organic compounds
2-Amino-3-methylpyridinium hydrogen phthalate
aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, cResearch Scholar in Physics, Mother Teresa University, Kodaikanal 624 102, India, dDepartment of Physics, Alagappa University, Karaikkudi 630 003, India, and ePost Graduate and Research Department of Physics, The American College, Madurai 625 002, India
*Correspondence e-mail: israel.samuel@gmail.com, chakkaravarthi_2005@yahoo.com
In the title molecular salt, C6H9N2+·C8H5O4−, the cation is protonated at the pyridine N atom and the anion is deprotonated at the hydroxy O atom. The anion features an intramolecular O—H⋯O hydrogen bond with the H atom located almost in the middle of the two O atoms. The dihedral angle between the pyridine and benzene rings is 19.17 (12)°. The N—H⋯O hydrogen bonds generate R22(8) and R24(18) ring motifs. The is stabilized by N—H⋯O hydrogen bonds. The structure is also influenced by weak π–π [centroid-to-centroid distance = 3.7347 (14) Å] interaction between the anions.
Keywords: crystal structure; molecular salt; hydrogen bonding.
CCDC reference: 1538296
Structure description
Pyridine derivatives exhibit antifungal, anticancer and anti-inflammatory activities (Liu & Hu, 2002; Spanka et al., 2010). We report herein the synthesis and the of the title molecular salt (Fig. 1). The bond lengths are comparable with those in related structures (Sivakumar, Devi et al., 2016; Sivakumar, Sudhahar et al., 2016). The title molecular salt (Fig. 1) comprises a 2-amino-3-methylpyridinium cation and a hydrogen phthalate anion. The cation is protonated at the pyridine N atom and the anion is deprotonated at one of the hydroxy O atoms. The anion features an intramolecular O—H—O hydrogen bond with the H atom located almost in the middle of the two O atoms. The dihedral angle between the pyridine and benzene rings is 19.17 (12)°.
In the A⋯O3 hydrogen bonds (Table 1) link the cation and anion, generating an R22(8) ring motif (Fig. 2). In the crystal, the N2—H2A⋯O3 and N2—H2B⋯O1i (Table 1) hydrogen bonds generate an R24(18) ring motif (Fig. 3). The structure is also influenced by a weak offset π–π [Cg1⋯Cg1(1 − x, 2 − y, 2 − z) = 3.7347 (14) Å; Cg1 is the centroid of the (C7–C12) ring] interaction between the anions.
the inter-ionic N1—H1⋯O4 and N2—H2Synthesis and crystallization
The title compound was synthesized using 2-amino-3-methylpyridine (0.54 g) and phthalic acid (0.83 g) in an equimolar ratio. These reactants were dissolved in 15 ml acetone. The white precipitate that formed was dissolved in water and kept at room temperature. Crystals suitable for X-ray diffraction were harvested after 90 d.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1538296
