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

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ISSN: 2414-3146

2-Amino-4-methyl­pyridinium 4-methyl­benzoate

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 ππ stacking [centroid–centroid separation = 3.8503 (18) Å] link the chains into a three-dimensional network.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

As part of our ongoing studies of hydrogen-bonding patterns in pyridyl mol­ecular salts (Sivakumar et al., 2016a[Sivakumar, P., Sudhahar, S., Israel, S. & Chakkaravarthi, G. (2016a). IUCrData, 1, x160747.],b[Sivakumar, P., Sudhahar, S., Gunasekaran, B., Israel, S. & Chakkaravarthi, G. (2016b). IUCrData, 1, x160817.]), we report herein the synthesis and crystal structure of the title mol­ecular salt (Fig. 1[link]).

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

Weak ππ [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[link]) into chains propagating along [001] (Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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]
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[link].

Table 2
Experimental details

Crystal data
Chemical formula C6H9N2+·C8H7O2
Mr 244.29
Crystal system, space group Orthorhombic, Pna21
Temperature (K) 295
a, b, c (Å) 16.7541 (18), 11.0261 (11), 7.2064 (7)
V3) 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[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.661, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections 17657, 2372, 1903
Rint 0.037
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.12, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2016 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. A71, 3-8.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Structural data


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+·C8H7O2Dx = 1.219 Mg m3
Mr = 244.29Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 6146 reflections
a = 16.7541 (18) Åθ = 2.4–23.5°
b = 11.0261 (11) ŵ = 0.08 mm1
c = 7.2064 (7) ÅT = 295 K
V = 1331.3 (2) Å3Block, colourless
Z = 40.28 × 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 scanRint = 0.037
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
θmax = 26.4°, θmin = 2.2°
Tmin = 0.661, Tmax = 0.745h = 2020
17657 measured reflectionsk = 1313
2372 independent reflectionsl = 96
Refinement top
Refinement on F24 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0394P)2 + 0.3164P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2372 reflectionsΔρmax = 0.12 e Å3
177 parametersΔρmin = 0.19 e Å3
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
xyzUiso*/Ueq
C10.03357 (17)0.1098 (2)0.5620 (5)0.0458 (7)
H10.0186680.0336380.6053720.055*
C20.07416 (19)0.1189 (3)0.4012 (5)0.0481 (8)
H20.0876270.0495390.3347450.058*
C30.09593 (17)0.2338 (3)0.3350 (4)0.0442 (7)
C40.07669 (17)0.3322 (2)0.4382 (4)0.0414 (7)
H40.0915820.4089500.3974870.050*
C50.03497 (16)0.3202 (2)0.6043 (4)0.0376 (6)
C60.1390 (2)0.2460 (3)0.1553 (5)0.0639 (9)
H6A0.1462600.3304020.1270610.096*
H6B0.1900960.2071610.1642160.096*
H6C0.1083060.2083990.0585670.096*
C70.2124 (2)0.1820 (5)0.5775 (5)0.0713 (11)
C80.2006 (2)0.0940 (4)0.4461 (6)0.0705 (11)
H80.2206750.0164440.4659410.085*
C90.1591 (2)0.1190 (3)0.2836 (5)0.0574 (9)
H90.1510110.0578530.1967780.069*
C100.12997 (17)0.2337 (3)0.2502 (4)0.0413 (7)
C110.1437 (2)0.3221 (3)0.3798 (5)0.0595 (9)
H110.1257390.4006430.3583550.071*
C120.1841 (2)0.2957 (4)0.5422 (6)0.0786 (12)
H120.1921680.3568140.6291740.094*
C130.2554 (3)0.1533 (5)0.7564 (6)0.1122 (19)
H13A0.2172020.1441620.8546560.168*
H13B0.2913740.2183010.7859600.168*
H13C0.2850050.0793650.7422030.168*
C140.08400 (17)0.2600 (2)0.0769 (4)0.0403 (7)
N10.01429 (14)0.2087 (2)0.6605 (3)0.0397 (6)
N20.01482 (18)0.4132 (2)0.7108 (4)0.0547 (7)
O10.06504 (14)0.17304 (17)0.0243 (3)0.0545 (6)
O20.06616 (14)0.36798 (18)0.0423 (3)0.0597 (7)
H2B0.0117 (17)0.402 (3)0.812 (3)0.056 (10)*
