloropyridinium trifluoroacetate top

Crystal data top

C₅H₆ClN₂⁺·C₂F₃O₂⁻	F(000) = 488
M_r = 242.59	D_x = 1.615 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 6764 reflections
a = 5.0377 (1) Å	θ = 2.9–23.0°
b = 11.2923 (2) Å	µ = 0.41 mm⁻¹
c = 17.5386 (3) Å	T = 296 K
β = 90.001 (1)°	Blcok, colourless
V = 997.72 (3) Å³	0.43 × 0.26 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4388 independent reflections
Radiation source: fine-focus sealed tube	3191 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.842, T_max = 0.945	k = −14→14
17652 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0449P)² + 0.0781P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4388 reflections	Δρ_max = 0.12 e Å⁻³
375 parameters	Δρ_min = −0.15 e Å⁻³
110 restraints	Absolute structure: Flack (1983), 2096 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (7)

Crystal data top

C₅H₆ClN₂⁺·C₂F₃O₂⁻	V = 997.72 (3) Å³
M_r = 242.59	Z = 4
Monoclinic, Pc	Mo Kα radiation
a = 5.0377 (1) Å	µ = 0.41 mm⁻¹
b = 11.2923 (2) Å	T = 296 K
c = 17.5386 (3) Å	0.43 × 0.26 × 0.14 mm
β = 90.001 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4388 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3191 reflections with I > 2σ(I)
T_min = 0.842, T_max = 0.945	R_int = 0.027
17652 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	Δρ_max = 0.12 e Å⁻³
S = 1.03	Δρ_min = −0.15 e Å⁻³
4388 reflections	Absolute structure: Flack (1983), 2096 Friedel pairs
375 parameters	Absolute structure parameter: 0.01 (7)
110 restraints

