4-Methyl­pyridinium 2-carboxy-6-nitrobenzoate

Devi, S.R.; Kalaiyarasi, S.; Akilan, R.; Kumar, R.M.; Chakkaravarthi, G.

doi:10.1107/S2414314616018034

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161803

https://doi.org/10.1107/S2414314616018034

Open

access

4-Methylpyridinium 2-carboxy-6-nitrobenzoate

S. Reena Devi,^a S. Kalaiyarasi,^a R. Akilan,^b R. Mohan Kumar ^a ^* and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: mohan66@hotmail.com, chakkaravarthi_2005@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 November 2016; accepted 9 November 2016; online 15 November 2016)

In the title molecular salt, C₆H₈N⁺·C₈H₄NO₆⁻, the anion is deprotonated at the carboxylic acid group adjacent to the nitro group. In the crystal, the anions are linked into an [001] chain by O—H⋯O hydrogen bonds. The cations are linked to these chains by N—H⋯O hydrogen bonds and weak C—H⋯O contacts, generating a three-dimensional network.

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

CCDC reference: 1515803

Structure description

As part of our ongoing studies of molecular salts (Sivakumar et al., 2016 ), we now report the synthesis and the crystal structure of the title compound (Fig. 1). Its geometric parameters are comparable with those of reported structures (Li & Chai, 2007 )

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

The anion is deprotonated at the central carboxylic acid group (C8/O3/O4), but not the other (C7/O5/O6), hence a 1:1 stoichiometry salt arises. The dihedral angles between the C1–C6 benzene ring and the C7/O5/O6, C8/O3/O4 and N1/O1/O2 substituents are 27.09 (11), 71.59 (10) and 68.44 (11)°, respectively.

In the crystal, the N2—H2A⋯O4 hydrogen bond and C13—H13⋯O6 contact generate an R₂²(10) ring-set motif (Table 1, Fig. 2). The O6—H6⋯O3ⁱ hydrogen bond (Table 1) links adjacent anions into an infinite chain along [001]. The crystal structure is consolidated by weak C—H⋯O contacts to form a three dimensional network (Table 1, Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4	0.86 (3)	1.87 (3)	2.699 (2)	160 (2)
O6—H6⋯O3ⁱ	0.84 (1)	1.65 (1)	2.484 (2)	170 (3)
C13—H13⋯O6	0.93	2.44	3.219 (3)	141
C2—H2⋯O4ⁱⁱ	0.93	2.36	3.171 (3)	145
C10—H10⋯O3ⁱⁱⁱ	0.93	2.54	3.191 (3)	127
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) -x, -y, -z+1.

Figure 2
A partial view of the crystal packing showing ring-set motif.

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

Synthesis and crystallization

The title salt was synthesized from 4-methylpyridine (4.90 g) and 3-nitrophthalic acid (5.28 g) in a 2:1 ratio. These reactants were dissolved in water and continuously stirred about 5 h and kept at 35°C using a constant temperature bath. After 20 days, crystals suitable for X-ray diffraction were harvested.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₄NO₆·C₆H₈N
M_r	304.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.683 (5), 17.309 (6), 11.172 (5)
β (°)	109.260 (5)
V (Å³)	1402.6 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
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	0.504, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	18131, 4295, 2572
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.153, 1.04
No. of reflections	4295
No. of parameters	208
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.35
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1515803

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616018034/hb4095sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018034/hb4095Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616018034/hb4095Isup3.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).

4-Methylpyridinium 2-carboxy-6-nitrobenzoate top

Crystal data top

C₆H₈N⁺·C₈H₄NO₆⁻	F(000) = 632
M_r = 304.26	D_x = 1.441 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.683 (5) Å	Cell parameters from 5621 reflections
b = 17.309 (6) Å	θ = 2.3–31.0°
c = 11.172 (5) Å	µ = 0.12 mm⁻¹
β = 109.260 (5)°	T = 295 K
V = 1402.6 (12) Å³	Block, colourless
Z = 4	0.28 × 0.26 × 0.22 mm

