organic compounds
2-Amino-3-methylpyridinium 3,4-dimethoxybenzoate
aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, and cPost 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+·C9H9O4−, the cation is protonated at the pyridine N atom. In the crystal, N—H⋯O hydrogen bonds link the components into [010] chains, which feature R22(8) loops. The chains are linked by C—H⋯O hydrogen bonds, forming a three-dimensional network.
Keywords: Molecular salt; crystal structure; hydrogen bonding.
CCDC reference: 1499947
Structure description
We herewith report the synthesis and the ). The bond lengths are comparable with related structures we have reported recently (Sivakumar et al., 2016a,b). The cation is protonated at the pyridine N1 atom and the anion is deprotonated at hydroxyl O1 atom. In the anion, the dihedral angle between the carboxylate group and its attached benzene ring is 9.81 (9)° and both methoxy C atoms lie close to the plane of the ring [deviations for C13 and C14 = 0.172 (2) and 0.181 (2) Å, respectively].
of the title molecular salt (Fig. 1In the crystal, N—H⋯O hydrogen bonds connect the anions and cations into infinite chains along [010] and these chains are further consolidated by C—H⋯O hydrogen bonds (Table 1 and Fig. 2), forming a three-dimensional network. As part of the chain motif, a pair of N—H⋯O (N1—H1A⋯O1i and N2—H2A⋯O2i) hydrogen bonds generate R22(8) loops.
Synthesis and crystallization
The title compound was synthesized in acetone by mixing 2-amino-3-methylpyridine (0.27 g) and 3,4-dimethoxy benzoic acid (0.45 g) in an equimolar ratio. The solution was allowed to evaporate slowly at room temperature. After a period of 25 days, colourless blocks were grown, which were suitable for X-ray diffraction.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1499947
10.1107/S2414314616013328/hb4072sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616013328/hb4072Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616013328/hb4072Isup3.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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C6H9N2+·C9H9O4− | F(000) = 616 |
Mr = 290.31 | Dx = 1.320 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4375 reflections |
a = 11.6972 (8) Å | θ = 2.5–26.4° |
b = 6.6637 (5) Å | µ = 0.10 mm−1 |
c = 19.2325 (17) Å | T = 295 K |
β = 103.000 (2)° | Block, colourless |
V = 1460.7 (2) Å3 | 0.28 × 0.24 × 0.20 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 3587 independent reflections |
Radiation source: fine-focus sealed tube | 2388 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and φ scan | θmax = 28.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −15→15 |
Tmin = 0.973, Tmax = 0.981 | k = −8→8 |
