organic compounds
2-Carboxylatopyridinium–4-nitrophenol (1/1)
aDepartment of Physics, Presidency College, Chennai 600 005, India, and bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, srkanagadurai@yahoo.co.in
In the title 1:1 adduct, C6H5NO3·C6H5NO2, both molecules are almost planar (r.m.s. deviations for the non-H atoms = 0.027 and 0.023 Å for 4-nitrophenol and 2-carboxylatopyridinium, respectively). The pyridine molecule crystallizes as a zwitterion (nominal proton transfer from the carboxylic acid group to the N atom in the ring). In the crystal, inversion dimers of the linked by pairs of N—H⋯O hydrogen bonds generate R22(10) loops; two 4-nitrophenol molecules link to the dimer by O—H⋯O hydrogen bonds, generating a four-molecule aggregate. These are linked by C—H⋯O interactions, forming a three-dimensional network.
CCDC reference: 991427
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; 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.
Supporting information
CCDC reference: 991427
10.1107/S1600536814005650/hb7209sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005650/hb7209Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005650/hb7209Isup3.cml
The title material was synthesized by taking 2-carboxypyridine (1.2331 g) and p-nitrophenol (1.3911 g) in an equimolar ratio. 2-carboxypyridine was added gradually in the
of p-nitrophenol using methanol with continuous stirring for one hour and white precipitate was obtained. Then, the precipitate was dissolved using the same solvent. The prepared solution was allowed for slow evaporation at room temperature to yield colourless blocks after 10 days.H atoms for Caromatic were positioned geometrically and refined using riding model, with C-H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms bounded to N and O atoms were fixed from the fourier map and refined freely with the distance restraints: 0.82 (1)Å for O—H and 0.86 (1)Å for N—H.
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).Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms. | |
Fig. 2. The packing of (I), viewed down a axis. Intermolecular Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted. |
C6H5NO3·C6H5NO2 | Z = 2 |
Mr = 262.22 | F(000) = 272 |
Triclinic, P1 | Dx = 1.492 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1743 (4) Å | Cell parameters from 4728 reflections |
b = 7.0512 (3) Å | θ = 2.9–27.7° |
c = 14.2222 (8) Å | µ = 0.12 mm−1 |
α = 101.727 (3)° | T = 295 K |
β = 92.191 (2)° | Block, colourless |
γ = 104.758 (4)° | 0.32 × 0.24 × 0.20 mm |
V = 583.60 (6) Å3 |
Bruker Kappa APEXII CCD diffractometer | 3486 independent reflections |
