2-Amino-4-methyl­pyridin-1-ium 2-(4-nitro­phen­yl)acetate

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

doi:10.1107/S2414314616014334

organic compounds

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ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161433

doi:10.1107/S2414314616014334

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2-Amino-4-methylpyridin-1-ium 2-(4-nitrophenyl)acetate

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 R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 25 August 2016; accepted 9 September 2016; online 16 September 2016)

In the title molecular salt, C₆H₉N₂⁺·C₈H₆NO₄⁻, the cation is protonated at its pyridine N atom. In the crystal, the anion and cation are connected by weak N—H⋯O hydrogen bonds, generating an R₂²(8) ring motif. A pair of N—H⋯O hydrogen bonds and a C—H⋯O contact generate an R₂³(19) ring motif. In the crystal, adjacent anions and cations are linked by N—H⋯O hydrogen bonds into infinite chains along [001]. The components are further linked by weak C—H⋯O contacts and C—H⋯π interactions, forming a three-dimensional network.

Keywords: molecular salt; crystal structure; hydrogen bonding.

CCDC reference: 1503502

Structure description

Pyridine derivatives show a wide range of biological activities such as anti-inflammatory (Rupert et al., 2003 ), antiviral (Hamdouchi et al., 1999 ) and antibacterial (Rival et al., 1992 ). We herein report the synthesis and crystal structure of the title molecular salt (Fig. 1). The geometric parameters are agree well with those for similar reported structures (Sivakumar et al., 2016a ,b ).

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

The asymmetric unit (Fig. 1) comprises a 2-amino-4-methylpyridin-1-ium cation and 2-(4-nitrophenyl)acetate anion. The cation is protonated at the N1 atom and the anion is deprotonated at the hydroxyl O3 atom. In the crystal, the anion and cation are connected by weak N1—H1A⋯O3 and N2—H2B⋯O4 hydrogen bonds, by generating an R₂²(8) ring-motif (Fig. 2). The N2—H2B⋯O4 and N2—H2A⋯O3ⁱ hydrogen bonds and C12—H12⋯O1ⁱ contact generate an R₂³(19) ring motif (Fig. 2).

Figure 2
A partial view of the crystal packing of the title molecular salt, showing the ring motifs. Symmetry code: (i) x, 1 − y, − $[{1\over 2}]$ + z.

In the crystal, adjacent anions and cations are linked by N2—H2A⋯O3ⁱ hydrogen bonds (Table 1) into infinite chains along [00] . The components are further linked by weak C—H⋯O and C—H⋯π interactions (Table 1), forming a three-dimensional network (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N1/C1–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.86 (1)	1.79 (2)	2.643 (5)	169 (5)
N2—H2B⋯O4	0.86 (1)	1.97 (2)	2.822 (6)	173 (4)
N2—H2A⋯O3ⁱ	0.86 (1)	2.03 (2)	2.885 (5)	174 (4)
C2—H2⋯O2ⁱⁱ	0.93	2.57	3.420 (6)	152
C6—H6C⋯O1ⁱⁱⁱ	0.96	2.44	3.371 (6)	163
C9—H9⋯O4^iv	0.93	2.50	3.328 (5)	149
C12—H12⋯O1ⁱ	0.93	2.59	3.249 (6)	128
C6—H6C⋯Cg2^v	0.96	2.71	3.448 (4)	134
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x-1, -y+2, z-{\script{1\over 2}}]$ ; (iii) x-1, y, z-1; (iv) $[x, -y, z+{\script{1\over 2}}]$ ; (v) x, y+1, z.

Figure 3
The crystal packing of the title molecular salt viewed along b axis. The hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.

Synthesis and crystallization

The title compound was synthesized by mixing 4-methylpyridine (0.93 g) and 4-nitrophenylacetic acid (1.81 g) in (1:1) ratio in 10 ml acetone. This saturated solution was allowed to evaporate slowly at room temperature, yielding single crystals suitable for X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The reflections ( $[\overline{1}]$ 00) and (100) were omitted during refinement due to probable shadowing by the beam stop.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₈H₆NO₄⁻
M_r	289.29
Crystal system, space group	Monoclinic, Pc
Temperature (K)	295
a, b, c (Å)	13.856 (2), 4.5401 (7), 11.926 (2)
β (°)	111.173 (5)
V (Å³)	699.6 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.604, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8319, 2718, 1886
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.101, 1.03
No. of reflections	2718
No. of parameters	203
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1503502

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616014334/bg4002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014334/bg4002Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014334/bg4002Isup3.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) and PLATON (Spek, 2009).