H2A0.0303 (17)0.4832 (16)0.675 (4)0.054 (10)*
H1A0.0133 (15)0.200 (2)0.760 (3)0.039 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0521 (16)0.0305 (14)0.0548 (19)0.0018 (12)0.0027 (16)0.0029 (15)
C20.0507 (17)0.0412 (16)0.052 (2)0.0013 (13)0.0055 (15)0.0108 (15)
C30.0377 (15)0.0546 (18)0.0403 (17)0.0010 (13)0.0007 (13)0.0005 (15)
C40.0438 (15)0.0376 (14)0.0426 (19)0.0020 (12)0.0046 (13)0.0059 (14)
C50.0422 (14)0.0312 (13)0.0394 (17)0.0007 (11)0.0005 (13)0.0029 (13)
C60.059 (2)0.081 (2)0.052 (2)0.0050 (19)0.0138 (17)0.0044 (19)
C70.0448 (18)0.125 (3)0.045 (2)0.004 (2)0.0062 (17)0.011 (2)
C80.058 (2)0.083 (3)0.070 (3)0.0028 (19)0.0138 (19)0.029 (2)
C90.061 (2)0.0524 (19)0.059 (2)0.0040 (15)0.0159 (17)0.0100 (16)
C100.0395 (15)0.0471 (16)0.0373 (15)0.0038 (12)0.0023 (13)0.0028 (14)
C110.058 (2)0.067 (2)0.053 (2)0.0074 (17)0.0110 (16)0.0150 (18)
C120.063 (2)0.118 (3)0.055 (3)0.006 (2)0.0154 (19)0.029 (2)
C130.068 (3)0.217 (6)0.052 (3)0.015 (3)0.019 (2)0.019 (3)
C140.0480 (16)0.0367 (14)0.0362 (16)0.0021 (12)0.0008 (14)0.0005 (14)
N10.0468 (14)0.0346 (13)0.0378 (14)0.0034 (10)0.0087 (11)0.0045 (11)
N20.081 (2)0.0319 (14)0.0516 (18)0.0052 (13)0.0215 (15)0.0002 (13)
O10.0787 (15)0.0360 (10)0.0489 (14)0.0060 (11)0.0226 (11)0.0005 (11)
O20.0981 (17)0.0337 (10)0.0474 (15)0.0131 (11)0.0163 (13)0.0015 (10)
Geometric parameters (Å, º) top
C1—N11.340 (4)C8—C91.389 (5)
C1—C21.347 (4)C8—H80.9300
C1—H10.9300C9—C101.377 (4)
C2—C31.403 (4)C9—H90.9300
C2—H20.9300C10—C111.369 (4)
C3—C41.354 (4)C10—C141.495 (4)
C3—C61.489 (5)C11—C121.383 (5)
C4—C51.392 (4)C11—H110.9300
C4—H40.9300C12—H120.9300
C5—N21.325 (4)C13—H13A0.9600
C5—N11.340 (3)C13—H13B0.9600
C6—H6A0.9600C13—H13C0.9600
C6—H6B0.9600C14—O11.246 (3)
C6—H6C0.9600C14—O21.253 (3)
C7—C121.365 (6)N1—H1A0.858 (13)
C7—C81.370 (6)N2—H2B0.860 (13)
C7—C131.510 (5)N2—H2A0.855 (13)
N1—C1—C2121.1 (3)C10—C9—C8120.5 (3)
N1—C1—H1119.5C10—C9—H9119.8
C2—C1—H1119.5C8—C9—H9119.8
C1—C2—C3119.4 (3)C11—C10—C9118.3 (3)
C1—C2—H2120.3C11—C10—C14121.2 (3)
C3—C2—H2120.3C9—C10—C14120.4 (3)
C4—C3—C2118.4 (3)C10—C11—C12120.7 (3)
C4—C3—C6121.4 (3)C10—C11—H11119.7
C2—C3—C6120.2 (3)C12—C11—H11119.7
C3—C4—C5121.0 (3)C7—C12—C11121.4 (4)
C3—C4—H4119.5C7—C12—H12119.3
C5—C4—H4119.5C11—C12—H12119.3
N2—C5—N1118.0 (3)C7—C13—H13A109.5
N2—C5—C4123.5 (2)C7—C13—H13B109.5
N1—C5—C4118.5 (2)H13A—C13—H13B109.5
C3—C6—H6A109.5C7—C13—H13C109.5
C3—C6—H6B109.5H13A—C13—H13C109.5
H6A—C6—H6B109.5H13B—C13—H13C109.5
C3—C6—H6C109.5O1—C14—O2123.6 (3)
H6A—C6—H6C109.5O1—C14—C10118.1 (2)
H6B—C6—H6C109.5O2—C14—C10118.3 (2)
C12—C7—C8118.2 (3)C5—N1—C1121.6 (2)
C12—C7—C13121.1 (4)C5—N1—H1A119.7 (19)
C8—C7—C13120.7 (4)C1—N1—H1A118.7 (19)
C7—C8—C9120.9 (4)C5—N2—H2B120 (2)
C7—C8—H8119.5C5—N2—H2A116 (2)
C9—C8—H8119.5H2B—N2—H2A123 (3)
N1—C1—C2—C30.6 (5)C9—C10—C11—C121.7 (5)
C1—C2—C3—C41.4 (4)C14—C10—C11—C12177.9 (3)
C1—C2—C3—C6178.4 (3)C8—C7—C12—C110.8 (6)
C2—C3—C4—C51.2 (4)C13—C7—C12—C11179.1 (4)
C6—C3—C4—C5178.6 (3)C10—C11—C12—C70.9 (6)
C3—C4—C5—N2179.8 (3)C11—C10—C14—O1171.3 (3)
C3—C4—C5—N10.2 (4)C9—C10—C14—O18.2 (4)
C12—C7—C8—C91.7 (6)C11—C10—C14—O28.1 (4)
C13—C7—C8—C9178.2 (4)C9—C10—C14—O2172.3 (3)
C7—C8—C9—C101.0 (5)N2—C5—N1—C1178.9 (3)
C8—C9—C10—C110.7 (5)C4—C5—N1—C10.7 (4)
C8—C9—C10—C14178.8 (3)C2—C1—N1—C50.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.86 (2)1.80 (2)2.661 (3)175 (3)
N2—H2B···O2i0.86 (1)1.93 (1)2.792 (4)176 (3)
N2—H2A···O2ii0.85 (2)1.99 (2)2.835 (3)169 (3)
C1—H1···O1iii0.932.583.223 (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

First citationBruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. A71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSivakumar, P., Sudhahar, S., Gunasekaran, B., Israel, S. & Chakkaravarthi, G. (2016b). IUCrData, 1, x160817.  Google Scholar
First citationSivakumar, P., Sudhahar, S., Israel, S. & Chakkaravarthi, G. (2016a). IUCrData, 1, x160747.  Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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