2-Amino-4-methyl­pyridinium 2-(3-methyl­phen­yl)acetate

Sivakumar, P.; Sudhahar, S.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314616010981

organic compounds

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Volume 1| Part 7| July 2016| x161098

https://doi.org/10.1107/S2414314616010981

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2-Amino-4-methylpyridinium 2-(3-methylphenyl)acetate

P. Sivakumar,^a,^b S. Sudhahar,^c S. Israel ^d ^* and G. Chakkaravarthi ^b ^*

^aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^cDepartment of Physics, Alagappa University, Karaikkudi 630 003, India, and ^dPost 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 L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 5 July 2016; accepted 6 July 2016; online 12 July 2016)

In the title molecular salt, C₆H₉N₂⁺·C₉H₉O₂⁻, the cation is protonated at the pyridine N atom and the anion is deprotonated at the hydroxy O atom. The dihedral angle between the benzene and pyridine rings is 66.58 (10)°. In the molecular structure, a pair of N—H⋯O hydrogen bonds links the anion and cation, generating an R₂²(8) ring motif. These ring motifs are connected to adjacent anions and cations via intermolecular N—H⋯O hydrogen bonding, generating a bifurcated R₂²(8) ring motif. C—H⋯O, C—H⋯π and π–π [centroid-to-centroid distances = 3.7053 (11) and 3.9547 (13) Å] interactions lead to the formation of a three-dimensional network.

Keywords: molecular salt; crystal structure; hydrogen bonding.

CCDC reference: 1491153

Structure description

Pyridine derivatives exhibit antifungal, anticancer and anti-inflammatory activities (Luo & Hu, 2006 ; Liu & Hu, 2002 ). We herein report the synthesis and the crystal structure of the title compound (Fig. 1). The geometric parameters are comparable with those reported for similar structures (Divya Bharathi et al., 2015 ; Sivakumar et al., 2016 ).

Figure 1
The molecular structure of the title molecular salt, showing the atom labelling and 30% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines.

The asymmetric unit of (Fig. 1) consists of a 2-amino-4-methylpyridinium cation, which is protonated at atom N1, and a 3-methylphenylacetate anion, which is deprotonated at the hydroxy O atom. The dihedral angle between the benzene ring (C1–C6) and the pyridine ring (N2/C10–C14) is 66.58 (10)°. N1—H1⋯O1 and N2—H2A⋯O2 hydrogen bonds (Table 1) link the anion and cation, generating an R₂²(8) ring motif (Fig. 2). These ring motifs are connected with adjacent anions and cations via N2—H2B⋯O2ⁱ hydrogen bonds (Table 1), generating a bifurcated R₂²(8) ring motif (Fig. 2). Intermolecular C—H⋯O, C—H⋯π (Table 1) and π–π [Cg1⋯Cg1ⁱ = 3.9547 (13) Å; Cg2⋯Cg2 = 3.7053 (11) Å; symmetry odes: (i) 1 − x, 2 − y, 1 − z; (ii) −x, 1 − y, −z; Cg1 and Cg2 are the centroids of the rings (C1–C6) and (N2/C10–C14), respectively] interactions lead to the formation of a three dimensional network (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.88 (2)	1.75 (2)	2.627 (2)	172 (2)
N2—H2A⋯O2	0.86	2.01	2.845 (2)	163
N2—H2B⋯O2ⁱ	0.86	2.10	2.829 (2)	142
C14—H14⋯O1ⁱⁱ	0.93	2.43	3.347 (2)	168
C11—H11⋯Cg1ⁱ	0.93	2.81	3.706 (2)	161
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+2, -z.

Figure 2
A partial view of the crystal packing of the title molecular salt, showing the ring graph-set motifs. Hydrogen bonds are shown as dashed lines and C-bound H atoms which are not involved in interactions have been omitted for clarity.

Figure 3
The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines and C-bound H atoms which are not involved in interactions have been omitted for clarity.

