organic compounds
2-Amino-5-methylpyridinium 2-hydroxy-5-chlorobenzoate
aSchool of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bDepartment of Physics, Faculty of Science, University of Mazandaran, Babolsar, Iran
*Correspondence e-mail: arazaki@usm.my
In the 5-chlorosalicylate anion of the title salt, C6H9N2+·C7H4ClO3−, an intramolecular O—H⋯O hydrogen bond with an S(6) graph-set motif is observed and the dihedral angle between the benzene ring and the –CO2 group is 1.6 (6)°. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxylate O atoms via a pair of N—H⋯O hydrogen bonds, forming an R22(8) ring motif. The also features N—H⋯O and weak C—H⋯O interactions, resulting in a layer parallel to (10-1).
Related literature
For details of non-covalent interactions, see: Desiraju (2007); Aakeroy & Seddon (1993). For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For related structures, see: Nahringbauer & Kvick (1977); Raza et al. (2010); Thanigaimani et al. (2012a,b). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).
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
https://doi.org/10.1107/S160053681205101X/is5232sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681205101X/is5232Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S160053681205101X/is5232Isup3.cml
Hot methanol solutions (20 ml) of 2-amino5-methylpyridine (54 mg, Aldrich) and 5-chlorosalicylic acid (43 mg, Aldrich) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound (I) appeared after a few days.
O- and N-bound H atoms were located in a difference Fourier maps. Atoms H1O3, H1N1 and H2N2 were refined freely, while atom H1N2 was refined with a bond length restraint N—H = 0.85 (1) Å [refined distance: O3—H1O3 = 0.92 (7) Å, N1—H1N1 = 0.94 (6) Å, N2—H1N2 = 0.853 (10) Å and N2—H2N2 = 0.85 (7) Å]. The remaining hydrogen atoms were positioned geometrically (C—H = 0.95–0.98 Å) and were refined using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). A rotating group model was used for the methyl group.
Supramolecular architectures assembled via various delicate noncovalent interactions such as hydrogen bonds, π–π stacking and electrostatic interactions, etc., have attracted intense interest in recent years because of their fascinating structural diversity and potential applications for functional materials (Desiraju, 2007). Especially, the application of intermolecular hydrogen bonds is a well known and efficient tool in the field of organic crystal design owing to its strength and directional properties (Aakeroy & Seddon, 1993). Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). The are often involved in hydrogen-bond interactions. In order to study potential hydrogen bonding interactions, as part of our ongoing studies on pyridine derivatives (Thanigaimani et al., 2012a,b), the determination of the title compound (I) was carried out.
The
(Fig. 1) contains one 2-amino-5-methylpyridinium cation and one 5-chlorosalicylate anion. The proton transfers from the one of the carboxyl group oxygen atom (O2) to atom N1 of 2-amino-5-methylpyrimidine resulted in the widening of C1—N1—C5 angle of the pyridinium ring to 121.0 (5)°, compared to the corresponding angle of 117.4 (3)° in neutral 2-amino-5-methylpyridine (Nahringbauer & Kvick, 1977). The 2-amino-5-methylpyridinium cation is essentially planar, with a maximum diviation of 0.007 (6) Å for atom C3. The bond lengths (Allen et al., 1987) and angles are normal.In the crystal packing (Fig. 2), the protonated N1 atom and a nitrogen atom of the 2-amino group (N2) are hydrogen-bonded to the carboxylate oxygen atoms (O1 and O2) via a pair of intermolecular N1—H1N1···O2i and N2—H1N2···O1i hydrogen bonds (symmetry codes in Table 1), forming a ring motif of R22(8) (Bernstein et al., 1995). There is also an intramolecular O3—H1O3···O2 hydrogen bond in the 5-chlorosalicylate anion, which generates an S(6) ring motif. This motif is also observed in the 1) plane.
of 5-chloro-2-hydroxybenzoic acid (Raza et al., 2010). The is further stabilized by N2—H2N2···O1ii and C8—H8A···O3iii intermolecular interactions. These interactions have resulted in a molecular layer parallel to the (10For details of non-covalent interactions, see: Desiraju (2007); Aakeroy & Seddon (1993). For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For related structures, see: Nahringbauer & Kvick (1977); Raza et al. (2010); Thanigaimani et al. (2012a,b). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).