https://doi.org/10.1107/S2414314617004229/bt4045sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004229/bt4045Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617004229/bt4045Isup3.cml
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).C6H9N2+·C8H5O4− | Z = 2 |
Mr = 274.27 | F(000) = 288 |
Triclinic, P1 | Dx = 1.367 Mg m−3 |
a = 7.1675 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.8143 (6) Å | Cell parameters from 5483 reflections |
c = 10.6613 (7) Å | θ = 0.7–0.8° |
α = 91.968 (4)° | µ = 0.10 mm−1 |
β = 96.362 (3)° | T = 295 K |
γ = 94.745 (3)° | Block, colourless |
V = 666.46 (7) Å3 | 0.28 × 0.24 × 0.20 mm |
Bruker Kappa APEXII CCD diffractometer | 2056 reflections with I > 2σ(I) |
ω and φ scan | Rint = 0.032 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | θmax = 30.5°, θmin = 1.9° |
Tmin = 0.686, Tmax = 0.746 | h = −10→10 |
17030 measured reflections | k = −12→12 |
3982 independent reflections | l = −15→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.189 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.3832P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3982 reflections | Δρmax = 0.23 e Å−3 |
198 parameters | Δρmin = −0.21 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1981 (3) | 0.4914 (2) | 0.4055 (2) | 0.0475 (5) | |
C2 | 0.1063 (3) | 0.4009 (3) | 0.3006 (2) | 0.0541 (6) | |
C3 | 0.0722 (4) | 0.2491 (3) | 0.3165 (3) | 0.0643 (7) | |
H3 | 0.008907 | 0.188210 | 0.249572 | 0.077* | |
C4 | 0.1284 (4) | 0.1811 (3) | 0.4291 (3) | 0.0713 (8) | |
H4 | 0.105614 | 0.076634 | 0.437016 | 0.086* | |
C5 | 0.2171 (4) | 0.2715 (3) | 0.5265 (3) | 0.0652 (7) | |
H5 | 0.256743 | 0.229168 | 0.602565 | 0.078* | |
C6 | 0.0549 (4) | 0.4731 (4) | 0.1789 (3) | 0.0785 (8) | |
H6A | −0.003326 | 0.396615 | 0.117308 | 0.118* | |
H6B | 0.166452 | 0.520748 | 0.149629 | 0.118* | |
H6C | −0.031501 | 0.548357 | 0.191184 | 0.118* | |
C7 | 0.7494 (3) | 0.9694 (3) | 0.9900 (2) | 0.0530 (5) | |
H7 | 0.825134 | 1.060789 | 1.001807 | 0.064* | |
C8 | 0.6526 (3) | 0.9306 (2) | 0.8717 (2) | 0.0454 (5) | |
C9 | 0.5434 (3) | 0.7897 (2) | 0.85357 (19) | 0.0449 (5) | |
C10 | 0.5318 (4) | 0.6995 (3) | 0.9578 (2) | 0.0551 (6) | |
H10 | 0.458464 | 0.606925 | 0.947484 | 0.066* | |
C11 | 0.6243 (4) | 0.7420 (3) | 1.0749 (2) | 0.0624 (6) | |
H11 | 0.610918 | 0.680227 | 1.142917 | 0.075* | |
C12 | 0.7365 (4) | 0.8762 (3) | 1.0907 (2) | 0.0606 (6) | |
H12 | 0.803702 | 0.904462 | 1.168821 | 0.073* | |
C13 | 0.6793 (3) | 1.0500 (3) | 0.7754 (2) | 0.0550 (6) | |
C14 | 0.4398 (3) | 0.7183 (3) | 0.7314 (2) | 0.0513 (5) | |
N1 | 0.2482 (3) | 0.4225 (2) | 0.5137 (2) | 0.0549 (5) | |
H1 | 0.305 (4) | 0.489 (3) | 0.587 (3) | 0.081 (9)* | |