2-Amino-4-methylpyridin-1-ium 2-(4-nitrophenyl)acetate top

Crystal data top

C₆H₉N₂⁺·C₈H₆NO₄⁻	F(000) = 304
M_r = 289.29	D_x = 1.373 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 13.856 (2) Å	Cell parameters from 3185 reflections
b = 4.5401 (7) Å	θ = 3.2–27.2°
c = 11.926 (2) Å	µ = 0.10 mm⁻¹
β = 111.173 (5)°	T = 295 K
V = 699.6 (2) Å³	Block, colourless
Z = 2	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1886 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 27.2°, θ_min = 3.2°
T_min = 0.604, T_max = 0.746	h = −17→16
8319 measured reflections	k = −5→5
2718 independent reflections	l = −15→15

Refinement top

Refinement on F²	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0206P)² + 0.4424P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2718 reflections	Δρ_max = 0.22 e Å⁻³
203 parameters	Δρ_min = −0.20 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	−0.0033 (4)	0.6796 (10)	0.5037 (4)	0.0498 (12)
H1	−0.011296	0.607231	0.572757	0.060*
C2	−0.0719 (4)	0.8768 (10)	0.4360 (4)	0.0506 (12)
H2	−0.125667	0.944028	0.458519	0.061*
C3	−0.0605 (3)	0.9792 (9)	0.3303 (4)	0.0437 (10)
C4	0.0203 (3)	0.8827 (10)	0.3020 (4)	0.0425 (10)
H4	0.028963	0.953470	0.233113	0.051*
C5	0.0910 (3)	0.6783 (9)	0.3748 (3)	0.0383 (10)
C6	−0.1387 (4)	1.1939 (11)	0.2509 (5)	0.0598 (14)
H6A	−0.106304	1.314928	0.208587	0.090*
H6B	−0.164471	1.316119	0.299533	0.090*
H6C	−0.195057	1.087173	0.194049	0.090*
C7	0.5945 (3)	0.4240 (11)	0.9353 (4)	0.0405 (10)
C8	0.5118 (3)	0.3703 (11)	0.9693 (4)	0.0501 (12)
H8	0.509297	0.451168	1.039877	0.060*
C9	0.4324 (3)	0.1949 (11)	0.8978 (4)	0.0479 (11)
H9	0.376499	0.154529	0.920964	0.057*
C10	0.4348 (3)	0.0787 (10)	0.7924 (3)	0.0408 (10)
C11	0.5190 (3)	0.1367 (11)	0.7598 (4)	0.0482 (12)
H11	0.521242	0.058504	0.688750	0.058*
C12	0.5998 (4)	0.3095 (11)	0.8314 (4)	0.0512 (12)
H12	0.656653	0.347214	0.809596	0.061*
C13	0.3445 (4)	−0.0941 (10)	0.7099 (4)	0.0518 (12)
H13A	0.307906	−0.186722	0.756152	0.062*