Radiation source: fine-focus sealed tube | 2327 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω and ϕ scan | θmax = 30.4°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −8→8 |
Tmin = 0.963, Tmax = 0.977 | k = −10→9 |
13952 measured reflections | l = −17→20 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0602P)2 + 0.0686P] where P = (Fo2 + 2Fc2)/3 |
3486 reflections | (Δ/σ)max < 0.001 |
180 parameters | Δρmax = 0.14 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
C6H5NO3·C6H5NO2 | γ = 104.758 (4)° |
Mr = 262.22 | V = 583.60 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.1743 (4) Å | Mo Kα radiation |
b = 7.0512 (3) Å | µ = 0.12 mm−1 |
c = 14.2222 (8) Å | T = 295 K |
α = 101.727 (3)° | 0.32 × 0.24 × 0.20 mm |
β = 92.191 (2)° |
Bruker Kappa APEXII CCD diffractometer | 3486 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2327 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.977 | Rint = 0.028 |
13952 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 2 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.14 e Å−3 |
3486 reflections | Δρmin = −0.24 e Å−3 |
180 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3865 (2) | 0.38442 (18) | 0.19001 (9) | 0.0451 (3) | |
C2 | 0.2381 (2) | 0.2646 (2) | 0.11160 (10) | 0.0498 (3) | |
H2A | 0.0853 | 0.2230 | 0.1187 | 0.060* | |
C3 | 0.3152 (2) | 0.20783 (19) | 0.02422 (9) | 0.0474 (3) | |
H3 | 0.2155 | 0.1288 | −0.0281 | 0.057* | |
C4 | 0.5424 (2) | 0.26918 (17) | 0.01464 (9) | 0.0414 (3) | |
C5 | 0.6929 (2) | 0.38640 (18) | 0.09160 (9) | 0.0459 (3) | |
H5 | 0.8455 | 0.4274 | 0.0840 | 0.055* | |
C6 | 0.6153 (2) | 0.44171 (18) | 0.17923 (9) | 0.0474 (3) | |
H6 | 0.7161 | 0.5179 | 0.2317 | 0.057* | |
C7 | 0.1820 (2) | 0.19479 (19) | 0.45093 (8) | 0.0429 (3) | |
C8 | −0.1051 (2) | 0.1161 (2) | 0.32506 (10) | 0.0512 (3) | |
H8 | −0.2284 | 0.1462 | 0.2981 | 0.061* | |
C9 | −0.0352 (3) | −0.0443 (2) | 0.27958 (10) | 0.0550 (3) | |
H9 | −0.1090 | −0.1236 | 0.2211 | 0.066* | |
C10 | 0.1445 (3) | −0.0868 (2) | 0.32101 (10) | 0.0589 (4) | |
H10 | 0.1930 | −0.1968 | 0.2912 | 0.071* | |
C11 | 0.2543 (3) | 0.0336 (2) | 0.40725 (9) | 0.0529 (3) | |
H11 | 0.3772 | 0.0051 | 0.4356 | 0.063* | |
C12 | 0.2879 (2) | 0.3378 (2) | 0.54544 (9) | 0.0477 (3) | |
N1 | 0.6252 (2) | 0.21159 (16) | −0.07787 (8) | 0.0501 (3) | |
N2 | 0.00405 (19) | 0.22997 (16) | 0.40848 (7) | 0.0452 (3) | |
O1 | 0.29906 (19) | 0.44091 (17) | 0.27221 (8) | 0.0619 (3) | |
O2 | 0.4895 (2) | 0.11237 (18) | −0.14600 (7) | 0.0689 (3) | |
O3 | 0.82814 (19) | 0.26305 (17) | −0.08431 (8) | 0.0714 (3) | |
O4 | 0.2047 (2) | 0.47818 (17) | 0.57395 (7) | 0.0701 (3) | |
O5 | 0.44519 (18) | 0.29715 (16) | 0.58610 (7) | 0.0666 (3) | |
H2 | −0.039 (3) | 0.3351 (18) | 0.4342 (11) | 0.066 (5)* | |