Data collection top

Bruker axs kappa apex2 CCD diffractometer	2572 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.054
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 30.8°, θ_min = 2.3°
T_min = 0.504, T_max = 0.746	h = −10→9
18131 measured reflections	k = −24→24
4295 independent reflections	l = −14→16

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.0595P)² + 0.4448P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.153	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.58 e Å⁻³
4295 reflections	Δρ_min = −0.35 e Å⁻³
208 parameters	Extinction correction: SHELXL-2016/4 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.015 (3)
Primary atom site location: structure-invariant direct methods

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	0.5227 (2)	0.13436 (10)	0.49500 (16)	0.0344 (4)
C2	0.7063 (2)	0.15506 (12)	0.54221 (19)	0.0455 (5)
H2	0.792007	0.132931	0.510103	0.055*
C3	0.7598 (3)	0.20898 (13)	0.6376 (2)	0.0515 (5)
H3	0.883187	0.223208	0.670951	0.062*
C4	0.6323 (3)	0.24217 (12)	0.68415 (19)	0.0455 (5)
H4	0.670037	0.278336	0.749197	0.055*
C5	0.4471 (2)	0.22170 (10)	0.63407 (16)	0.0333 (4)
C6	0.3892 (2)	0.16713 (9)	0.53821 (15)	0.0292 (3)
C7	0.3055 (2)	0.26237 (10)	0.67731 (17)	0.0380 (4)
C8	0.1850 (2)	0.14998 (9)	0.48115 (15)	0.0307 (3)
C9	0.1140 (3)	−0.02111 (13)	0.75650 (18)	0.0462 (5)
H9	0.057618	−0.038361	0.673896	0.055*
C10	0.1235 (3)	−0.06817 (12)	0.8561 (2)	0.0490 (5)
H10	0.072761	−0.117460	0.841181	0.059*
C11	0.2077 (3)	−0.04341 (12)	0.97884 (19)	0.0474 (5)
C12	0.2786 (4)	0.03076 (14)	0.9961 (2)	0.0599 (6)
H12	0.335995	0.049530	1.077639	0.072*
C13	0.2645 (3)	0.07629 (13)	0.8942 (2)	0.0594 (6)
H13	0.310476	0.126439	0.906422	0.071*
C14	0.2237 (4)	−0.09521 (17)	1.0893 (2)	0.0760 (8)
H14A	0.110131	−0.122777	1.074606	0.114*
H14B	0.249051	−0.064691	1.164917	0.114*
H14C	0.322252	−0.131367	1.099301	0.114*
N1	0.4690 (2)	0.07633 (10)	0.39439 (15)	0.0455 (4)
N2	0.1856 (2)	0.04959 (11)	0.77753 (17)	0.0471 (4)
O1	0.5633 (2)	0.07038 (13)	0.32559 (17)	0.0863 (6)
