2-Methyl­pyridinium 2-carb­oxy-6-nitro­benzoate

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

doi:10.1107/S2414314616011044

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161104

https://doi.org/10.1107/S2414314616011044

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2-Methylpyridinium 2-carboxy-6-nitrobenzoate

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 H. Ishida, Okayama University, Japan (Received 4 July 2016; accepted 7 July 2016; online 12 July 2016)

In the title molecular salt, C₆H₈N⁺·C₈H₄NO₆⁻, the pyridine ring is protonated at the N atom and the anion is deprotonated at one of the hydroxy O atoms. The dihedral angle between the planes of the benzene and pyridine rings is 8.45 (9)°. In the anion, the deprotonated carboxylate group is twisted at an angle of 73.78 (11)° from the attached benzene ring, whereas the carboxy group is slightly oriented at an angle of 14.98 (10)°. N—H⋯O and O—H⋯O hydrogen bonds link the anions and cations into an infinite chain along the c axis and these chains are further consolidated by C—H⋯O hydrogen bonds to form a three-dimensional network. The crystals structure is also influenced by weak π–π interactions [centroid–centroid distance = 3.9055 (9) Å].

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1491386

Structure description

Pyridine derivatives have been reported for their wide range of applications, such as antimicrobial, analgesic, antihyperglycemic, antiproliferative and antitumor activities (Brandt et al., 2010 ; El-Sayed et al., 2011 ). We herein report the synthesis and crystal structure of 2-methylpyridinium 2-carboxy-6-nitrobenzoate (Fig. 1). The geometric parameters are comparable with similar structures reported previously (Divya Bharathi et al., 2015 ; Sivakumar et al., 2016 ).

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

The dihedral angle between the planes of the benzene (C1–C6) and pyridine (N2/C9–C13) rings is 8.45 (9)°. In the anion, the deprotonated carboxylate group (O3/C7/O4) is twisted at an angle of 73.78 (11)° from the attached benzene ring, whereas the carboxy group (O5/C8/O6) is slightly oriented at an angle of 14.98 (10)°. N—H⋯O and O—H⋯O hydrogen bonds (Table 1) link the anions and cations into an infinite chain along the c axis and these chains are further consolidated by C—H⋯O contacts (Table 1) to form a three-dimensional network (Fig. 2). The crystal structure is also influenced by a weak π–π interaction between the benzene rings [Cg⋯Cgⁱ distance = 3.9055 (9) Å; symmetry code: (i) −x, −y + 1, −z + 2].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.88 (1)	1.74 (1)	2.6156 (17)	173 (2)
O6—H6⋯O4ⁱⁱ	0.82 (1)	1.72 (1)	2.5381 (17)	176 (3)
C4—H4⋯O6ⁱⁱⁱ	0.93	2.60	3.493 (2)	161
C10—H10⋯O4^iv	0.93	2.50	3.189 (2)	131
C11—H11⋯O1^v	0.93	2.45	3.346 (3)	162
C14—H14C⋯O5	0.96	2.52	3.428 (3)	158
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x, y, z-1; (v) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A packing diagram of the title compound, viewed along the b axis Hydrogen bonds are shown as dashed lines and C-bound H atoms which are not involved in the interactions have been omitted for clarity.

Synthesis and crystallization

When 3-nitrophthalic acid (2.11 g) and 2-methylpyridine (0.931 g) were added to 15 ml of acetone, a white precipitate formed. The precipitate was dissolved in 20 ml of distilled water and kept for slow evaporation at room temperature. Single crystals suitable for X-ray diffraction study were harvested after 45 d.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₈N⁺·C₈H₄NO₆⁻
M_r	304.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	13.1617 (6), 14.1804 (4), 7.4923 (3)
β (°)	98.758 (2)
V (Å³)	1382.04 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.26 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.970, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	30283, 4541, 3030
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.733

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.163, 1.08
No. of reflections	4541
No. of parameters	207
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)	0.31, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1491386

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616011044/is4010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011044/is4010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616011044/is4010Isup3.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-Methylpyridinium 2-carboxy-6-nitrobenzoate top