N2 | 0.2385 (3) | 0.6404 (2) | 0.4039 (2) | 0.0616 (6) | |
H2A | 0.295 (4) | 0.692 (3) | 0.475 (3) | 0.069 (8)* | |
H2B | 0.214 (5) | 0.690 (4) | 0.329 (4) | 0.102 (11)* | |
O1 | 0.8082 (3) | 1.1491 (2) | 0.7962 (2) | 0.0837 (6) | |
O2 | 0.5619 (3) | 1.0490 (2) | 0.67375 (17) | 0.0682 (5) | |
H2 | 0.458 (4) | 0.927 (3) | 0.658 (3) | 0.073 (8)* | |
O3 | 0.3884 (3) | 0.8012 (2) | 0.64200 (17) | 0.0697 (5) | |
O4 | 0.4074 (3) | 0.57795 (19) | 0.72482 (17) | 0.0698 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0440 (11) | 0.0456 (11) | 0.0546 (12) | 0.0028 (9) | 0.0125 (9) | 0.0049 (9) |
C2 | 0.0457 (12) | 0.0579 (13) | 0.0590 (13) | 0.0013 (10) | 0.0116 (10) | −0.0018 (11) |
C3 | 0.0598 (15) | 0.0574 (14) | 0.0748 (17) | −0.0079 (11) | 0.0181 (13) | −0.0106 (13) |
C4 | 0.0817 (19) | 0.0452 (13) | 0.090 (2) | −0.0019 (12) | 0.0298 (16) | 0.0021 (13) |
C5 | 0.0791 (17) | 0.0515 (14) | 0.0687 (16) | 0.0057 (12) | 0.0204 (14) | 0.0156 (12) |
C6 | 0.0835 (19) | 0.089 (2) | 0.0596 (16) | 0.0048 (16) | −0.0041 (14) | 0.0064 (14) |
C7 | 0.0506 (12) | 0.0498 (12) | 0.0576 (13) | 0.0043 (10) | −0.0002 (10) | 0.0059 (10) |
C8 | 0.0430 (11) | 0.0459 (11) | 0.0488 (11) | 0.0094 (9) | 0.0050 (9) | 0.0110 (9) |
C9 | 0.0481 (11) | 0.0427 (11) | 0.0454 (11) | 0.0107 (9) | 0.0053 (9) | 0.0077 (9) |
C10 | 0.0710 (15) | 0.0419 (11) | 0.0532 (13) | 0.0086 (10) | 0.0055 (11) | 0.0122 (10) |
C11 | 0.0827 (17) | 0.0547 (14) | 0.0508 (13) | 0.0121 (12) | 0.0031 (12) | 0.0151 (11) |
C12 | 0.0698 (15) | 0.0622 (15) | 0.0488 (13) | 0.0101 (12) | −0.0029 (11) | 0.0067 (11) |
C13 | 0.0545 (13) | 0.0506 (13) | 0.0612 (14) | 0.0055 (10) | 0.0072 (11) | 0.0150 (10) |
C14 | 0.0511 (12) | 0.0530 (13) | 0.0502 (12) | 0.0038 (10) | 0.0063 (10) | 0.0095 (10) |
N1 | 0.0619 (12) | 0.0476 (11) | 0.0554 (11) | 0.0023 (9) | 0.0079 (9) | 0.0065 (9) |
N2 | 0.0789 (15) | 0.0460 (11) | 0.0576 (13) | −0.0022 (10) | 0.0026 (11) | 0.0049 (10) |
O1 | 0.0794 (13) | 0.0740 (13) | 0.0917 (14) | −0.0203 (10) | −0.0063 (11) | 0.0352 (11) |
O2 | 0.0857 (12) | 0.0547 (10) | 0.0608 (10) | 0.0000 (9) | −0.0071 (9) | 0.0206 (8) |
O3 | 0.0829 (12) | 0.0593 (11) | 0.0597 (10) | −0.0096 (9) | −0.0156 (9) | 0.0151 (8) |
O4 | 0.0957 (14) | 0.0493 (10) | 0.0600 (10) | −0.0054 (9) | −0.0018 (9) | 0.0042 (8) |
C1—N2 | 1.322 (3) | C8—C13 | 1.511 (3) |
C1—N1 | 1.350 (3) | C9—C10 | 1.394 (3) |
C1—C2 | 1.417 (3) | C9—C14 | 1.516 (3) |
C2—C3 | 1.360 (3) | C10—C11 | 1.372 (3) |
C2—C6 | 1.488 (4) | C10—H10 | 0.9300 |
C3—C4 | 1.395 (4) | C11—C12 | 1.369 (4) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.353 (4) | C12—H12 | 0.9300 |
C4—H4 | 0.9300 | C13—O1 | 1.214 (3) |
C5—N1 | 1.345 (3) | C13—O2 | 1.295 (3) |
C5—H5 | 0.9300 | C14—O4 | 1.238 (3) |