17370 measured reflections | l = −25→24 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.5181P] where P = (Fo2 + 2Fc2)/3 |
3587 reflections | (Δ/σ)max < 0.001 |
197 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.23 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. |
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 > 2sigma(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 | ||
C1 | 0.41591 (14) | −0.5512 (3) | 1.29093 (10) | 0.0411 (4) | |
H1 | 0.4753 | −0.4995 | 1.2711 | 0.049* | |
C2 | 0.43583 (16) | −0.7179 (3) | 1.33117 (11) | 0.0469 (5) | |
H2 | 0.5086 | −0.7810 | 1.3404 | 0.056* | |
C3 | 0.34363 (16) | −0.7937 (3) | 1.35878 (11) | 0.0463 (5) | |
H3 | 0.3562 | −0.9089 | 1.3868 | 0.056* | |
C4 | 0.23615 (15) | −0.7048 (3) | 1.34609 (9) | 0.0372 (4) | |
C5 | 0.22031 (13) | −0.5260 (2) | 1.30491 (9) | 0.0320 (4) | |
C6 | 0.13643 (17) | −0.7891 (3) | 1.37408 (11) | 0.0519 (5) | |
H6A | 0.0757 | −0.8340 | 1.3349 | 0.078* | |
H6B | 0.1058 | −0.6871 | 1.4001 | 0.078* | |
H6C | 0.1639 | −0.9002 | 1.4051 | 0.078* | |
C7 | 0.21553 (13) | −0.8319 (2) | 1.14744 (9) | 0.0308 (4) | |
C8 | 0.12877 (14) | −0.6888 (3) | 1.13558 (10) | 0.0384 (4) | |
H8 | 0.0636 | −0.7047 | 1.1552 | 0.046* | |
C9 | 0.13749 (15) | −0.5203 (3) | 1.09443 (10) | 0.0437 (4) | |
H9 | 0.0783 | −0.4242 | 1.0870 | 0.052* | |
C10 | 0.23282 (15) | −0.4946 (2) | 1.06465 (9) | 0.0382 (4) | |
C11 | 0.32175 (14) | −0.6394 (2) | 1.07619 (9) | 0.0357 (4) | |
C12 | 0.31268 (14) | −0.8051 (2) | 1.11728 (9) | 0.0335 (4) | |
H12 | 0.3721 | −0.9008 | 1.1251 | 0.040* | |
C13 | 0.1576 (2) | −0.1972 (3) | 1.00187 (13) | 0.0630 (6) | |
H13A | 0.0883 | −0.2660 | 0.9770 | 0.094* | |
H13B | 0.1795 | −0.0982 | 0.9710 | 0.094* | |
H13C | 0.1421 | −0.1326 | 1.0434 | 0.094* | |
C14 | 0.49645 (19) | −0.7559 (3) | 1.04719 (14) | 0.0650 (7) | |
H14A | 0.5383 | −0.7744 | 1.0957 | 0.098* | |
H14B | 0.5505 | −0.7192 | 1.0185 | 0.098* | |
H14C | 0.4577 | −0.8787 | 1.0295 | 0.098* | |
C15 | 0.20866 (13) | −1.0170 (2) | 1.19126 (9) | 0.0334 (4) | |
N1 | 0.31064 (12) | −0.4576 (2) | 1.27889 (8) | 0.0357 (3) | |
N2 | 0.12124 (12) | −0.4201 (2) | 1.29070 (8) | 0.0437 (4) | |
H2A | 0.1166 | −0.3122 | 1.2657 | 0.052* | |
H2B | 0.0619 | −0.4597 | 1.3065 | 0.052* | |
O1 | 0.29953 (10) | −1.12424 (18) | 1.20672 (7) | 0.0466 (3) | |
O2 | 0.11498 (10) | −1.05519 (19) | 1.20953 (7) | 0.0475 (4) | |
O3 | 0.24997 (13) | −0.3368 (2) | 1.02274 (8) | 0.0570 (4) | |
O4 | 0.41272 (11) | −0.60306 (19) | 1.04403 (8) | 0.0512 (4) | |
H1A | 0.3010 (17) | −0.345 (2) | 1.2541 (10) | 0.057 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0280 (8) | 0.0509 (11) | 0.0454 (11) | −0.0045 (8) | 0.0102 (7) | −0.0035 (9) |
C2 | 0.0340 (9) | 0.0511 (11) | 0.0534 (12) | 0.0080 (8) | 0.0050 (8) | −0.0004 (9) |