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)
Cl1A	1.1299 (2)	0.65347 (8)	0.53508 (6)	0.0863 (3)
N1A	0.6452 (5)	0.84270 (19)	0.40858 (15)	0.0509 (6)
N2A	0.5936 (6)	1.0402 (2)	0.38078 (18)	0.0688 (7)
C1A	0.7219 (6)	0.9568 (2)	0.41821 (16)	0.0535 (7)
C2A	0.9320 (6)	0.9791 (3)	0.46873 (17)	0.0620 (7)
C3A	1.0548 (7)	0.8880 (3)	0.50499 (18)	0.0657 (8)
C4A	0.9711 (6)	0.7707 (2)	0.49139 (16)	0.0598 (7)
C5A	0.7678 (6)	0.7505 (3)	0.44427 (18)	0.0547 (7)
Cl1B	0.6300 (2)	0.84657 (8)	0.66202 (6)	0.0862 (3)
N1B	0.1456 (5)	0.65696 (18)	0.78845 (16)	0.0515 (6)
N2B	0.0936 (6)	0.4597 (2)	0.81654 (19)	0.0696 (7)
C1B	0.2208 (6)	0.5431 (2)	0.77885 (16)	0.0536 (7)
C2B	0.4312 (6)	0.5216 (3)	0.72826 (17)	0.0622 (7)
C3B	0.5552 (7)	0.6116 (3)	0.69219 (18)	0.0647 (8)
C4B	0.4720 (6)	0.7291 (2)	0.70553 (16)	0.0592 (7)
C5B	0.2675 (6)	0.7496 (2)	0.75301 (17)	0.0543 (7)
F1A	0.1120 (15)	0.2688 (5)	0.6659 (3)	0.103 (2)	0.672 (12)
F2A	−0.2319 (10)	0.2039 (11)	0.7180 (3)	0.145 (3)	0.672 (12)
F3A	−0.002 (2)	0.0953 (5)	0.6438 (3)	0.133 (3)	0.672 (12)
F1C	−0.050 (4)	0.2829 (7)	0.6917 (10)	0.120 (5)	0.328 (12)
F2C	−0.217 (2)	0.1179 (12)	0.6924 (8)	0.113 (4)	0.328 (12)
F3C	0.135 (3)	0.1402 (18)	0.6367 (6)	0.143 (6)	0.328 (12)
O1A	0.2546 (5)	0.21708 (17)	0.80805 (12)	0.0645 (5)
O2A	0.1855 (6)	0.0286 (2)	0.77827 (16)	0.0847 (7)
C6A	0.1664 (6)	0.1353 (3)	0.76755 (19)	0.0562 (7)
C7A	0.0082 (7)	0.1732 (3)	0.69751 (19)	0.0725 (9)
F1B	0.6266 (18)	0.7635 (7)	1.0334 (4)	0.106 (2)	0.587 (15)
F2B	0.2762 (14)	0.7160 (13)	0.9780 (4)	0.134 (3)	0.587 (15)
F3B	0.473 (3)	0.5940 (5)	1.0508 (5)	0.129 (3)	0.587 (15)
F1D	0.490 (4)	0.7839 (5)	1.0133 (8)	0.120 (4)	0.413 (15)
F2D	0.2692 (17)	0.6301 (14)	0.9986 (7)	0.123 (4)	0.413 (15)
F3D	0.615 (3)	0.6227 (14)	1.0603 (5)	0.134 (4)	0.413 (15)
O1B	0.7544 (5)	0.71703 (17)	0.88936 (12)	0.0642 (5)
O2B	0.6855 (6)	0.5286 (2)	0.91889 (15)	0.0840 (7)
C6B	0.6665 (6)	0.6354 (3)	0.92942 (19)	0.0560 (7)
C7B	0.5093 (7)	0.6735 (3)	0.99991 (19)	0.0718 (9)
H1NA	0.507 (7)	0.829 (3)	0.3734 (17)	0.059 (8)*
H2NA	0.470 (6)	1.021 (3)	0.3463 (17)	0.073 (10)*
H3NA	0.652 (7)	1.112 (2)	0.388 (2)	0.071 (10)*
H2AA	0.998 (8)	1.056 (4)	0.477 (2)	0.081 (10)*
H3AA	1.194 (7)	0.905 (3)	0.543 (2)	0.073 (10)*
H5AA	0.694 (6)	0.673 (3)	0.4342 (16)	0.050 (7)*
H1NB	0.023 (7)	0.672 (3)	0.8221 (18)	0.059 (9)*
H2NB	−0.023 (5)	0.479 (2)	0.8537 (14)	0.057 (8)*
H3NB	0.143 (8)	0.386 (2)	0.811 (2)	0.079 (11)*
H2BA	0.494 (7)	0.448 (3)	0.719 (2)	0.077 (10)*
H3BA	0.701 (8)	0.598 (4)	0.656 (2)	0.081 (11)*
H5BA	0.192 (7)	0.826 (3)	0.7621 (19)	0.065 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0909 (6)	0.0709 (6)	0.0971 (6)	0.0149 (5)	−0.0160 (5)	0.0077 (5)
N1A	0.0552 (15)	0.0349 (13)	0.0625 (15)	−0.0015 (9)	−0.0004 (12)	−0.0045 (10)
N2A	0.082 (2)	0.0340 (13)	0.0903 (19)	−0.0087 (13)	−0.0106 (16)	0.0013 (13)
C1A	0.0606 (17)	0.0382 (15)	0.0618 (17)	−0.0065 (12)	0.0072 (14)	−0.0057 (12)
C2A	0.0690 (19)	0.0444 (15)	0.0727 (18)	−0.0111 (14)	0.0036 (15)	−0.0073 (13)
C3A	0.065 (2)	0.067 (2)	0.0655 (19)	−0.0096 (16)	−0.0006 (16)	−0.0126 (15)
C4A	0.0682 (19)	0.0514 (15)	0.0597 (15)	0.0034 (14)	0.0031 (14)	−0.0035 (12)
C5A	0.0636 (19)	0.0372 (14)	0.0634 (16)	−0.0017 (13)	0.0059 (14)	−0.0033 (12)
Cl1B	0.0915 (6)	0.0693 (6)	0.0976 (6)	−0.0155 (5)	0.0171 (5)	0.0067 (5)
N1B	0.0584 (16)	0.0329 (13)	0.0632 (16)	0.0015 (10)	0.0008 (12)	−0.0044 (10)
N2B	0.084 (2)	0.0342 (13)	0.0906 (19)	0.0067 (13)	0.0139 (16)	0.0000 (13)
C1B	0.0582 (17)	0.0381 (16)	0.0644 (18)	0.0067 (12)	−0.0075 (14)	−0.0054 (12)
C2B	0.0684 (19)	0.0443 (15)	0.0737 (18)	0.0119 (14)	−0.0043 (15)	−0.0100 (13)
C3B	0.067 (2)	0.0648 (19)	0.0627 (18)	0.0089 (16)	0.0010 (16)	−0.0096 (15)
C4B	0.0669 (18)	0.0516 (15)	0.0592 (15)	−0.0050 (14)	−0.0034 (14)	−0.0023 (12)
C5B	0.0641 (19)	0.0370 (14)	0.0617 (16)	0.0009 (13)	−0.0068 (14)	−0.0045 (12)
F1A	0.137 (5)	0.087 (3)	0.085 (3)	−0.028 (3)	−0.016 (2)	0.036 (2)
F2A	0.079 (3)	0.232 (8)	0.126 (4)	0.045 (4)	−0.002 (2)	0.037 (5)
F3A	0.211 (7)	0.091 (3)	0.096 (3)	−0.004 (3)	−0.049 (4)	−0.036 (2)
F1C	0.159 (10)	0.061 (4)	0.141 (8)	0.016 (6)	−0.064 (7)	−0.002 (5)
F2C	0.088 (6)	0.104 (7)	0.147 (8)	−0.016 (5)	−0.041 (5)	0.011 (6)
F3C	0.148 (9)	0.204 (11)	0.078 (6)	−0.006 (7)	0.005 (6)	−0.007 (7)
O1A	0.0824 (15)	0.0373 (11)	0.0737 (13)	0.0111 (9)	−0.0104 (11)	−0.0062 (9)
O2A	0.1066 (19)	0.0374 (13)	0.110 (2)	0.0061 (12)	−0.0211 (15)	−0.0014 (12)
C6A	0.0601 (18)	0.0410 (16)	0.0676 (18)	0.0045 (13)	0.0056 (13)	−0.0019 (13)
C7A	0.089 (3)	0.0580 (19)	0.071 (2)	−0.0068 (18)	−0.0022 (18)	−0.0009 (15)
F1B	0.122 (5)	0.110 (5)	0.085 (3)	−0.021 (3)	0.008 (3)	−0.041 (3)
F2B	0.086 (4)	0.196 (8)	0.122 (4)	0.049 (5)	0.006 (3)	−0.022 (5)
F3B	0.188 (8)	0.085 (3)	0.116 (4)	−0.012 (4)	0.061 (5)	0.028 (3)
F1D	0.174 (9)	0.052 (3)	0.134 (7)	0.006 (5)	0.077 (7)	−0.007 (4)
F2D	0.072 (4)	0.141 (8)	0.156 (7)	−0.012 (5)	0.030 (4)	−0.026 (6)
F3D	0.150 (8)	0.184 (9)	0.066 (4)	−0.001 (6)	0.001 (5)	0.033 (5)
O1B	0.0833 (15)	0.0377 (11)	0.0715 (13)	0.0099 (9)	0.0124 (11)	0.0067 (9)
O2B	0.1067 (19)	0.0370 (12)	0.1083 (19)	0.0034 (12)	0.0226 (14)	0.0008 (12)
C6B	0.0605 (18)	0.0381 (16)	0.0696 (18)	0.0039 (13)	−0.0061 (13)	0.0001 (13)
C7B	0.089 (3)	0.0571 (19)	0.070 (2)	−0.0047 (18)	0.0054 (18)	0.0018 (15)

