organic compounds
2-Methylpyridinium 2-carboxy-6-nitrobenzoate
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
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 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).
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 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].
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 .
details are summarized in Table 2
|
Structural data
CCDC reference: 1491386
https://doi.org/10.1107/S2414314616011044/is4010sup1.cif
contains datablocks I, global. DOI: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
Data collection: APEX2 (Bruker, 2004); cell
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).C6H8N+·C8H4NO6− | F(000) = 632 |
Mr = 304.26 | Dx = 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 |
Bruker Kappa APEXII CCD diffractometer | 4541 independent reflections |
Radiation source: fine-focus sealed tube | 3030 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω and φ scan | θmax = 31.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −18→19 |
Tmin = 0.970, Tmax = 0.979 | k = −20→20 |
30283 measured reflections | l = −10→10 |
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(Fo2) + (0.0726P)2 + 0.3878P] where P = (Fo2 + 2Fc2)/3 |
4541 reflections | (Δ/σ)max < 0.001 |
207 parameters | Δρmax = 0.31 e Å−3 |
2 restraints | Δρmin = −0.27 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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···O4iv | 0.93 | 2.50 | 3.189 (2) | 131 |
C11—H11···O1v | 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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