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 molecular structure of the title compound with atom labels with 50% probability displacement ellipsoids. | |
Fig. 2. The crystal packing of the title compound. The H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity. |
C6H9N2+·C7H4ClO3− | F(000) = 292 |
Mr = 280.70 | Dx = 1.423 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1722 reflections |
a = 9.004 (7) Å | θ = 2.8–29.7° |
b = 5.767 (5) Å | µ = 0.30 mm−1 |
c = 12.617 (10) Å | T = 100 K |
β = 90.415 (16)° | Block, colourless |
V = 655.2 (9) Å3 | 0.46 × 0.18 × 0.07 mm |
Z = 2 |
Bruker SMART APEXII Duo CCD area-detector diffractometer | 2204 independent reflections |
Radiation source: fine-focus sealed tube | 1539 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
φ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.877, Tmax = 0.979 | k = −6→6 |
4785 measured reflections | l = −14→15 |
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)] = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.201 | w = 1/[σ2(Fo2) + (0.1249P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
2204 reflections | Δρmax = 0.47 e Å−3 |
189 parameters | Δρmin = −0.44 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 941 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.09 (16) |
C6H9N2+·C7H4ClO3− | V = 655.2 (9) Å3 |
Mr = 280.70 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.004 (7) Å | µ = 0.30 mm−1 |
b = 5.767 (5) Å | T = 100 K |
c = 12.617 (10) Å | 0.46 × 0.18 × 0.07 mm |
β = 90.415 (16)° |
Bruker SMART APEXII Duo CCD area-detector diffractometer | 2204 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1539 reflections with I > 2σ(I) |
Tmin = 0.877, Tmax = 0.979 | Rint = 0.061 |
4785 measured reflections |
R[F2 > 2σ(F2)] = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.201 | Δρmax = 0.47 e Å−3 |
S = 1.01 | Δρmin = −0.44 e Å−3 |
2204 reflections | Absolute structure: Flack (1983), 941 Friedel pairs |
189 parameters | Absolute structure parameter: 0.09 (16) |
2 restraints |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.49320 (17) | 0.7884 (3) | 0.59756 (12) | 0.0882 (6) | |
O1 | 0.1352 (4) | 0.0724 (8) | 0.6317 (2) | 0.0718 (11) | |
O2 | 0.1487 (4) | −0.0555 (7) | 0.7972 (2) | 0.0665 (10) | |
O3 | 0.3088 (5) | 0.1483 (9) | 0.9319 (3) | 0.0809 (13) | |
N1 | 0.9568 (5) | 0.6055 (9) | 0.7468 (3) | 0.0581 (11) | |
N2 | 0.9360 (7) | 0.7221 (10) | 0.5745 (4) | 0.0730 (15) | |
C1 | 0.8976 (5) | 0.5709 (10) | 0.6496 (3) | 0.0555 (13) | |
C2 | 0.8031 (5) | 0.3909 (10) | 0.6344 (4) | 0.0613 (15) | |
H2A | 0.7593 | 0.3646 | 0.5667 | 0.074* | |
C3 | 0.7716 (6) | 0.2485 (12) | 0.7170 (4) | 0.0724 (17) | |
H3A | 0.7049 | 0.1232 | 0.7056 | 0.087* | |
C4 | 0.8336 (6) | 0.2786 (13) | 0.8183 (4) | 0.0683 (14) | |
C5 | 0.9247 (6) | 0.4608 (11) | 0.8286 (4) | 0.0622 (14) | |
H5A | 0.9688 | 0.4902 | 0.8959 | 0.075* | |
C6 | 0.8003 (8) | 0.1215 (15) | 0.9103 (5) | 0.093 (2) | |
H6A | 0.8451 | 0.1854 | 0.9750 | 0.139* | |
H6B | 0.8416 | −0.0328 | 0.8966 | 0.139* | |