Geometric parameters (Å, º) top

Cl1A—C4A	1.726 (3)	C2B—H2BA	0.90 (4)
N1A—C1A	1.355 (4)	C3B—C4B	1.411 (5)
N1A—C5A	1.362 (4)	C3B—H3BA	0.98 (4)
N1A—H1NA	0.94 (3)	C4B—C5B	1.345 (4)
N2A—C1A	1.317 (4)	C5B—H5BA	0.95 (4)
N2A—H2NA	0.90 (2)	F1A—C7A	1.321 (4)
N2A—H3NA	0.87 (2)	F2A—C7A	1.308 (5)
C1A—C2A	1.403 (4)	F3A—C7A	1.290 (5)
C2A—C3A	1.358 (5)	F1C—C7A	1.276 (7)
C2A—H2AA	0.94 (4)	F2C—C7A	1.299 (7)
C3A—C4A	1.411 (5)	F3C—C7A	1.299 (7)
C3A—H3AA	0.98 (4)	O1A—C6A	1.247 (4)
C4A—C5A	1.336 (4)	O2A—C6A	1.223 (4)
C5A—H5AA	0.97 (3)	C6A—C7A	1.525 (5)
Cl1B—C4B	1.725 (3)	F1B—C7B	1.314 (5)
N1B—C1B	1.351 (4)	F2B—C7B	1.325 (5)
N1B—C5B	1.363 (4)	F3B—C7B	1.280 (5)
N1B—H1NB	0.87 (3)	F1D—C7B	1.272 (6)
N2B—C1B	1.317 (4)	F2D—C7B	1.306 (6)
N2B—H2NB	0.902 (19)	F3D—C7B	1.317 (7)
N2B—H3NB	0.87 (2)	O1B—C6B	1.240 (4)
C1B—C2B	1.404 (4)	O2B—C6B	1.224 (4)
C2B—C3B	1.351 (5)	C6B—C7B	1.530 (5)

