2-Amino-4-methyl­pyridinium 4-methyl­benzoate

Sivakumar, P.; Anzline, C.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314616014115

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161411

doi:10.1107/S2414314616014115

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2-Amino-4-methylpyridinium 4-methylbenzoate

P. Sivakumar,^a,^b C. Anzline,^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, ^cResearch Scholar in Physics, Mother Teresa University, Kodaikanal 624 102, 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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 3 September 2016; accepted 5 September 2016; online 9 September 2016)

In the title molecular salt, C₆H₉N₂⁺·C₈H₇O₂⁻, the cation is protonated at its pyridine N atom and the dihedral angle between the carboxylate group and its attached benzene ring in the anion is 8.54 (17)°. In the crystal, N—H⋯O hydrogen bonds link the components into [001] chains. Weak C—H⋯O and aromatic π–π stacking [centroid–centroid separation = 3.8503 (18) Å] link the chains into a three-dimensional network.

Keywords: molecular salt; crystal structure; hydrogen bonding..

CCDC reference: 1502522

Structure description

As part of our ongoing studies of hydrogen-bonding patterns in pyridyl molecular salts (Sivakumar et al., 2016a ,b ), we report herein the synthesis and crystal structure of the title molecular salt (Fig. 1).

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

Weak π–π [Cg1⋯Cg2 = 3.850 (1) Å; Cg1 and Cg2 are the centroids of the rings C7–C12 and N1/C1–C5, respectively] interactions are observed between the benzene and pyridine rings. In the crystal, adjacent anions and cations are connected by N—H⋯O (N1—H1A⋯O1ⁱ and N2—H2B⋯O2ⁱ) hydrogen bonds, thereby generating an R₂²(8) ring-motif; these units are further linked by an N2—H2A⋯O2ⁱⁱ hydrogen bond and a C1—H1⋯O1ⁱⁱⁱ contact (Table 1) into chains propagating along [001] (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86 (2)	1.80 (2)	2.661 (3)	175 (3)
N2—H2B⋯O2ⁱ	0.86 (1)	1.93 (1)	2.792 (4)	176 (3)
N2—H2A⋯O2ⁱⁱ	0.85 (2)	1.99 (2)	2.835 (3)	169 (3)
C1—H1⋯O1ⁱⁱⁱ	0.93	2.58	3.223 (3)	126
Symmetry codes: (i) x, y, z+1; (ii) $[-x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x, -y, z+{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the title molecular salt viewed along c 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 salt was synthesized by mixing 2-amino-4-methylpyridine(1.081 g) and p-toluic acid (1.361 g) in an equimolar ratio in an acetone and methanol (1:1) solvent mixture. After a period of 30 days, colourless blocks of the title compound were obtained.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₈H₇O₂⁻
M_r	244.29
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	295
a, b, c (Å)	16.7541 (18), 11.0261 (11), 7.2064 (7)
V (Å³)	1331.3 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.28 × 0.26 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.661, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	17657, 2372, 1903
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.102, 1.11
No. of reflections	2372
No. of parameters	177
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1502522

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616014115/hb4078sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014115/hb4078Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014115/hb4078Isup3.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: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).

2-Amino-4-methylpyridinium 4-methylbenzoate top

Crystal data top

C₆H₉N₂⁺·C₈H₇O₂⁻	D_x = 1.219 Mg m⁻³
M_r = 244.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 6146 reflections
a = 16.7541 (18) Å	θ = 2.4–23.5°
b = 11.0261 (11) Å	µ = 0.08 mm⁻¹
c = 7.2064 (7) Å	T = 295 K
V = 1331.3 (2) Å³	Block, colourless
Z = 4	0.28 × 0.26 × 0.22 mm
F(000) = 520

Data collection top

Bruker Kappa APEXII CCD diffractometer	1903 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 26.4°, θ_min = 2.2°
T_min = 0.661, T_max = 0.745	h = −20→20
17657 measured reflections	k = −13→13
2372 independent reflections	l = −9→6

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0394P)² + 0.3164P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2372 reflections	Δρ_max = 0.12 e Å⁻³
177 parameters	Δρ_min = −0.19 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.

