organic compounds
2-Amino-5-chloropyridinium trifluoroacetate
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: hkfun@usm.my
The 5H6ClN2+·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).
of the title salt, CRelated 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
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536810008196/ci5043sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810008196/ci5043Isup2.hkl
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.
All H atoms were located in a difference Fourier map and refined [N—H =0.87 (2)–0.94 (3) Å and C—H =0.94 (4)–0.98 (4) Å]; the N–H distances of the NH2 groups were restrained to be equal. The F atoms of both anions are disordered over two positions, with site occupancies of 0.672 (12) and 0.328 (12) in one of the anions, and 0.587 (15):0.413 (15) in the other anion. In each anion, the C—F distances were restrained to be equal and the Uij components of F atoms were restrained to an approximate isotropic behaviour.
Data collection: APEX2 (Bruker, 2009); cell
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).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. |
C5H6ClN2+·C2F3O2− | F(000) = 488 |
Mr = 242.59 | Dx = 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 |
Bruker SMART APEXII CCD area-detector diffractometer | 4388 independent reflections |
Radiation source: fine-focus sealed tube | 3191 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −6→6 |
Tmin = 0.842, Tmax = 0.945 | k = −14→14 |
17652 measured reflections | l = −22→22 |
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(Fo2) + (0.0449P)2 + 0.0781P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
4388 reflections | Δρmax = 0.12 e Å−3 |
375 parameters | Δρmin = −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) |
C5H6ClN2+·C2F3O2− | V = 997.72 (3) Å3 |
Mr = 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)° |
Bruker SMART APEXII CCD area-detector diffractometer | 4388 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3191 reflections with I > 2σ(I) |
Tmin = 0.842, Tmax = 0.945 | Rint = 0.027 |
17652 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.094 | Δρmax = 0.12 e Å−3 |
S = 1.03 | Δρmin = −0.15 e Å−3 |
4388 reflections | Absolute structure: Flack (1983), 2096 Friedel pairs |
375 parameters | Absolute structure parameter: 0.01 (7) |
110 restraints |
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. |
x | y | z | Uiso*/Ueq | 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)* |
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) |
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) |
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···O2Aiv | 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− |
Mr | 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) |
Tmin, Tmax | 0.842, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17652, 4388, 3191 |
Rint | 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 |
Δρmax, Δρmin (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).
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···O2Aiv | 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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.