C1A—N1A—C5A	122.7 (3)	C2B—C3B—C4B	119.5 (3)
C1A—N1A—H1NA	116.9 (18)	C2B—C3B—H3BA	122 (3)
C5A—N1A—H1NA	120.4 (18)	C4B—C3B—H3BA	119 (3)
C1A—N2A—H2NA	120 (2)	C5B—C4B—C3B	119.5 (3)
C1A—N2A—H3NA	115 (3)	C5B—C4B—Cl1B	119.7 (2)
H2NA—N2A—H3NA	124 (3)	C3B—C4B—Cl1B	120.8 (3)
N2A—C1A—N1A	118.5 (3)	C4B—C5B—N1B	119.7 (3)
N2A—C1A—C2A	123.8 (3)	C4B—C5B—H5BA	124 (2)
N1A—C1A—C2A	117.7 (3)	N1B—C5B—H5BA	116 (2)
C3A—C2A—C1A	120.2 (3)	O2A—C6A—O1A	127.9 (3)
C3A—C2A—H2AA	118 (2)	O2A—C6A—C7A	116.2 (3)
C1A—C2A—H2AA	122 (2)	O1A—C6A—C7A	115.9 (3)
C2A—C3A—C4A	119.7 (3)	F1C—C7A—F3C	109.0 (10)
C2A—C3A—H3AA	120 (2)	F1C—C7A—F2C	105.1 (8)
C4A—C3A—H3AA	121 (2)	F3C—C7A—F2C	103.6 (9)
C5A—C4A—C3A	119.6 (3)	F3A—C7A—F2A	110.2 (6)
C5A—C4A—Cl1A	119.9 (2)	F3A—C7A—F1A	105.4 (5)
C3A—C4A—Cl1A	120.4 (3)	F2A—C7A—F1A	105.4 (5)
C4A—C5A—N1A	120.1 (3)	F3A—C7A—C6A	114.6 (4)
C4A—C5A—H5AA	124.3 (18)	F2A—C7A—C6A	109.6 (3)
N1A—C5A—H5AA	115.6 (18)	F1A—C7A—C6A	111.1 (3)
C1B—N1B—C5B	123.2 (3)	O2B—C6B—O1B	128.2 (3)
C1B—N1B—H1NB	118 (2)	O2B—C6B—C7B	116.1 (3)
C5B—N1B—H1NB	118 (2)	O1B—C6B—C7B	115.7 (3)
C1B—N2B—H2NB	120.5 (18)	F1D—C7B—F2D	107.5 (7)
C1B—N2B—H3NB	119 (3)	F3B—C7B—F1B	107.1 (6)
H2NB—N2B—H3NB	119 (3)	F1D—C7B—F3D	108.0 (9)
N2B—C1B—N1B	118.8 (3)	F2D—C7B—F3D	103.0 (7)
N2B—C1B—C2B	124.1 (3)	F3B—C7B—F2B	109.3 (6)
N1B—C1B—C2B	117.1 (3)	F1B—C7B—F2B	104.3 (5)
C3B—C2B—C1B	121.0 (3)	F3B—C7B—C6B	116.1 (4)
C3B—C2B—H2BA	117 (2)	F1B—C7B—C6B	110.3 (4)
C1B—C2B—H2BA	122 (2)	F2B—C7B—C6B	109.0 (4)