Crystal data top

C₆H₈N⁺·C₈H₄NO₆⁻	F(000) = 632
M_r = 304.26	D_x = 1.462 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8089 reflections
a = 13.1617 (6) Å	θ = 2.4–30.4°
b = 14.1804 (4) Å	µ = 0.12 mm⁻¹
c = 7.4923 (3) Å	T = 295 K
β = 98.758 (2)°	Block, colourless
V = 1382.04 (9) Å³	0.26 × 0.22 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	4541 independent reflections
Radiation source: fine-focus sealed tube	3030 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and φ scan	θ_max = 31.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −18→19
T_min = 0.970, T_max = 0.979	k = −20→20
30283 measured reflections	l = −10→10

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0726P)² + 0.3878P] where P = (F_o² + 2F_c²)/3
4541 reflections	(Δ/σ)_max < 0.001
207 parameters	Δρ_max = 0.31 e Å⁻³
2 restraints	Δρ_min = −0.27 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	0.14459 (11)	0.37567 (10)	0.85916 (19)	0.0288 (3)
C2	0.05285 (13)	0.37663 (12)	0.7378 (2)	0.0379 (4)
H2	0.0297	0.3214	0.6781	0.045*
C3	−0.00370 (14)	0.45810 (14)	0.7053 (2)	0.0430 (4)
H3	−0.0651	0.4573	0.6254	0.052*
C4	0.03003 (13)	0.54042 (12)	0.7901 (2)	0.0382 (4)
H4	−0.0066	0.5962	0.7657	0.046*
C5	0.12005 (11)	0.53859 (10)	0.9131 (2)	0.0301 (3)
C6	0.17868 (11)	0.45788 (10)	0.95374 (18)	0.0259 (3)
C7	0.27615 (11)	0.45897 (9)	1.09188 (19)	0.0269 (3)
C8	0.20863 (13)	0.28803 (11)	0.8768 (2)	0.0332 (3)
C9	0.40945 (12)	0.51335 (12)	0.6703 (2)	0.0337 (3)
C10	0.32040 (14)	0.55589 (14)	0.5859 (3)	0.0471 (5)
H10	0.2695	0.5200	0.5178	0.057*
C11	0.30748 (17)	0.65092 (16)	0.6028 (3)	0.0605 (6)
H11	0.2471	0.6795	0.5479	0.073*
C12	0.38325 (19)	0.70445 (15)	0.7007 (3)	0.0655 (7)
H12	0.3751	0.7692	0.7120	0.079*
C13	0.47059 (16)	0.66071 (14)	0.7808 (3)	0.0533 (5)
H13	0.5229	0.6957	0.8474	0.064*
C14	0.42969 (16)	0.41122 (13)	0.6643 (3)	0.0472 (4)
H14A	0.5019	0.4008	0.6656	0.071*
H14B	0.3919	0.3850	0.5559	0.071*
H14C	0.4085	0.3813	0.7675	0.071*
N1	0.15079 (11)	0.62778 (10)	1.0041 (2)	0.0419 (4)
N2	0.48092 (10)	0.56815 (10)	0.76378 (19)	0.0366 (3)