H6C | 0.6925 | 0.1096 | 0.9191 | 0.139* | |
C7 | 0.3500 (5) | 0.2962 (12) | 0.8536 (3) | 0.0604 (13) | |
C8 | 0.4479 (6) | 0.4684 (11) | 0.8751 (4) | 0.0681 (16) | |
H8A | 0.4865 | 0.4834 | 0.9450 | 0.082* | |
C9 | 0.4933 (6) | 0.6238 (11) | 0.7977 (4) | 0.0666 (15) | |
H9A | 0.5615 | 0.7446 | 0.8138 | 0.080* | |
C10 | 0.4360 (5) | 0.5971 (11) | 0.6960 (4) | 0.0620 (13) | |
C11 | 0.3378 (6) | 0.4262 (11) | 0.6724 (4) | 0.0581 (13) | |
H11A | 0.3005 | 0.4116 | 0.6021 | 0.070* | |
C12 | 0.2916 (5) | 0.2732 (11) | 0.7495 (3) | 0.0507 (11) | |
C13 | 0.1848 (5) | 0.0861 (11) | 0.7244 (3) | 0.0579 (13) | |
H1N1 | 1.019 (6) | 0.735 (11) | 0.754 (4) | 0.070 (17)* | |
H1N2 | 0.985 (6) | 0.846 (7) | 0.587 (5) | 0.09 (3)* | |
H2N2 | 0.888 (7) | 0.705 (14) | 0.517 (5) | 0.09 (2)* | |
H1O3 | 0.225 (7) | 0.071 (13) | 0.909 (5) | 0.083 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0888 (9) | 0.0908 (11) | 0.0850 (10) | −0.0173 (9) | 0.0112 (7) | 0.0067 (10) |
O1 | 0.076 (2) | 0.099 (3) | 0.0404 (16) | −0.016 (2) | −0.0140 (14) | −0.001 (2) |
O2 | 0.076 (2) | 0.080 (3) | 0.0430 (16) | −0.011 (2) | −0.0066 (14) | 0.0066 (19) |
O3 | 0.103 (3) | 0.103 (4) | 0.0371 (17) | −0.013 (3) | −0.0145 (17) | 0.0037 (19) |
N1 | 0.066 (2) | 0.068 (3) | 0.0402 (19) | −0.005 (2) | −0.0016 (16) | −0.002 (2) |
N2 | 0.095 (3) | 0.082 (4) | 0.042 (2) | −0.012 (3) | −0.009 (2) | −0.009 (2) |
C1 | 0.058 (3) | 0.070 (4) | 0.038 (2) | 0.004 (3) | 0.0016 (19) | −0.005 (3) |
C2 | 0.067 (3) | 0.073 (4) | 0.044 (2) | −0.004 (3) | −0.003 (2) | −0.010 (3) |
C3 | 0.070 (3) | 0.077 (5) | 0.070 (3) | −0.010 (3) | 0.004 (2) | −0.014 (3) |
C4 | 0.067 (3) | 0.079 (4) | 0.059 (3) | 0.004 (3) | 0.007 (2) | −0.002 (3) |
C5 | 0.076 (3) | 0.072 (4) | 0.038 (2) | 0.003 (3) | 0.001 (2) | 0.002 (2) |
C6 | 0.108 (5) | 0.098 (5) | 0.072 (3) | −0.003 (4) | 0.014 (3) | 0.017 (4) |
C7 | 0.058 (3) | 0.083 (4) | 0.040 (2) | 0.003 (3) | −0.0017 (18) | −0.006 (3) |
C8 | 0.070 (3) | 0.087 (5) | 0.047 (2) | −0.002 (3) | −0.007 (2) | −0.016 (3) |
C9 | 0.063 (3) | 0.068 (4) | 0.069 (3) | 0.000 (3) | 0.003 (2) | −0.018 (3) |
C10 | 0.053 (2) | 0.075 (4) | 0.058 (3) | −0.005 (3) | 0.005 (2) | −0.004 (3) |
C11 | 0.064 (3) | 0.069 (3) | 0.042 (2) | 0.003 (3) | 0.0054 (19) | −0.008 (2) |
C12 | 0.048 (2) | 0.068 (3) | 0.036 (2) | 0.010 (3) | −0.0010 (15) | −0.009 (3) |
C13 | 0.060 (3) | 0.069 (4) | 0.044 (2) | 0.000 (3) | −0.0012 (19) | 0.005 (3) |
Cl1—C10 | 1.742 (6) | C4—C5 | 1.339 (9) |
O1—C13 | 1.251 (5) | C4—C6 | 1.504 (9) |
O2—C13 | 1.273 (6) | C5—H5A | 0.9500 |
O3—C7 | 1.359 (7) | C6—H6A | 0.9800 |
O3—H1O3 | 0.92 (7) | C6—H6B | 0.9800 |
N1—C1 | 1.349 (6) | C6—H6C | 0.9800 |
N1—C5 | 1.359 (7) | C7—C8 | 1.354 (9) |
N1—H1N1 | 0.94 (6) | C7—C12 | 1.417 (6) |
N2—C1 | 1.335 (7) | C8—C9 | 1.389 (8) |
N2—H1N2 | 0.853 (10) | C8—H8A | 0.9500 |
N2—H2N2 | 0.85 (7) | C9—C10 | 1.388 (7) |
C1—C2 | 1.355 (8) | C9—H9A | 0.9500 |
C2—C3 | 1.358 (8) | C10—C11 | 1.356 (8) |
C2—H2A | 0.9500 | C11—C12 | 1.380 (8) |
C3—C4 | 1.403 (8) | C11—H11A | 0.9500 |