C5A—N1A—C1A—N2A	179.3 (3)	O2A—C6A—C7A—F3A	−24.8 (7)
C5A—N1A—C1A—C2A	−1.7 (4)	O1A—C6A—C7A—F3A	157.0 (6)
N2A—C1A—C2A—C3A	−179.8 (3)	O2A—C6A—C7A—F3C	−66.6 (11)
N1A—C1A—C2A—C3A	1.2 (4)	O1A—C6A—C7A—F3C	115.3 (11)
C1A—C2A—C3A—C4A	0.3 (5)	O2A—C6A—C7A—F2C	47.5 (10)
C2A—C3A—C4A—C5A	−1.5 (5)	O1A—C6A—C7A—F2C	−130.6 (9)
C2A—C3A—C4A—Cl1A	178.4 (2)	O2A—C6A—C7A—F2A	99.7 (7)
C3A—C4A—C5A—N1A	1.1 (4)	O1A—C6A—C7A—F2A	−78.4 (7)
Cl1A—C4A—C5A—N1A	−178.8 (2)	O2A—C6A—C7A—F1A	−144.2 (5)
C1A—N1A—C5A—C4A	0.5 (4)	O1A—C6A—C7A—F1A	37.6 (5)
C5B—N1B—C1B—N2B	178.9 (3)	O2B—C6B—C7B—F1D	178.7 (12)
C5B—N1B—C1B—C2B	−1.5 (4)	O1B—C6B—C7B—F1D	−2.6 (12)
N2B—C1B—C2B—C3B	−179.1 (3)	O2B—C6B—C7B—F3B	17.6 (8)
N1B—C1B—C2B—C3B	1.3 (4)	O1B—C6B—C7B—F3B	−163.7 (8)
C1B—C2B—C3B—C4B	0.0 (5)	O2B—C6B—C7B—F2D	−56.8 (10)
C2B—C3B—C4B—C5B	−1.1 (5)	O1B—C6B—C7B—F2D	121.9 (9)
C2B—C3B—C4B—Cl1B	178.7 (3)	O2B—C6B—C7B—F1B	139.6 (6)
C3B—C4B—C5B—N1B	0.9 (4)	O1B—C6B—C7B—F1B	−41.6 (6)
Cl1B—C4B—C5B—N1B	−178.8 (2)	O2B—C6B—C7B—F3D	55.7 (9)
C1B—N1B—C5B—C4B	0.4 (4)	O1B—C6B—C7B—F3D	−125.6 (9)
O2A—C6A—C7A—F1C	169.3 (13)	O2B—C6B—C7B—F2B	−106.4 (8)
O1A—C6A—C7A—F1C	−8.9 (13)	O1B—C6B—C7B—F2B	72.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1Aⁱ	0.94 (3)	1.79 (3)	2.727 (3)	173 (3)
N2A—H2NA···O2Aⁱ	0.90 (3)	1.95 (3)	2.840 (4)	175 (3)
N2A—H3NA···O1Bⁱⁱ	0.87 (3)	2.00 (2)	2.863 (3)	171 (4)
N1B—H1NB···O1Bⁱⁱⁱ	0.87 (3)	1.87 (3)	2.734 (3)	175 (3)
N2B—H2NB···O2Bⁱⁱⁱ	0.90 (2)	1.94 (2)	2.838 (4)	170 (2)
N2B—H3NB···O1A	0.87 (3)	1.99 (2)	2.861 (3)	175 (4)
C5A—H5AA···O2Bⁱ	0.97 (3)	2.29 (3)	3.210 (4)	158 (3)
C5B—H5BA···O2A^iv	0.96 (3)	2.31 (3)	3.208 (3)	157 (3)

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

Experimental details

Crystal data
Chemical formula	C₅H₆ClN₂⁺·C₂F₃O₂⁻
M_r	242.59
Crystal system, space group	Monoclinic, Pc
Temperature (K)	296
a, b, c (Å)	5.0377 (1), 11.2923 (2), 17.5386 (3)
β (°)	90.001 (1)
V (Å³)	997.72 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.43 × 0.26 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.842, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	17652, 4388, 3191
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.03
No. of reflections	4388
No. of parameters	375
No. of restraints	110
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.15
Absolute structure	Flack (1983), 2096 Friedel pairs
Absolute structure parameter	0.01 (7)

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···O1Aⁱ	0.94 (3)	1.79 (3)	2.727 (3)	173 (3)
N2A—H2NA···O2Aⁱ	0.90 (3)	1.95 (3)	2.840 (4)	175 (3)
N2A—H3NA···O1Bⁱⁱ	0.87 (3)	2.00 (2)	2.863 (3)	171 (4)
N1B—H1NB···O1Bⁱⁱⁱ	0.87 (3)	1.87 (3)	2.734 (3)	175 (3)
N2B—H2NB···O2Bⁱⁱⁱ	0.90 (2)	1.94 (2)	2.838 (4)	170 (2)
N2B—H3NB···O1A	0.87 (3)	1.99 (2)	2.861 (3)	175 (4)
C5A—H5AA···O2Bⁱ	0.97 (3)	2.29 (3)	3.210 (4)	158 (3)
C5B—H5BA···O2A^iv	0.96 (3)	2.31 (3)	3.208 (3)	157 (3)

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

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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