2-Amino-3-methyl­pyridinium 3,4-di­meth­oxy­benzoate

Sivakumar, P.; Devi, R.N.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314616013328

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161332

doi:10.1107/S2414314616013328

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2-Amino-3-methylpyridinium 3,4-dimethoxybenzoate

P. Sivakumar,^a,^b R. Niranjana Devi,^c S. Israel ^c ^* and G. Chakkaravarthi ^b ^*

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 August 2016; accepted 19 August 2016; online 26 August 2016)

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 crystal structure of the title molecular salt (Fig. 1). 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].

Figure 1
The molecular structure of the title molecular salt, with 30% probability displacement ellipsoids.

In 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.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (iii) -x+1, -y-1, -z+2.

Figure 2
The crystal packing of the title molecular salt viewed along the b axis. Hydrogen bonds are shown as dashed lines. H atoms not involving in hydrogen bonding have been omitted for clarity.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₉H₉O₄⁻
M_r	290.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	11.6972 (8), 6.6637 (5), 19.2325 (17)
β (°)	103.000 (2)
V (Å³)	1460.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.973, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	17370, 3587, 2388
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.128, 1.03
No. of reflections	3587
No. of parameters	197
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1499947

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616013328/hb4072sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616013328/hb4072Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616013328/hb4072Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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).

2-Amino-3-methylpyridinium 3,4-dimethoxybenzoate top

Crystal data top

C₆H₉N₂⁺·C₉H₉O₄⁻	F(000) = 616
M_r = 290.31	D_x = 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

Data collection top

Bruker Kappa APEXII CCD diffractometer	3587 independent reflections
Radiation source: fine-focus sealed tube	2388 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and φ scan	θ_max = 28.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→15
T_min = 0.973, T_max = 0.981	k = −8→8
17370 measured reflections	l = −25→24

Refinement top

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(F_o²) + (0.0509P)² + 0.5181P] where P = (F_o² + 2F_c²)/3
3587 reflections	(Δ/σ)_max < 0.001
197 parameters	Δρ_max = 0.23 e Å⁻³
1 restraint	Δρ_min = −0.23 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

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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
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