O2	0.3329 (2)	0.03729 (9)	0.38272 (15)	0.0610 (4)
O3	0.10343 (16)	0.17716 (8)	0.37237 (12)	0.0429 (3)
O4	0.10975 (16)	0.11345 (8)	0.54551 (12)	0.0433 (3)
O5	0.1921 (3)	0.30446 (12)	0.60735 (17)	0.0875 (7)
O6	0.3113 (2)	0.24557 (9)	0.78951 (14)	0.0574 (4)
H2A	0.180 (3)	0.0781 (15)	0.713 (2)	0.064 (7)*
H6	0.233 (3)	0.2727 (16)	0.808 (3)	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0292 (8)	0.0394 (9)	0.0369 (9)	0.0043 (7)	0.0142 (7)	0.0024 (7)
C2	0.0279 (8)	0.0576 (12)	0.0550 (11)	0.0066 (8)	0.0191 (8)	0.0051 (10)
C3	0.0278 (8)	0.0607 (13)	0.0629 (13)	−0.0068 (8)	0.0110 (9)	0.0018 (11)
C4	0.0393 (10)	0.0460 (11)	0.0470 (11)	−0.0085 (8)	0.0084 (8)	−0.0049 (9)
C5	0.0337 (8)	0.0316 (8)	0.0367 (9)	−0.0002 (6)	0.0146 (7)	0.0014 (7)
C6	0.0245 (7)	0.0322 (8)	0.0333 (8)	0.0008 (6)	0.0126 (6)	0.0036 (7)
C7	0.0430 (10)	0.0330 (9)	0.0408 (10)	0.0019 (7)	0.0176 (8)	−0.0023 (8)
C8	0.0264 (7)	0.0337 (8)	0.0351 (9)	0.0005 (6)	0.0143 (6)	−0.0013 (7)
C9	0.0410 (10)	0.0577 (13)	0.0397 (10)	−0.0020 (9)	0.0133 (8)	−0.0031 (9)
C10	0.0513 (11)	0.0430 (11)	0.0528 (12)	−0.0065 (9)	0.0173 (9)	−0.0006 (9)
C11	0.0506 (11)	0.0501 (12)	0.0432 (11)	0.0058 (9)	0.0176 (9)	0.0062 (9)
C12	0.0750 (15)	0.0550 (13)	0.0436 (12)	−0.0034 (11)	0.0113 (11)	−0.0079 (10)
C13	0.0696 (14)	0.0409 (11)	0.0643 (15)	−0.0078 (10)	0.0173 (11)	−0.0011 (10)
C14	0.0891 (19)	0.0815 (18)	0.0584 (14)	0.0061 (15)	0.0256 (13)	0.0259 (13)
N1	0.0381 (8)	0.0537 (10)	0.0452 (9)	0.0135 (7)	0.0145 (7)	−0.0059 (8)
N2	0.0437 (9)	0.0529 (10)	0.0486 (10)	0.0029 (8)	0.0204 (8)	0.0125 (9)
O1	0.0699 (11)	0.1304 (18)	0.0740 (12)	0.0046 (11)	0.0447 (9)	−0.0371 (11)
O2	0.0559 (9)	0.0570 (9)	0.0707 (10)	−0.0050 (7)	0.0215 (8)	−0.0227 (8)
O3	0.0320 (6)	0.0555 (8)	0.0393 (7)	−0.0012 (5)	0.0093 (5)	0.0098 (6)
O4	0.0311 (6)	0.0563 (8)	0.0458 (7)	−0.0048 (5)	0.0170 (5)	0.0100 (6)
O5	0.1094 (15)	0.0963 (14)	0.0725 (11)	0.0649 (12)	0.0511 (11)	0.0296 (10)
O6	0.0695 (10)	0.0642 (10)	0.0476 (8)	0.0214 (8)	0.0315 (7)	0.0034 (7)