Synthesis and crystallization

The title compound was synthesized using the raw materials m-tolylacetic acid (1.001 g) and 2-amino-4-methylpyridine (0.72 g) in an equimolar ratio. These reactants were dissolved in 15 ml acetone and kept for slow evaporation at room temperature. Crystals suitable for X-ray diffraction were harvested after two weeks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₉H₉O₂⁻
M_r	258.31
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	8.3253 (4), 9.5065 (5), 9.5909 (5)
α, β, γ (°)	85.526 (3), 70.885 (3), 78.863 (3)
V (Å³)	703.62 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.979, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	15018, 3059, 1885
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.150, 1.02
No. of reflections	3059
No. of parameters	178
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1491153

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616010981/vm4010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010981/vm4010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010981/vm4010Isup3.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-4-methylpyridinium 2-(3-methylphenyl)acetate top

Crystal data top

C₆H₉N₂⁺·C₉H₉O₂⁻	Z = 2
M_r = 258.31	F(000) = 276
Triclinic, P1	D_x = 1.219 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3253 (4) Å	Cell parameters from 4380 reflections
b = 9.5065 (5) Å	θ = 2.2–27.0°
c = 9.5909 (5) Å	µ = 0.08 mm⁻¹
α = 85.526 (3)°	T = 293 K
β = 70.885 (3)°	Block, colourless
γ = 78.863 (3)°	0.26 × 0.24 × 0.20 mm
V = 703.62 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3059 independent reflections
Radiation source: fine-focus sealed tube	1885 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and φ scan	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.979, T_max = 0.984	k = −12→12
15018 measured reflections	l = −12→12

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0613P)² + 0.2177P] where P = (F_o² + 2F_c²)/3
3059 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.22 e Å⁻³
2 restraints	Δρ_min = −0.21 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	0.4822 (2)	0.8660 (2)	0.3042 (2)	0.0475 (5)
C2	0.6275 (3)	0.9154 (2)	0.3021 (2)	0.0490 (5)
H2	0.6663	0.9857	0.2329	0.059*
C3	0.7182 (3)	0.8647 (2)	0.3985 (2)	0.0558 (6)
C4	0.6600 (3)	0.7610 (3)	0.4989 (3)	0.0699 (6)
H4	0.7180	0.7261	0.5659	0.084*
C5	0.5160 (4)	0.7072 (3)	0.5021 (3)	0.0730 (7)
H5	0.4787	0.6356	0.5701	0.088*
C6	0.4279 (3)	0.7596 (2)	0.4047 (3)	0.0619 (6)
H6	0.3312	0.7230	0.4069	0.074*
C7	0.8749 (3)	0.9245 (3)	0.3939 (3)	0.0870 (9)