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

	x	y	z	U_iso*/U_eq
C1	−0.03357 (17)	0.1098 (2)	0.5620 (5)	0.0458 (7)
H1	−0.018668	0.033638	0.605372	0.055*
C2	−0.07416 (19)	0.1189 (3)	0.4012 (5)	0.0481 (8)
H2	−0.087627	0.049539	0.334745	0.058*
C3	−0.09593 (17)	0.2338 (3)	0.3350 (4)	0.0442 (7)
C4	−0.07669 (17)	0.3322 (2)	0.4382 (4)	0.0414 (7)
H4	−0.091582	0.408950	0.397487	0.050*
C5	−0.03497 (16)	0.3202 (2)	0.6043 (4)	0.0376 (6)
C6	−0.1390 (2)	0.2460 (3)	0.1553 (5)	0.0639 (9)
H6A	−0.146260	0.330402	0.127061	0.096*
H6B	−0.190096	0.207161	0.164216	0.096*
H6C	−0.108306	0.208399	0.058567	0.096*
C7	0.2124 (2)	0.1820 (5)	0.5775 (5)	0.0713 (11)
C8	0.2006 (2)	0.0940 (4)	0.4461 (6)	0.0705 (11)
H8	0.220675	0.016444	0.465941	0.085*
C9	0.1591 (2)	0.1190 (3)	0.2836 (5)	0.0574 (9)
H9	0.151011	0.057853	0.196778	0.069*
C10	0.12997 (17)	0.2337 (3)	0.2502 (4)	0.0413 (7)
C11	0.1437 (2)	0.3221 (3)	0.3798 (5)	0.0595 (9)
H11	0.125739	0.400643	0.358355	0.071*
C12	0.1841 (2)	0.2957 (4)	0.5422 (6)	0.0786 (12)
H12	0.192168	0.356814	0.629174	0.094*
C13	0.2554 (3)	0.1533 (5)	0.7564 (6)	0.1122 (19)
H13A	0.217202	0.144162	0.854656	0.168*
H13B	0.291374	0.218301	0.785960	0.168*
H13C	0.285005	0.079365	0.742203	0.168*
C14	0.08400 (17)	0.2600 (2)	0.0769 (4)	0.0403 (7)
N1	−0.01429 (14)	0.2087 (2)	0.6605 (3)	0.0397 (6)
N2	−0.01482 (18)	0.4132 (2)	0.7108 (4)	0.0547 (7)
O1	0.06504 (14)	0.17304 (17)	−0.0243 (3)	0.0545 (6)
O2	0.06616 (14)	0.36798 (18)	0.0423 (3)	0.0597 (7)
H2B	0.0117 (17)	0.402 (3)	0.812 (3)	0.056 (10)*
H2A	−0.0303 (17)	0.4832 (16)	0.675 (4)	0.054 (10)*
H1A	0.0133 (15)	0.200 (2)	0.760 (3)	0.039 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0521 (16)	0.0305 (14)	0.0548 (19)	0.0018 (12)	−0.0027 (16)	0.0029 (15)
C2	0.0507 (17)	0.0412 (16)	0.052 (2)	−0.0013 (13)	−0.0055 (15)	−0.0108 (15)
C3	0.0377 (15)	0.0546 (18)	0.0403 (17)	0.0010 (13)	−0.0007 (13)	0.0005 (15)
C4	0.0438 (15)	0.0376 (14)	0.0426 (19)	0.0020 (12)	−0.0046 (13)	0.0059 (14)
C5	0.0422 (14)	0.0312 (13)	0.0394 (17)	0.0007 (11)	−0.0005 (13)	0.0029 (13)
C6	0.059 (2)	0.081 (2)	0.052 (2)	0.0050 (19)	−0.0138 (17)	−0.0044 (19)
C7	0.0448 (18)	0.125 (3)	0.045 (2)	0.004 (2)	−0.0062 (17)	0.011 (2)
C8	0.058 (2)	0.083 (3)	0.070 (3)	0.0028 (19)	−0.0138 (19)	0.029 (2)
C9	0.061 (2)	0.0524 (19)	0.059 (2)	−0.0040 (15)	−0.0159 (17)	0.0100 (16)
C10	0.0395 (15)	0.0471 (16)	0.0373 (15)	−0.0038 (12)	−0.0023 (13)	0.0028 (14)
C11	0.058 (2)	0.067 (2)	0.053 (2)	0.0074 (17)	−0.0110 (16)	−0.0150 (18)
C12	0.063 (2)	0.118 (3)	0.055 (3)	0.006 (2)	−0.0154 (19)	−0.029 (2)
C13	0.068 (3)	0.217 (6)	0.052 (3)	0.015 (3)	−0.019 (2)	0.019 (3)
C14	0.0480 (16)	0.0367 (14)	0.0362 (16)	0.0021 (12)	0.0008 (14)	0.0005 (14)
N1	0.0468 (14)	0.0346 (13)	0.0378 (14)	0.0034 (10)	−0.0087 (11)	0.0045 (11)
N2	0.081 (2)	0.0319 (14)	0.0516 (18)	0.0052 (13)	−0.0215 (15)	0.0002 (13)
O1	0.0787 (15)	0.0360 (10)	0.0489 (14)	0.0060 (11)	−0.0226 (11)	0.0005 (11)
O2	0.0981 (17)	0.0337 (10)	0.0474 (15)	0.0131 (11)	−0.0163 (13)	−0.0015 (10)