C6—H6A | 0.9600 | C14—O3 | 1.262 (3) |
C6—H6B | 0.9600 | N1—H1 | 0.99 (3) |
C6—H6C | 0.9600 | N2—H2A | 0.91 (3) |
C7—C12 | 1.380 (3) | N2—H2B | 0.93 (4) |
C7—C8 | 1.388 (3) | O2—H2 | 1.25 (3) |
C7—H7 | 0.9300 | O3—H2 | 1.18 (3) |
C8—C9 | 1.407 (3) | ||
N2—C1—N1 | 117.6 (2) | C10—C9—C8 | 117.8 (2) |
N2—C1—C2 | 123.9 (2) | C10—C9—C14 | 114.34 (19) |
N1—C1—C2 | 118.6 (2) | C8—C9—C14 | 127.84 (19) |
C3—C2—C1 | 117.4 (2) | C11—C10—C9 | 122.6 (2) |
C3—C2—C6 | 122.9 (2) | C11—C10—H10 | 118.7 |
C1—C2—C6 | 119.7 (2) | C9—C10—H10 | 118.7 |
C2—C3—C4 | 122.6 (3) | C12—C11—C10 | 119.3 (2) |
C2—C3—H3 | 118.7 | C12—C11—H11 | 120.3 |
C4—C3—H3 | 118.7 | C10—C11—H11 | 120.3 |
C5—C4—C3 | 118.0 (2) | C11—C12—C7 | 119.7 (2) |
C5—C4—H4 | 121.0 | C11—C12—H12 | 120.2 |
C3—C4—H4 | 121.0 | C7—C12—H12 | 120.2 |
N1—C5—C4 | 120.2 (3) | O1—C13—O2 | 120.6 (2) |
N1—C5—H5 | 119.9 | O1—C13—C8 | 119.3 (2) |
C4—C5—H5 | 119.9 | O2—C13—C8 | 120.1 (2) |
C2—C6—H6A | 109.5 | O4—C14—O3 | 122.6 (2) |
C2—C6—H6B | 109.5 | O4—C14—C9 | 117.2 (2) |
H6A—C6—H6B | 109.5 | O3—C14—C9 | 120.2 (2) |
C2—C6—H6C | 109.5 | C5—N1—C1 | 123.1 (2) |
H6A—C6—H6C | 109.5 | C5—N1—H1 | 119.8 (18) |
H6B—C6—H6C | 109.5 | C1—N1—H1 | 117.0 (18) |
C12—C7—C8 | 121.9 (2) | C1—N2—H2A | 119.4 (17) |
C12—C7—H7 | 119.1 | C1—N2—H2B | 120 (2) |
C8—C7—H7 | 119.1 | H2A—N2—H2B | 121 (3) |
C7—C8—C9 | 118.69 (19) | C13—O2—H2 | 111.5 (12) |
C7—C8—C13 | 113.89 (19) | C14—O3—H2 | 112.0 (13) |
C9—C8—C13 | 127.4 (2) | ||
N2—C1—C2—C3 | −179.4 (2) | C14—C9—C10—C11 | 176.7 (2) |
N1—C1—C2—C3 | 0.8 (3) | C9—C10—C11—C12 | −1.6 (4) |
N2—C1—C2—C6 | 1.7 (4) | C10—C11—C12—C7 | 2.4 (4) |
N1—C1—C2—C6 | −178.1 (2) | C8—C7—C12—C11 | −0.6 (4) |
C1—C2—C3—C4 | −1.8 (4) | C7—C8—C13—O1 | 16.2 (3) |
C6—C2—C3—C4 | 177.0 (3) | C9—C8—C13—O1 | −163.9 (2) |
C2—C3—C4—C5 | 1.3 (4) | C7—C8—C13—O2 | −161.7 (2) |
C3—C4—C5—N1 | 0.3 (4) | C9—C8—C13—O2 | 18.3 (4) |
C12—C7—C8—C9 | −2.1 (3) | C10—C9—C14—O4 | −21.6 (3) |
C12—C7—C8—C13 | 177.8 (2) | C8—C9—C14—O4 | 155.8 (2) |
C7—C8—C9—C10 | 2.8 (3) | C10—C9—C14—O3 | 157.6 (2) |
C13—C8—C9—C10 | −177.1 (2) | C8—C9—C14—O3 | −24.9 (3) |
C7—C8—C9—C14 | −174.5 (2) | C4—C5—N1—C1 | −1.4 (4) |
C13—C8—C9—C14 | 5.5 (4) | N2—C1—N1—C5 | −179.0 (2) |
C8—C9—C10—C11 | −1.0 (3) | C2—C1—N1—C5 | 0.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H2···O2 | 1.18 (3) | 1.25 (3) | 2.417 (2) | 169 (2) |
N1—H1···O4 | 0.99 (3) | 1.70 (3) | 2.685 (3) | 171 (3) |
N2—H2A···O3 | 0.91 (3) | 2.01 (3) | 2.916 (3) | 173 (2) |
N2—H2B···O1i | 0.93 (4) | 1.99 (4) | 2.885 (3) | 162 (3) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Acknowledgements
The authors acknowledge the SAIF, IIT, Madras, for the data collection.
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