C3 | 0.0473 (11) | 0.0395 (10) | 0.0488 (12) | 0.0028 (8) | 0.0035 (9) | 0.0073 (9) |
C4 | 0.0365 (9) | 0.0390 (9) | 0.0353 (10) | −0.0058 (8) | 0.0065 (7) | 0.0013 (8) |
C5 | 0.0276 (8) | 0.0360 (9) | 0.0322 (9) | −0.0042 (7) | 0.0064 (6) | −0.0019 (7) |
C6 | 0.0494 (11) | 0.0530 (12) | 0.0548 (13) | −0.0096 (9) | 0.0147 (9) | 0.0137 (10) |
C7 | 0.0287 (8) | 0.0297 (8) | 0.0343 (9) | −0.0034 (6) | 0.0079 (7) | −0.0018 (7) |
C8 | 0.0317 (8) | 0.0390 (9) | 0.0467 (11) | 0.0011 (7) | 0.0133 (7) | 0.0009 (8) |
C9 | 0.0388 (10) | 0.0395 (10) | 0.0530 (12) | 0.0106 (8) | 0.0106 (8) | 0.0041 (8) |
C10 | 0.0448 (10) | 0.0300 (8) | 0.0393 (10) | −0.0002 (7) | 0.0084 (8) | 0.0043 (7) |
C11 | 0.0362 (9) | 0.0336 (9) | 0.0400 (10) | −0.0027 (7) | 0.0144 (7) | 0.0007 (7) |
C12 | 0.0301 (8) | 0.0314 (8) | 0.0397 (10) | 0.0013 (7) | 0.0096 (7) | 0.0010 (7) |
C13 | 0.0771 (15) | 0.0417 (11) | 0.0633 (15) | 0.0094 (11) | 0.0014 (12) | 0.0126 (10) |
C14 | 0.0635 (13) | 0.0511 (12) | 0.0974 (19) | 0.0143 (10) | 0.0537 (13) | 0.0221 (12) |
C15 | 0.0288 (8) | 0.0325 (9) | 0.0401 (10) | −0.0036 (7) | 0.0101 (7) | −0.0029 (7) |
N1 | 0.0296 (7) | 0.0374 (8) | 0.0405 (9) | −0.0047 (6) | 0.0084 (6) | 0.0028 (7) |
N2 | 0.0319 (8) | 0.0446 (9) | 0.0580 (10) | 0.0007 (6) | 0.0171 (7) | 0.0125 (7) |
O1 | 0.0320 (6) | 0.0419 (7) | 0.0707 (10) | 0.0059 (5) | 0.0220 (6) | 0.0186 (6) |
O2 | 0.0307 (6) | 0.0470 (7) | 0.0699 (9) | 0.0008 (5) | 0.0222 (6) | 0.0142 (7) |
O3 | 0.0632 (9) | 0.0441 (8) | 0.0661 (10) | 0.0082 (7) | 0.0199 (7) | 0.0215 (7) |
O4 | 0.0521 (8) | 0.0425 (7) | 0.0687 (10) | 0.0046 (6) | 0.0342 (7) | 0.0172 (7) |
C1—C2 | 1.344 (3) | C9—H9 | 0.9300 |
C1—N1 | 1.353 (2) | C10—O3 | 1.367 (2) |
C1—H1 | 0.9300 | C10—C11 | 1.399 (2) |
C2—C3 | 1.399 (3) | C11—O4 | 1.367 (2) |
C2—H2 | 0.9300 | C11—C12 | 1.376 (2) |
C3—C4 | 1.361 (2) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—O3 | 1.414 (2) |
C4—C5 | 1.420 (2) | C13—H13A | 0.9600 |
C4—C6 | 1.499 (2) | C13—H13B | 0.9600 |
C5—N2 | 1.331 (2) | C13—H13C | 0.9600 |
C5—N1 | 1.346 (2) | C14—O4 | 1.405 (2) |
C6—H6A | 0.9600 | C14—H14A | 0.9600 |
C6—H6B | 0.9600 | C14—H14B | 0.9600 |
C6—H6C | 0.9600 | C14—H14C | 0.9600 |
C7—C8 | 1.374 (2) | C15—O2 | 1.2499 (18) |
C7—C12 | 1.399 (2) | C15—O1 | 1.2597 (19) |
C7—C15 | 1.506 (2) | N1—H1A | 0.881 (9) |
C8—C9 | 1.390 (3) | N2—H2A | 0.8600 |
C8—H8 | 0.9300 | N2—H2B | 0.8600 |
C9—C10 | 1.374 (2) | ||
C2—C1—N1 | 120.86 (17) | O3—C10—C11 | 114.93 (15) |
C2—C1—H1 | 119.6 | C9—C10—C11 | 119.47 (16) |
N1—C1—H1 | 119.6 | O4—C11—C12 | 124.78 (15) |
C1—C2—C3 | 117.92 (17) | O4—C11—C10 | 115.62 (15) |
C1—C2—H2 | 121.0 | C12—C11—C10 | 119.59 (15) |
C3—C2—H2 | 121.0 | C11—C12—C7 | 121.02 (15) |
C4—C3—C2 | 122.30 (18) | C11—C12—H12 | 119.5 |
C4—C3—H3 | 118.8 | C7—C12—H12 | 119.5 |