Geometric parameters (Å, º) top

C1—N1	1.340 (4)	C8—C9	1.389 (5)
C1—C2	1.347 (4)	C8—H8	0.9300
C1—H1	0.9300	C9—C10	1.377 (4)
C2—C3	1.403 (4)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.369 (4)
C3—C4	1.354 (4)	C10—C14	1.495 (4)
C3—C6	1.489 (5)	C11—C12	1.383 (5)
C4—C5	1.392 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—H12	0.9300
C5—N2	1.325 (4)	C13—H13A	0.9600
C5—N1	1.340 (3)	C13—H13B	0.9600
C6—H6A	0.9600	C13—H13C	0.9600
C6—H6B	0.9600	C14—O1	1.246 (3)
C6—H6C	0.9600	C14—O2	1.253 (3)
C7—C12	1.365 (6)	N1—H1A	0.858 (13)
C7—C8	1.370 (6)	N2—H2B	0.860 (13)
C7—C13	1.510 (5)	N2—H2A	0.855 (13)

N1—C1—C2	121.1 (3)	C10—C9—C8	120.5 (3)
N1—C1—H1	119.5	C10—C9—H9	119.8
C2—C1—H1	119.5	C8—C9—H9	119.8
C1—C2—C3	119.4 (3)	C11—C10—C9	118.3 (3)
C1—C2—H2	120.3	C11—C10—C14	121.2 (3)
C3—C2—H2	120.3	C9—C10—C14	120.4 (3)
C4—C3—C2	118.4 (3)	C10—C11—C12	120.7 (3)
C4—C3—C6	121.4 (3)	C10—C11—H11	119.7
C2—C3—C6	120.2 (3)	C12—C11—H11	119.7
C3—C4—C5	121.0 (3)	C7—C12—C11	121.4 (4)
C3—C4—H4	119.5	C7—C12—H12	119.3
C5—C4—H4	119.5	C11—C12—H12	119.3
N2—C5—N1	118.0 (3)	C7—C13—H13A	109.5
N2—C5—C4	123.5 (2)	C7—C13—H13B	109.5
N1—C5—C4	118.5 (2)	H13A—C13—H13B	109.5
C3—C6—H6A	109.5	C7—C13—H13C	109.5
C3—C6—H6B	109.5	H13A—C13—H13C	109.5
H6A—C6—H6B	109.5	H13B—C13—H13C	109.5
C3—C6—H6C	109.5	O1—C14—O2	123.6 (3)
H6A—C6—H6C	109.5	O1—C14—C10	118.1 (2)
H6B—C6—H6C	109.5	O2—C14—C10	118.3 (2)
C12—C7—C8	118.2 (3)	C5—N1—C1	121.6 (2)
C12—C7—C13	121.1 (4)	C5—N1—H1A	119.7 (19)
C8—C7—C13	120.7 (4)	C1—N1—H1A	118.7 (19)
C7—C8—C9	120.9 (4)	C5—N2—H2B	120 (2)
C7—C8—H8	119.5	C5—N2—H2A	116 (2)
C9—C8—H8	119.5	H2B—N2—H2A	123 (3)

N1—C1—C2—C3	0.6 (5)	C9—C10—C11—C12	−1.7 (5)
C1—C2—C3—C4	−1.4 (4)	C14—C10—C11—C12	177.9 (3)
C1—C2—C3—C6	178.4 (3)	C8—C7—C12—C11	0.8 (6)
C2—C3—C4—C5	1.2 (4)	C13—C7—C12—C11	−179.1 (4)
C6—C3—C4—C5	−178.6 (3)	C10—C11—C12—C7	0.9 (6)
C3—C4—C5—N2	−179.8 (3)	C11—C10—C14—O1	−171.3 (3)
C3—C4—C5—N1	−0.2 (4)	C9—C10—C14—O1	8.2 (4)
C12—C7—C8—C9	−1.7 (6)	C11—C10—C14—O2	8.1 (4)
C13—C7—C8—C9	178.2 (4)	C9—C10—C14—O2	−172.3 (3)
C7—C8—C9—C10	1.0 (5)	N2—C5—N1—C1	178.9 (3)
C8—C9—C10—C11	0.7 (5)	C4—C5—N1—C1	−0.7 (4)
C8—C9—C10—C14	−178.8 (3)	C2—C1—N1—C5	0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86 (2)	1.80 (2)	2.661 (3)	175 (3)
N2—H2B···O2ⁱ	0.86 (1)	1.93 (1)	2.792 (4)	176 (3)
N2—H2A···O2ⁱⁱ	0.85 (2)	1.99 (2)	2.835 (3)	169 (3)
C1—H1···O1ⁱⁱⁱ	0.93	2.58	3.223 (3)	126

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

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras for the data collection.

References

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