C3—H3A | 0.9500 | C12—C13 | 1.478 (8) |
C7—O3—H1O3 | 107 (4) | C4—C6—H6C | 109.5 |
C1—N1—C5 | 120.9 (5) | H6A—C6—H6C | 109.5 |
C1—N1—H1N1 | 116 (3) | H6B—C6—H6C | 109.5 |
C5—N1—H1N1 | 123 (3) | C8—C7—O3 | 119.7 (4) |
C1—N2—H1N2 | 124 (4) | C8—C7—C12 | 119.4 (5) |
C1—N2—H2N2 | 114 (5) | O3—C7—C12 | 120.9 (5) |
H1N2—N2—H2N2 | 121 (7) | C7—C8—C9 | 121.8 (4) |
N2—C1—N1 | 116.5 (5) | C7—C8—H8A | 119.1 |
N2—C1—C2 | 124.5 (4) | C9—C8—H8A | 119.1 |
N1—C1—C2 | 119.0 (5) | C10—C9—C8 | 118.0 (5) |
C1—C2—C3 | 119.3 (5) | C10—C9—H9A | 121.0 |
C1—C2—H2A | 120.4 | C8—C9—H9A | 121.0 |
C3—C2—H2A | 120.4 | C11—C10—C9 | 121.4 (5) |
C2—C3—C4 | 122.7 (6) | C11—C10—Cl1 | 120.0 (4) |
C2—C3—H3A | 118.6 | C9—C10—Cl1 | 118.6 (5) |
C4—C3—H3A | 118.6 | C10—C11—C12 | 120.6 (4) |
C5—C4—C3 | 115.1 (5) | C10—C11—H11A | 119.7 |
C5—C4—C6 | 121.6 (5) | C12—C11—H11A | 119.7 |
C3—C4—C6 | 123.3 (6) | C11—C12—C7 | 118.8 (5) |
C4—C5—N1 | 122.9 (5) | C11—C12—C13 | 121.0 (4) |
C4—C5—H5A | 118.6 | C7—C12—C13 | 120.2 (5) |
N1—C5—H5A | 118.6 | O1—C13—O2 | 122.9 (5) |
C4—C6—H6A | 109.5 | O1—C13—C12 | 118.3 (4) |
C4—C6—H6B | 109.5 | O2—C13—C12 | 118.8 (4) |
H6A—C6—H6B | 109.5 | ||
C5—N1—C1—N2 | −179.9 (5) | C8—C9—C10—Cl1 | −179.3 (4) |
C5—N1—C1—C2 | 1.0 (7) | C9—C10—C11—C12 | 0.2 (8) |
N2—C1—C2—C3 | −179.7 (5) | Cl1—C10—C11—C12 | 179.9 (4) |
N1—C1—C2—C3 | −0.7 (8) | C10—C11—C12—C7 | −0.8 (7) |
C1—C2—C3—C4 | −0.3 (9) | C10—C11—C12—C13 | −179.9 (5) |
C2—C3—C4—C5 | 1.0 (9) | C8—C7—C12—C11 | 0.8 (7) |
C2—C3—C4—C6 | −179.7 (6) | O3—C7—C12—C11 | −179.4 (5) |
C3—C4—C5—N1 | −0.7 (8) | C8—C7—C12—C13 | 179.9 (5) |
C6—C4—C5—N1 | 180.0 (5) | O3—C7—C12—C13 | −0.3 (7) |
C1—N1—C5—C4 | −0.3 (8) | C11—C12—C13—O1 | −1.3 (7) |
O3—C7—C8—C9 | 180.0 (5) | C7—C12—C13—O1 | 179.6 (5) |
C12—C7—C8—C9 | −0.2 (8) | C11—C12—C13—O2 | 177.8 (4) |
C7—C8—C9—C10 | −0.4 (8) | C7—C12—C13—O2 | −1.2 (7) |
C8—C9—C10—C11 | 0.4 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1O3···O2 | 0.92 (6) | 1.73 (7) | 2.512 (6) | 141 (6) |
N1—H1N1···O2i | 0.94 (6) | 1.76 (6) | 2.683 (7) | 166 (5) |
N2—H1N2···O1i | 0.85 (5) | 1.96 (5) | 2.793 (8) | 165 (4) |
N2—H2N2···O1ii | 0.85 (6) | 2.04 (7) | 2.811 (6) | 152 (7) |
C8—H8A···O3iii | 0.95 | 2.58 | 3.425 (7) | 148 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, y+1/2, −z+1; (iii) −x+1, y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C6H9N2+·C7H4ClO3− |
Mr | 280.70 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 9.004 (7), 5.767 (5), 12.617 (10) |
β (°) | 90.415 (16) |
V (Å3) | 655.2 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.46 × 0.18 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART APEXII Duo CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.877, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4785, 2204, 1539 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.201, 1.01 |
No. of reflections | 2204 |
No. of parameters | 189 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.44 |
Absolute structure | Flack (1983), 941 Friedel pairs |