O1	0.12179 (15)	0.70028 (10)	0.9258 (3)	0.0865 (7)
O2	0.20205 (12)	0.62608 (9)	1.1529 (2)	0.0536 (4)
O3	0.35201 (8)	0.49864 (9)	1.04405 (16)	0.0389 (3)
O4	0.27360 (10)	0.42200 (8)	1.24116 (15)	0.0392 (3)
O5	0.29721 (10)	0.28674 (8)	0.94647 (19)	0.0488 (4)
O6	0.15868 (10)	0.21431 (9)	0.8020 (2)	0.0511 (4)
H2A	0.5366 (11)	0.5419 (14)	0.822 (3)	0.053 (6)*
H6	0.1968 (18)	0.1700 (14)	0.787 (4)	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0275 (7)	0.0311 (7)	0.0266 (6)	−0.0022 (6)	0.0001 (5)	−0.0017 (5)
C2	0.0329 (8)	0.0446 (9)	0.0328 (8)	−0.0056 (7)	−0.0055 (6)	−0.0061 (7)
C3	0.0305 (8)	0.0566 (11)	0.0374 (9)	−0.0006 (8)	−0.0086 (7)	0.0036 (8)
C4	0.0303 (8)	0.0409 (9)	0.0414 (9)	0.0055 (7)	−0.0016 (6)	0.0102 (7)
C5	0.0285 (7)	0.0280 (7)	0.0326 (7)	−0.0015 (6)	0.0009 (6)	0.0040 (6)
C6	0.0240 (6)	0.0281 (7)	0.0245 (6)	−0.0017 (5)	0.0003 (5)	0.0031 (5)
C7	0.0278 (7)	0.0227 (6)	0.0278 (7)	−0.0020 (5)	−0.0040 (5)	0.0002 (5)
C8	0.0356 (8)	0.0314 (8)	0.0315 (7)	−0.0027 (6)	0.0014 (6)	−0.0053 (6)
C9	0.0323 (8)	0.0401 (8)	0.0280 (7)	0.0019 (6)	0.0024 (6)	−0.0004 (6)
C10	0.0381 (9)	0.0525 (11)	0.0450 (10)	0.0061 (8)	−0.0122 (7)	−0.0087 (8)
C11	0.0508 (12)	0.0596 (13)	0.0636 (13)	0.0228 (10)	−0.0156 (10)	−0.0056 (10)
C12	0.0685 (15)	0.0424 (11)	0.0782 (16)	0.0159 (10)	−0.0126 (12)	−0.0103 (10)
C13	0.0499 (11)	0.0426 (10)	0.0617 (12)	−0.0012 (9)	−0.0094 (9)	−0.0071 (9)
C14	0.0537 (11)	0.0395 (9)	0.0474 (10)	0.0018 (8)	0.0049 (8)	−0.0008 (8)
N1	0.0356 (7)	0.0270 (7)	0.0613 (10)	−0.0008 (6)	0.0015 (7)	0.0022 (6)
N2	0.0296 (7)	0.0414 (7)	0.0365 (7)	0.0014 (6)	−0.0019 (5)	0.0027 (6)
O1	0.0902 (14)	0.0297 (7)	0.1243 (16)	−0.0004 (8)	−0.0329 (12)	0.0156 (8)
O2	0.0592 (9)	0.0382 (7)	0.0583 (9)	−0.0027 (6)	−0.0076 (7)	−0.0118 (6)
O3	0.0269 (6)	0.0467 (7)	0.0408 (6)	−0.0058 (5)	−0.0024 (5)	0.0093 (5)
O4	0.0495 (7)	0.0361 (6)	0.0285 (5)	−0.0101 (5)	−0.0054 (5)	0.0065 (4)
O5	0.0402 (7)	0.0359 (6)	0.0636 (8)	0.0062 (5)	−0.0132 (6)	−0.0091 (6)
O6	0.0388 (7)	0.0353 (7)	0.0764 (10)	−0.0018 (5)	−0.0002 (6)	−0.0223 (6)