H13B	0.369170	−0.247746	0.670433	0.062*
C14	0.2711 (3)	0.1111 (10)	0.6155 (4)	0.0444 (10)
N1	0.0765 (3)	0.5834 (9)	0.4748 (3)	0.0404 (8)
N2	0.1693 (3)	0.5673 (10)	0.3502 (4)	0.0552 (10)
N3	0.6791 (3)	0.6122 (10)	1.0109 (4)	0.0572 (11)
O1	0.6716 (3)	0.7190 (10)	1.1007 (3)	0.0894 (14)
O2	0.7543 (3)	0.6494 (10)	0.9824 (3)	0.0849 (12)
O3	0.1947 (2)	0.2097 (8)	0.6360 (3)	0.0552 (9)
O4	0.2937 (3)	0.1761 (9)	0.5275 (3)	0.0723 (11)
H1A	0.119 (3)	0.455 (8)	0.520 (3)	0.060 (16)*
H2A	0.181 (3)	0.635 (9)	0.289 (2)	0.048 (12)*
H2B	0.211 (3)	0.452 (8)	0.403 (3)	0.046 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.061 (3)	0.057 (3)	0.046 (3)	0.004 (2)	0.036 (2)	−0.003 (2)
C2	0.051 (3)	0.051 (3)	0.058 (3)	0.004 (2)	0.031 (2)	−0.009 (2)
C3	0.050 (3)	0.036 (2)	0.045 (3)	−0.006 (2)	0.017 (2)	−0.0051 (19)
C4	0.050 (3)	0.042 (2)	0.038 (2)	−0.006 (2)	0.020 (2)	0.000 (2)
C5	0.044 (3)	0.041 (3)	0.035 (2)	−0.007 (2)	0.0198 (19)	−0.0056 (19)
C6	0.058 (3)	0.052 (3)	0.066 (3)	0.001 (3)	0.018 (3)	−0.003 (3)
C7	0.036 (2)	0.045 (3)	0.040 (2)	−0.004 (2)	0.0129 (19)	0.005 (2)
C8	0.049 (3)	0.064 (3)	0.044 (3)	−0.007 (3)	0.025 (2)	0.002 (2)
C9	0.040 (2)	0.061 (3)	0.051 (3)	−0.002 (2)	0.026 (2)	0.010 (2)
C10	0.039 (2)	0.037 (2)	0.046 (3)	0.003 (2)	0.016 (2)	0.0096 (19)
C11	0.052 (3)	0.055 (3)	0.045 (3)	0.001 (2)	0.026 (2)	−0.003 (2)
C12	0.044 (3)	0.065 (3)	0.054 (3)	−0.003 (2)	0.030 (2)	0.001 (3)
C13	0.056 (3)	0.040 (3)	0.062 (3)	−0.004 (2)	0.025 (2)	0.001 (2)
C14	0.045 (3)	0.044 (2)	0.047 (3)	−0.005 (2)	0.019 (2)	−0.008 (2)
N1	0.045 (2)	0.045 (2)	0.036 (2)	0.0017 (18)	0.0202 (18)	−0.0008 (17)
N2	0.055 (3)	0.071 (3)	0.049 (2)	0.007 (2)	0.031 (2)	0.008 (2)
N3	0.050 (3)	0.071 (3)	0.050 (2)	−0.013 (2)	0.017 (2)	0.007 (2)
O1	0.079 (3)	0.125 (4)	0.071 (3)	−0.036 (3)	0.035 (2)	−0.037 (3)
O2	0.058 (2)	0.118 (3)	0.087 (3)	−0.034 (2)	0.035 (2)	−0.012 (2)
O3	0.053 (2)	0.072 (2)	0.0488 (18)	0.0082 (17)	0.0286 (16)	0.0008 (16)
O4	0.074 (3)	0.099 (3)	0.058 (2)	0.030 (2)	0.041 (2)	0.016 (2)