Absolute structure parameter | 0.09 (16) |
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 |
O3—H1O3···O2 | 0.92 (6) | 1.73 (7) | 2.512 (6) | 141 (6) |
N1—H1N1···O2i | 0.94 (6) | 1.76 (6) | 2.683 (7) | 166 (5) |
N2—H1N2···O1i | 0.85 (5) | 1.96 (5) | 2.793 (8) | 165 (4) |
N2—H2N2···O1ii | 0.85 (6) | 2.04 (7) | 2.811 (6) | 152 (7) |
C8—H8A···O3iii | 0.95 | 2.58 | 3.425 (7) | 148 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, y+1/2, −z+1; (iii) −x+1, y+1/2, −z+2. |
Footnotes
‡Thomson Reuters ResearcherID: A-5599-2009.
Acknowledgements
The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and USM Short Term Grant No. 304/PFIZIK/6312078 to conduct this work. KT thanks The Academy of Sciences for the Developing World and USM for a TWAS–USM 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.
Supramolecular architectures assembled via various delicate noncovalent interactions such as hydrogen bonds, π–π stacking and electrostatic interactions, etc., have attracted intense interest in recent years because of their fascinating structural diversity and potential applications for functional materials (Desiraju, 2007). Especially, the application of intermolecular hydrogen bonds is a well known and efficient tool in the field of organic crystal design owing to its strength and directional properties (Aakeroy & Seddon, 1993). Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). The are often involved in hydrogen-bond interactions. In order to study potential hydrogen bonding interactions, as part of our ongoing studies on pyridine derivatives (Thanigaimani et al., 2012a,b), the crystal structure determination of the title compound (I) was carried out.
The asymmetric unit (Fig. 1) contains one 2-amino-5-methylpyridinium cation and one 5-chlorosalicylate anion. The proton transfers from the one of the carboxyl group oxygen atom (O2) to atom N1 of 2-amino-5-methylpyrimidine resulted in the widening of C1—N1—C5 angle of the pyridinium ring to 121.0 (5)°, compared to the corresponding angle of 117.4 (3)° in neutral 2-amino-5-methylpyridine (Nahringbauer & Kvick, 1977). The 2-amino-5-methylpyridinium cation is essentially planar, with a maximum diviation of 0.007 (6) Å for atom C3. The bond lengths (Allen et al., 1987) and angles are normal.
In the crystal packing (Fig. 2), the protonated N1 atom and a nitrogen atom of the 2-amino group (N2) are hydrogen-bonded to the carboxylate oxygen atoms (O1 and O2) via a pair of intermolecular N1—H1N1···O2i and N2—H1N2···O1i hydrogen bonds (symmetry codes in Table 1), forming a ring motif of R22(8) (Bernstein et al., 1995). There is also an intramolecular O3—H1O3···O2 hydrogen bond in the 5-chlorosalicylate anion, which generates an S(6) ring motif. This motif is also observed in the crystal structure of 5-chloro-2-hydroxybenzoic acid (Raza et al., 2010). The crystal structure is further stabilized by N2—H2N2···O1ii and C8—H8A···O3iii intermolecular interactions. These interactions have resulted in a molecular layer parallel to the (101) plane.