Geometric parameters (Å, º) top

C1—C2	1.380 (2)	C9—C10	1.362 (3)
C1—C6	1.391 (2)	C9—H9	0.9300
C1—N1	1.462 (2)	C10—C11	1.377 (3)
C2—C3	1.373 (3)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.383 (3)
C3—C4	1.377 (3)	C11—C14	1.497 (3)
C3—H3	0.9300	C12—C13	1.359 (3)
C4—C5	1.392 (3)	C12—H12	0.9300
C4—H4	0.9300	C13—N2	1.327 (3)
C5—C6	1.387 (2)	C13—H13	0.9300
C5—C7	1.503 (2)	C14—H14A	0.9600
C6—C8	1.515 (2)	C14—H14B	0.9600
C7—O5	1.205 (2)	C14—H14C	0.9600
C7—O6	1.273 (2)	N1—O2	1.216 (2)
C8—O4	1.2350 (19)	N1—O1	1.222 (2)
C8—O3	1.260 (2)	N2—H2A	0.86 (3)
C9—N2	1.330 (3)	O6—H6	0.842 (10)

C2—C1—C6	122.63 (17)	C10—C9—H9	120.1
C2—C1—N1	117.77 (15)	C9—C10—C11	120.56 (19)
C6—C1—N1	119.59 (15)	C9—C10—H10	119.7
C3—C2—C1	118.66 (16)	C11—C10—H10	119.7
C3—C2—H2	120.7	C10—C11—C12	117.50 (19)
C1—C2—H2	120.7	C10—C11—C14	121.2 (2)
C2—C3—C4	120.55 (17)	C12—C11—C14	121.3 (2)
C2—C3—H3	119.7	C13—C12—C11	120.2 (2)
C4—C3—H3	119.7	C13—C12—H12	119.9
C3—C4—C5	120.14 (18)	C11—C12—H12	119.9
C3—C4—H4	119.9	N2—C13—C12	120.4 (2)
C5—C4—H4	119.9	N2—C13—H13	119.8
C6—C5—C4	120.57 (15)	C12—C13—H13	119.8
C6—C5—C7	119.04 (15)	C11—C14—H14A	109.5
C4—C5—C7	120.26 (16)	C11—C14—H14B	109.5
C5—C6—C1	117.42 (15)	H14A—C14—H14B	109.5
C5—C6—C8	118.83 (13)	C11—C14—H14C	109.5
C1—C6—C8	123.64 (15)	H14A—C14—H14C	109.5
O5—C7—O6	124.05 (17)	H14B—C14—H14C	109.5
O5—C7—C5	121.33 (17)	O2—N1—O1	123.59 (18)
O6—C7—C5	114.54 (16)	O2—N1—C1	118.63 (15)
O4—C8—O3	124.97 (15)	O1—N1—C1	117.77 (18)
O4—C8—C6	118.29 (14)	C13—N2—C9	121.48 (19)
O3—C8—C6	116.68 (13)	C13—N2—H2A	120.1 (17)
N2—C9—C10	119.90 (19)	C9—N2—H2A	118.4 (17)
N2—C9—H9	120.1	C7—O6—H6	109 (2)

C6—C1—C2—C3	1.4 (3)	C4—C5—C7—O6	−71.7 (2)
N1—C1—C2—C3	−179.43 (17)	C5—C6—C8—O4	−72.1 (2)
C1—C2—C3—C4	−0.6 (3)	C1—C6—C8—O4	111.72 (19)
C2—C3—C4—C5	−0.5 (3)	C5—C6—C8—O3	105.15 (18)
C3—C4—C5—C6	0.9 (3)	C1—C6—C8—O3	−71.0 (2)
C3—C4—C5—C7	−175.09 (18)	N2—C9—C10—C11	−0.4 (3)
C4—C5—C6—C1	−0.1 (2)	C9—C10—C11—C12	1.0 (3)
C7—C5—C6—C1	175.92 (15)	C9—C10—C11—C14	−178.3 (2)
C4—C5—C6—C8	−176.47 (16)	C10—C11—C12—C13	−0.2 (3)
C7—C5—C6—C8	−0.5 (2)	C14—C11—C12—C13	179.1 (2)
C2—C1—C6—C5	−1.1 (3)	C11—C12—C13—N2	−1.1 (4)
N1—C1—C6—C5	179.78 (15)	C2—C1—N1—O2	153.77 (18)
C2—C1—C6—C8	175.13 (16)	C6—C1—N1—O2	−27.0 (2)
N1—C1—C6—C8	−4.0 (2)	C2—C1—N1—O1	−26.9 (3)
C6—C5—C7—O5	−64.6 (3)	C6—C1—N1—O1	152.23 (19)
C4—C5—C7—O5	111.4 (2)	C12—C13—N2—C9	1.8 (3)
C6—C5—C7—O6	112.27 (19)	C10—C9—N2—C13	−1.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4	0.86 (3)	1.87 (3)	2.699 (2)	160 (2)
O6—H6···O3ⁱ	0.84 (1)	1.65 (1)	2.484 (2)	170 (3)
C13—H13···O6	0.93	2.44	3.219 (3)	141
C2—H2···O4ⁱⁱ	0.93	2.36	3.171 (3)	145
C10—H10···O3ⁱⁱⁱ	0.93	2.54	3.191 (3)	127

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

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
Li, Z.-S. & Chai, J.-S. (2007). Acta Cryst. E63, o2857–o2859. Web of Science CSD CrossRef IUCr Journals 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. (2016). IUCrData, 1, x160817. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.