Geometric parameters (Å, º) top

C1—C2	1.397 (2)	C9—C10	1.383 (2)
C1—C6	1.4021 (19)	C9—C14	1.474 (3)
C1—C8	1.496 (2)	C10—C11	1.366 (3)
C2—C3	1.376 (3)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.373 (3)
C3—C4	1.370 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.362 (3)
C4—C5	1.386 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—N2	1.328 (2)
C5—C6	1.388 (2)	C13—H13	0.9300
C5—N1	1.465 (2)	C14—H14A	0.9600
C6—C7	1.5208 (19)	C14—H14B	0.9600
C7—O4	1.2403 (18)	C14—H14C	0.9600
C7—O3	1.2453 (19)	N1—O2	1.212 (2)
C8—O5	1.203 (2)	N1—O1	1.216 (2)
C8—O6	1.3141 (19)	N2—H2A	0.876 (9)
C9—N2	1.334 (2)	O6—H6	0.822 (10)

C2—C1—C6	119.96 (14)	C10—C9—C14	123.99 (16)
C2—C1—C8	119.03 (13)	C11—C10—C9	119.77 (17)
C6—C1—C8	120.88 (13)	C11—C10—H10	120.1
C3—C2—C1	120.95 (15)	C9—C10—H10	120.1
C3—C2—H2	119.5	C10—C11—C12	120.28 (18)
C1—C2—H2	119.5	C10—C11—H11	119.9
C4—C3—C2	120.33 (15)	C12—C11—H11	119.9
C4—C3—H3	119.8	C13—C12—C11	118.62 (19)
C2—C3—H3	119.8	C13—C12—H12	120.7
C3—C4—C5	118.43 (15)	C11—C12—H12	120.7
C3—C4—H4	120.8	N2—C13—C12	119.97 (18)
C5—C4—H4	120.8	N2—C13—H13	120.0
C4—C5—C6	123.49 (14)	C12—C13—H13	120.0
C4—C5—N1	116.18 (14)	C9—C14—H14A	109.5
C6—C5—N1	120.32 (13)	C9—C14—H14B	109.5
C5—C6—C1	116.75 (13)	H14A—C14—H14B	109.5
C5—C6—C7	121.62 (13)	C9—C14—H14C	109.5
C1—C6—C7	121.62 (12)	H14A—C14—H14C	109.5
O4—C7—O3	125.69 (13)	H14B—C14—H14C	109.5
O4—C7—C6	118.26 (13)	O2—N1—O1	123.40 (16)
O3—C7—C6	116.04 (12)	O2—N1—C5	119.14 (13)
O5—C8—O6	124.19 (15)	O1—N1—C5	117.45 (16)
O5—C8—C1	123.15 (14)	C13—N2—C9	123.51 (16)
O6—C8—C1	112.61 (13)	C13—N2—H2A	117.5 (14)
N2—C9—C10	117.84 (16)	C9—N2—H2A	118.9 (14)
N2—C9—C14	118.17 (15)	C8—O6—H6	113 (2)

C6—C1—C2—C3	1.8 (3)	C1—C6—C7—O3	105.86 (16)
C8—C1—C2—C3	−174.11 (17)	C2—C1—C8—O5	163.55 (17)
C1—C2—C3—C4	0.9 (3)	C6—C1—C8—O5	−12.4 (2)
C2—C3—C4—C5	−2.2 (3)	C2—C1—C8—O6	−14.0 (2)
C3—C4—C5—C6	0.7 (3)	C6—C1—C8—O6	170.11 (15)
C3—C4—C5—N1	−178.05 (16)	N2—C9—C10—C11	−1.1 (3)
C4—C5—C6—C1	1.9 (2)	C14—C9—C10—C11	178.4 (2)
N1—C5—C6—C1	−179.33 (14)	C9—C10—C11—C12	1.1 (4)
C4—C5—C6—C7	−179.05 (15)	C10—C11—C12—C13	−0.5 (4)
N1—C5—C6—C7	−0.3 (2)	C11—C12—C13—N2	−0.2 (4)
C2—C1—C6—C5	−3.2 (2)	C4—C5—N1—O2	152.73 (17)
C8—C1—C6—C5	172.70 (14)	C6—C5—N1—O2	−26.1 (2)
C2—C1—C6—C7	177.83 (14)	C4—C5—N1—O1	−26.3 (2)
C8—C1—C6—C7	−6.3 (2)	C6—C5—N1—O1	154.86 (19)
C5—C6—C7—O4	106.09 (17)	C12—C13—N2—C9	0.2 (3)
C1—C6—C7—O4	−74.96 (19)	C10—C9—N2—C13	0.5 (3)
C5—C6—C7—O3	−73.09 (19)	C14—C9—N2—C13	−179.03 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.88 (1)	1.74 (1)	2.6156 (17)	173 (2)
O6—H6···O4ⁱⁱ	0.82 (1)	1.72 (1)	2.5381 (17)	176 (3)
C4—H4···O6ⁱⁱⁱ	0.93	2.60	3.493 (2)	161
C10—H10···O4^iv	0.93	2.50	3.189 (2)	131
C11—H11···O1^v	0.93	2.45	3.346 (3)	162
C14—H14C···O5	0.96	2.52	3.428 (3)	158

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+3/2; (iv) x, y, z−1; (v) x, −y+3/2, z−1/2.

Acknowledgements

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

References

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