H7A	0.8417	1.0247	0.4162	0.131*
H7B	0.9586	0.9121	0.2973	0.131*
H7C	0.9243	0.8747	0.4654	0.131*
C8	0.3800 (3)	0.9344 (2)	0.2050 (3)	0.0600 (6)
H8A	0.2665	0.9784	0.2672	0.072*
H8B	0.4360	1.0111	0.1492	0.072*
C9	0.3557 (2)	0.83992 (19)	0.0971 (2)	0.0458 (5)
C10	0.2100 (2)	0.58859 (19)	−0.1350 (2)	0.0409 (4)
C11	0.1335 (2)	0.5018 (2)	−0.1964 (2)	0.0443 (5)
H11	0.1923	0.4106	−0.2283	0.053*
C12	−0.0260 (2)	0.5491 (2)	−0.2101 (2)	0.0447 (5)
C13	−0.1123 (3)	0.6872 (2)	−0.1610 (2)	0.0526 (5)
H13	−0.2218	0.7217	−0.1680	0.063*
C14	−0.0352 (3)	0.7693 (2)	−0.1038 (2)	0.0524 (5)
H14	−0.0921	0.8610	−0.0720	0.063*
C15	−0.1096 (3)	0.4565 (2)	−0.2745 (3)	0.0619 (6)
H15A	−0.0876	0.4791	−0.3776	0.093*
H15B	−0.2320	0.4735	−0.2246	0.093*
H15C	−0.0630	0.3575	−0.2624	0.093*
N1	0.1233 (2)	0.72080 (16)	−0.09179 (18)	0.0446 (4)
N2	0.3643 (2)	0.54781 (18)	−0.1174 (2)	0.0547 (5)
H2A	0.4059	0.6054	−0.0794	0.066*
H2B	0.4226	0.4638	−0.1441	0.066*
O1	0.23722 (19)	0.88996 (14)	0.04377 (17)	0.0591 (4)
O2	0.45236 (18)	0.72287 (15)	0.06398 (18)	0.0653 (5)
H1	0.170 (2)	0.7762 (19)	−0.053 (2)	0.056 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0480 (11)	0.0395 (10)	0.0534 (12)	−0.0016 (9)	−0.0159 (9)	−0.0084 (9)
C2	0.0526 (11)	0.0435 (11)	0.0482 (12)	−0.0073 (9)	−0.0121 (9)	−0.0053 (9)
C3	0.0525 (12)	0.0572 (13)	0.0575 (14)	0.0028 (10)	−0.0204 (10)	−0.0190 (11)
C4	0.0866 (15)	0.0690 (16)	0.0532 (14)	0.0105 (12)	−0.0327 (13)	−0.0107 (12)
C5	0.0947 (17)	0.0595 (14)	0.0528 (14)	−0.0116 (12)	−0.0110 (13)	0.0098 (12)
C6	0.0562 (13)	0.0530 (13)	0.0717 (16)	−0.0133 (10)	−0.0109 (11)	−0.0044 (12)
C7	0.0654 (15)	0.096 (2)	0.110 (2)	−0.0045 (14)	−0.0388 (15)	−0.0381 (17)
C8	0.0659 (13)	0.0416 (11)	0.0808 (16)	−0.0003 (10)	−0.0380 (12)	−0.0078 (11)
C9	0.0432 (10)	0.0340 (10)	0.0603 (13)	−0.0046 (8)	−0.0180 (10)	−0.0009 (9)
C10	0.0424 (10)	0.0351 (10)	0.0391 (10)	0.0012 (8)	−0.0099 (8)	0.0011 (8)
C11	0.0497 (11)	0.0347 (10)	0.0428 (11)	0.0011 (8)	−0.0116 (9)	−0.0033 (8)
C12	0.0494 (11)	0.0418 (11)	0.0411 (11)	−0.0067 (9)	−0.0134 (9)	0.0026 (8)
C13	0.0489 (11)	0.0459 (11)	0.0617 (14)	0.0041 (9)	−0.0229 (10)	−0.0005 (10)
C14	0.0546 (12)	0.0343 (10)	0.0639 (14)	0.0115 (9)	−0.0232 (10)	−0.0042 (9)
C15	0.0673 (14)	0.0570 (13)	0.0660 (15)	−0.0108 (11)	−0.0271 (12)	−0.0035 (11)
N1	0.0511 (9)	0.0319 (8)	0.0509 (10)	−0.0001 (7)	−0.0205 (8)	−0.0015 (7)
N2	0.0480 (9)	0.0461 (10)	0.0690 (12)	0.0067 (7)	−0.0235 (9)	−0.0115 (8)
O1	0.0656 (9)	0.0387 (8)	0.0813 (11)	0.0062 (7)	−0.0416 (8)	−0.0081 (7)
O2	0.0612 (9)	0.0488 (9)	0.0902 (12)	0.0131 (7)	−0.0384 (8)	−0.0210 (8)