Geometric parameters (Å, º) top

C1—C2	1.342 (6)	C8—H8	0.9300
C1—N1	1.345 (5)	C9—C10	1.375 (6)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.405 (6)	C10—C11	1.381 (5)
C2—H2	0.9300	C10—C13	1.503 (6)
C3—C4	1.353 (6)	C11—C12	1.382 (6)
C3—C6	1.510 (6)	C11—H11	0.9300
C4—C5	1.400 (6)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.531 (6)
C5—N2	1.321 (6)	C13—H13A	0.9700
C5—N1	1.350 (5)	C13—H13B	0.9700
C6—H6A	0.9600	C14—O4	1.234 (5)
C6—H6B	0.9600	C14—O3	1.253 (5)
C6—H6C	0.9600	N1—H1A	0.862 (14)
C7—C8	1.368 (6)	N2—H2A	0.858 (13)
C7—C12	1.371 (6)	N2—H2B	0.860 (14)
C7—N3	1.467 (6)	N3—O1	1.214 (5)
C8—C9	1.377 (6)	N3—O2	1.219 (5)

C2—C1—N1	122.1 (4)	C8—C9—H9	119.6
C2—C1—H1	118.9	C9—C10—C11	119.1 (4)
N1—C1—H1	118.9	C9—C10—C13	120.6 (4)
C1—C2—C3	118.4 (4)	C11—C10—C13	120.2 (4)
C1—C2—H2	120.8	C10—C11—C12	120.9 (4)
C3—C2—H2	120.8	C10—C11—H11	119.6
C4—C3—C2	119.2 (4)	C12—C11—H11	119.6
C4—C3—C6	121.6 (4)	C7—C12—C11	118.5 (4)
C2—C3—C6	119.3 (4)	C7—C12—H12	120.7
C3—C4—C5	121.2 (4)	C11—C12—H12	120.7
C3—C4—H4	119.4	C10—C13—C14	109.8 (4)
C5—C4—H4	119.4	C10—C13—H13A	109.7
N2—C5—N1	118.1 (4)	C14—C13—H13A	109.7
N2—C5—C4	124.2 (4)	C10—C13—H13B	109.7
N1—C5—C4	117.7 (4)	C14—C13—H13B	109.7
C3—C6—H6A	109.5	H13A—C13—H13B	108.2
C3—C6—H6B	109.5	O4—C14—O3	124.9 (4)
H6A—C6—H6B	109.5	O4—C14—C13	117.8 (4)
C3—C6—H6C	109.5	O3—C14—C13	117.2 (4)
H6A—C6—H6C	109.5	C1—N1—C5	121.4 (4)
H6B—C6—H6C	109.5	C1—N1—H1A	119 (3)
C8—C7—C12	121.7 (4)	C5—N1—H1A	119 (3)
C8—C7—N3	119.4 (4)	C5—N2—H2A	118 (3)
C12—C7—N3	118.9 (4)	C5—N2—H2B	118 (3)
C7—C8—C9	119.1 (4)	H2A—N2—H2B	123 (4)
C7—C8—H8	120.4	O1—N3—O2	122.9 (5)
C9—C8—H8	120.4	O1—N3—C7	118.1 (4)
C10—C9—C8	120.7 (4)	O2—N3—C7	119.0 (4)
C10—C9—H9	119.6

N1—C1—C2—C3	1.5 (7)	C8—C7—C12—C11	0.3 (7)
C1—C2—C3—C4	−1.8 (6)	N3—C7—C12—C11	−178.9 (4)
C1—C2—C3—C6	178.1 (4)	C10—C11—C12—C7	−0.4 (7)
C2—C3—C4—C5	1.5 (6)	C9—C10—C13—C14	92.7 (5)
C6—C3—C4—C5	−178.5 (4)	C11—C10—C13—C14	−83.7 (5)
C3—C4—C5—N2	177.5 (4)	C10—C13—C14—O4	80.8 (5)
C3—C4—C5—N1	−0.8 (6)	C10—C13—C14—O3	−96.4 (5)
C12—C7—C8—C9	0.5 (7)	C2—C1—N1—C5	−0.8 (7)
N3—C7—C8—C9	179.6 (4)	N2—C5—N1—C1	−178.0 (4)
C7—C8—C9—C10	−1.1 (7)	C4—C5—N1—C1	0.4 (6)
C8—C9—C10—C11	0.9 (7)	C8—C7—N3—O1	−1.3 (7)
C8—C9—C10—C13	−175.5 (4)	C12—C7—N3—O1	177.8 (5)
C9—C10—C11—C12	−0.2 (7)	C8—C7—N3—O2	177.1 (5)
C13—C10—C11—C12	176.3 (4)	C12—C7—N3—O2	−3.7 (7)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the N1/C1–C5 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86 (1)	1.79 (2)	2.643 (5)	169 (5)
N2—H2B···O4	0.86 (1)	1.97 (2)	2.822 (6)	173 (4)
N2—H2A···O3ⁱ	0.86 (1)	2.03 (2)	2.885 (5)	174 (4)
C2—H2···O2ⁱⁱ	0.93	2.57	3.420 (6)	152
C6—H6C···O1ⁱⁱⁱ	0.96	2.44	3.371 (6)	163
C9—H9···O4^iv	0.93	2.50	3.328 (5)	149
C12—H12···O1ⁱ	0.93	2.59	3.249 (6)	128
C6—H6C···Cg2^v	0.96	2.71	3.448 (4)	134

Symmetry codes: (i) x, −y+1, z−1/2; (ii) x−1, −y+2, z−1/2; (iii) x−1, y, z−1; (iv) x, −y, z+1/2; (v) x, y+1, 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
Hamdouchi, C., de Blas, J., del Prado, M., Gruber, J., Heinz, B. A. & Vance, L. (1999). J. Med. Chem. 42, 50–59. Web of Science CrossRef CAS PubMed Google Scholar
Rival, Y., Grassy, G. & Michel, G. (1992). Chem. Pharm. Bull. 40, 1170–1176. CrossRef PubMed CAS Google Scholar
Rupert, K. C., Henry, J. R., Dodd, J. H., Wadsworth, S. A., Cavender, D. E., Olini, G. C., Fahmy, B. & Siekierka, J. J. (2003). Bioorg. Med. Chem. Lett. 13, 347–350. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef 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 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-methyl­pyridin-1-ium 2-(4-nitro­phen­yl)acetate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

2-Amino-4-methylpyridin-1-ium 2-(4-nitrophenyl)acetate