C2—C3—H3 | 118.8 | O3—C13—H13A | 109.5 |
C3—C4—C5 | 117.70 (16) | O3—C13—H13B | 109.5 |
C3—C4—C6 | 122.29 (17) | H13A—C13—H13B | 109.5 |
C5—C4—C6 | 120.01 (16) | O3—C13—H13C | 109.5 |
N2—C5—N1 | 117.63 (15) | H13A—C13—H13C | 109.5 |
N2—C5—C4 | 123.89 (15) | H13B—C13—H13C | 109.5 |
N1—C5—C4 | 118.48 (15) | O4—C14—H14A | 109.5 |
C4—C6—H6A | 109.5 | O4—C14—H14B | 109.5 |
C4—C6—H6B | 109.5 | H14A—C14—H14B | 109.5 |
H6A—C6—H6B | 109.5 | O4—C14—H14C | 109.5 |
C4—C6—H6C | 109.5 | H14A—C14—H14C | 109.5 |
H6A—C6—H6C | 109.5 | H14B—C14—H14C | 109.5 |
H6B—C6—H6C | 109.5 | O2—C15—O1 | 124.38 (16) |
C8—C7—C12 | 118.78 (15) | O2—C15—C7 | 118.98 (14) |
C8—C7—C15 | 122.07 (14) | O1—C15—C7 | 116.63 (14) |
C12—C7—C15 | 119.15 (14) | C5—N1—C1 | 122.70 (16) |
C7—C8—C9 | 120.60 (16) | C5—N1—H1A | 118.3 (14) |
C7—C8—H8 | 119.7 | C1—N1—H1A | 119.0 (14) |
C9—C8—H8 | 119.7 | C5—N2—H2A | 120.0 |
C10—C9—C8 | 120.54 (16) | C5—N2—H2B | 120.0 |
C10—C9—H9 | 119.7 | H2A—N2—H2B | 120.0 |
C8—C9—H9 | 119.7 | C10—O3—C13 | 117.98 (16) |
O3—C10—C9 | 125.60 (16) | C11—O4—C14 | 117.25 (14) |
N1—C1—C2—C3 | 1.4 (3) | C9—C10—C11—C12 | −0.1 (3) |
C1—C2—C3—C4 | 0.1 (3) | O4—C11—C12—C7 | −179.09 (16) |
C2—C3—C4—C5 | −1.8 (3) | C10—C11—C12—C7 | 0.4 (3) |
C2—C3—C4—C6 | 178.35 (19) | C8—C7—C12—C11 | −0.2 (3) |
C3—C4—C5—N2 | −177.50 (17) | C15—C7—C12—C11 | 179.22 (15) |
C6—C4—C5—N2 | 2.4 (3) | C8—C7—C15—O2 | 9.6 (3) |
C3—C4—C5—N1 | 2.0 (2) | C12—C7—C15—O2 | −169.85 (16) |
C6—C4—C5—N1 | −178.12 (16) | C8—C7—C15—O1 | −170.75 (16) |
C12—C7—C8—C9 | −0.1 (3) | C12—C7—C15—O1 | 9.8 (2) |
C15—C7—C8—C9 | −179.54 (16) | N2—C5—N1—C1 | 178.94 (16) |
C7—C8—C9—C10 | 0.3 (3) | C4—C5—N1—C1 | −0.6 (2) |
C8—C9—C10—O3 | 179.19 (17) | C2—C1—N1—C5 | −1.1 (3) |
C8—C9—C10—C11 | −0.2 (3) | C9—C10—O3—C13 | −6.7 (3) |
O3—C10—C11—O4 | −0.1 (2) | C11—C10—O3—C13 | 172.67 (17) |
C9—C10—C11—O4 | 179.35 (16) | C12—C11—O4—C14 | 6.9 (3) |
O3—C10—C11—C12 | −179.59 (16) | C10—C11—O4—C14 | −172.55 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.88 (2) | 1.73 (2) | 2.6071 (19) | 173 (2) |
N2—H2A···O2i | 0.86 | 2.02 | 2.8816 (19) | 177 |
N2—H2B···O2ii | 0.86 | 2.12 | 2.9051 (19) | 152 |
C14—H14B···O4iii | 0.96 | 2.54 | 3.281 (3) | 134 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+5/2; (iii) −x+1, −y−1, −z+2. |
Acknowledgements
The authors acknowledge the SAIF, IIT, Madras for the data collection.
References
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sivakumar, P., Sudhahar, S., Gunasekaran, B., Israel, S. & Chakkaravarthi, G. (2016b). IUCrData, 1, x160817. Google Scholar
Sivakumar, P., Sudhahar, S., Israel, S. & Chakkaravarthi, G. (2016a). IUCrData, 1, x160747. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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.