Geometric parameters (Å, º) top

C1—C2	1.374 (3)	C9—O1	1.254 (2)
C1—C6	1.377 (3)	C10—N2	1.330 (2)
C1—C8	1.507 (3)	C10—N1	1.344 (2)
C2—C3	1.380 (3)	C10—C11	1.400 (3)
C2—H2	0.9300	C11—C12	1.363 (2)
C3—C4	1.366 (3)	C11—H11	0.9300
C3—C7	1.507 (3)	C12—C13	1.405 (3)
C4—C5	1.381 (4)	C12—C15	1.498 (3)
C4—H4	0.9300	C13—C14	1.346 (3)
C5—C6	1.376 (3)	C13—H13	0.9300
C5—H5	0.9300	C14—N1	1.350 (2)
C6—H6	0.9300	C14—H14	0.9300
C7—H7A	0.9600	C15—H15A	0.9600
C7—H7B	0.9600	C15—H15B	0.9600
C7—H7C	0.9600	C15—H15C	0.9600
C8—C9	1.507 (3)	N1—H1	0.877 (9)
C8—H8A	0.9700	N2—H2A	0.8600
C8—H8B	0.9700	N2—H2B	0.8600
C9—O2	1.236 (2)

C2—C1—C6	118.3 (2)	O2—C9—O1	124.30 (18)
C2—C1—C8	120.02 (19)	O2—C9—C8	119.97 (17)
C6—C1—C8	121.54 (19)	O1—C9—C8	115.70 (16)
C1—C2—C3	122.6 (2)	N2—C10—N1	118.07 (17)
C1—C2—H2	118.7	N2—C10—C11	123.63 (17)
C3—C2—H2	118.7	N1—C10—C11	118.30 (16)
C4—C3—C2	118.0 (2)	C12—C11—C10	120.93 (17)
C4—C3—C7	121.4 (2)	C12—C11—H11	119.5
C2—C3—C7	120.6 (2)	C10—C11—H11	119.5
C3—C4—C5	120.9 (2)	C11—C12—C13	118.45 (18)
C3—C4—H4	119.6	C11—C12—C15	121.33 (18)
C5—C4—H4	119.6	C13—C12—C15	120.22 (18)
C6—C5—C4	120.0 (2)	C14—C13—C12	119.53 (18)
C6—C5—H5	120.0	C14—C13—H13	120.2
C4—C5—H5	120.0	C12—C13—H13	120.2
C5—C6—C1	120.2 (2)	C13—C14—N1	121.13 (18)
C5—C6—H6	119.9	C13—C14—H14	119.4
C1—C6—H6	119.9	N1—C14—H14	119.4
C3—C7—H7A	109.5	C12—C15—H15A	109.5
C3—C7—H7B	109.5	C12—C15—H15B	109.5
H7A—C7—H7B	109.5	H15A—C15—H15B	109.5
C3—C7—H7C	109.5	C12—C15—H15C	109.5
H7A—C7—H7C	109.5	H15A—C15—H15C	109.5
H7B—C7—H7C	109.5	H15B—C15—H15C	109.5
C9—C8—C1	117.78 (17)	C10—N1—C14	121.64 (17)
C9—C8—H8A	107.9	C10—N1—H1	119.1 (14)
C1—C8—H8A	107.9	C14—N1—H1	119.2 (13)
C9—C8—H8B	107.9	C10—N2—H2A	120.0
C1—C8—H8B	107.9	C10—N2—H2B	120.0
H8A—C8—H8B	107.2	H2A—N2—H2B	120.0

C6—C1—C2—C3	−1.4 (3)	C1—C8—C9—O2	−18.8 (3)
C8—C1—C2—C3	174.70 (19)	C1—C8—C9—O1	162.85 (19)
C1—C2—C3—C4	0.3 (3)	N2—C10—C11—C12	179.30 (18)
C1—C2—C3—C7	−178.7 (2)	N1—C10—C11—C12	−1.0 (3)
C2—C3—C4—C5	0.9 (3)	C10—C11—C12—C13	0.0 (3)
C7—C3—C4—C5	179.9 (2)	C10—C11—C12—C15	−179.46 (18)
C3—C4—C5—C6	−0.9 (4)	C11—C12—C13—C14	0.8 (3)
C4—C5—C6—C1	−0.2 (4)	C15—C12—C13—C14	−179.8 (2)
C2—C1—C6—C5	1.4 (3)	C12—C13—C14—N1	−0.5 (3)
C8—C1—C6—C5	−174.7 (2)	N2—C10—N1—C14	−178.95 (18)
C2—C1—C8—C9	121.8 (2)	C11—C10—N1—C14	1.3 (3)
C6—C1—C8—C9	−62.2 (3)	C13—C14—N1—C10	−0.6 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88 (2)	1.75 (2)	2.627 (2)	172 (2)
N2—H2A···O2	0.86	2.01	2.845 (2)	163
N2—H2B···O2ⁱ	0.86	2.10	2.829 (2)	142
C14—H14···O1ⁱⁱ	0.93	2.43	3.347 (2)	168
C11—H11···Cg1ⁱ	0.93	2.81	3.706 (2)	161

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z.

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
Divya Bharathi, M., Ahila, G., Mohana, J., Chakkaravarthi, G. & Anbalagan, G. (2015). Acta Cryst. E71, o261–o262. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, T. & Hu, Y. (2002). Bioorg. Med. Chem. Lett. 12, 2411–2413. Web of Science CrossRef PubMed CAS Google Scholar
Luo, Y. & Hu, Y. (2006). Arch. Pharm. Chem. Life Sci. 339, 262–266. Web of Science CrossRef CAS 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. (2016). IUCrData, 1, x160747. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Amino-4-methyl­pyridinium 2-(3-methyl­phen­yl)acetate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

2-Amino-4-methylpyridinium 2-(3-methylphenyl)acetate