H1 | 0.400 (3) | 0.524 (2) | 0.3119 (12) | 0.085 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0519 (7) | 0.0382 (6) | 0.0449 (6) | 0.0139 (5) | −0.0003 (5) | 0.0071 (5) |
C2 | 0.0394 (6) | 0.0514 (7) | 0.0550 (7) | 0.0101 (5) | −0.0036 (5) | 0.0075 (6) |
C3 | 0.0460 (7) | 0.0433 (6) | 0.0476 (7) | 0.0104 (5) | −0.0116 (5) | 0.0030 (5) |
C4 | 0.0478 (7) | 0.0346 (6) | 0.0427 (6) | 0.0150 (5) | −0.0034 (5) | 0.0066 (5) |
C5 | 0.0404 (6) | 0.0410 (6) | 0.0525 (7) | 0.0091 (5) | −0.0041 (5) | 0.0054 (5) |
C6 | 0.0476 (7) | 0.0409 (6) | 0.0469 (6) | 0.0078 (5) | −0.0091 (5) | 0.0019 (5) |
C7 | 0.0500 (7) | 0.0472 (7) | 0.0334 (5) | 0.0184 (5) | 0.0041 (5) | 0.0067 (5) |
C8 | 0.0550 (8) | 0.0496 (7) | 0.0459 (7) | 0.0160 (6) | −0.0074 (6) | 0.0034 (5) |
C9 | 0.0678 (9) | 0.0471 (7) | 0.0443 (7) | 0.0161 (6) | −0.0051 (6) | −0.0021 (5) |
C10 | 0.0792 (10) | 0.0547 (8) | 0.0458 (7) | 0.0334 (7) | 0.0042 (7) | −0.0016 (6) |
C11 | 0.0617 (8) | 0.0616 (8) | 0.0412 (6) | 0.0335 (7) | 0.0005 (6) | 0.0039 (6) |
C12 | 0.0572 (8) | 0.0530 (7) | 0.0350 (5) | 0.0238 (6) | 0.0008 (5) | 0.0034 (5) |
N1 | 0.0602 (7) | 0.0435 (6) | 0.0477 (6) | 0.0192 (5) | −0.0009 (5) | 0.0071 (5) |
N2 | 0.0544 (6) | 0.0435 (6) | 0.0386 (5) | 0.0206 (5) | −0.0001 (4) | 0.0024 (4) |
O1 | 0.0611 (7) | 0.0658 (7) | 0.0513 (6) | 0.0141 (5) | 0.0066 (5) | −0.0004 (5) |
O2 | 0.0762 (7) | 0.0787 (7) | 0.0460 (6) | 0.0263 (6) | −0.0106 (5) | −0.0033 (5) |
O3 | 0.0627 (7) | 0.0734 (7) | 0.0691 (7) | 0.0119 (6) | 0.0161 (5) | 0.0013 (6) |
O4 | 0.0938 (8) | 0.0667 (7) | 0.0520 (6) | 0.0483 (6) | −0.0173 (5) | −0.0117 (5) |
O5 | 0.0763 (7) | 0.0785 (7) | 0.0471 (5) | 0.0448 (6) | −0.0138 (5) | −0.0082 (5) |
C1—O1 | 1.3363 (16) | C8—N2 | 1.3349 (16) |
C1—C6 | 1.3902 (19) | C8—C9 | 1.3626 (19) |
C1—C2 | 1.3934 (18) | C8—H8 | 0.9300 |
C2—C3 | 1.3679 (19) | C9—C10 | 1.364 (2) |
C2—H2A | 0.9300 | C9—H9 | 0.9300 |
C3—C4 | 1.3796 (18) | C10—C11 | 1.3801 (19) |
C3—H3 | 0.9300 | C10—H10 | 0.9300 |
C4—C5 | 1.3813 (17) | C11—H11 | 0.9300 |
C4—N1 | 1.4482 (17) | C12—O4 | 1.2325 (16) |
C5—C6 | 1.3705 (19) | C12—O5 | 1.2356 (15) |
C5—H5 | 0.9300 | N1—O2 | 1.2222 (15) |
C6—H6 | 0.9300 | N1—O3 | 1.2252 (15) |
C7—N2 | 1.3352 (16) | N2—H2 | 0.866 (9) |
C7—C11 | 1.3676 (18) | O1—H1 | 0.838 (9) |
C7—C12 | 1.5156 (17) | ||
O1—C1—C6 | 123.25 (12) | N2—C8—H8 | 120.1 |
O1—C1—C2 | 117.49 (12) | C9—C8—H8 | 120.1 |
C6—C1—C2 | 119.25 (12) | C8—C9—C10 | 119.09 (13) |
C3—C2—C1 | 120.57 (12) | C8—C9—H9 | 120.5 |
C3—C2—H2A | 119.7 | C10—C9—H9 | 120.5 |
C1—C2—H2A | 119.7 | C9—C10—C11 | 119.88 (13) |
C2—C3—C4 | 119.23 (12) | C9—C10—H10 | 120.1 |
C2—C3—H3 | 120.4 | C11—C10—H10 | 120.1 |
C4—C3—H3 | 120.4 | C7—C11—C10 | 119.84 (13) |
C3—C4—C5 | 121.20 (12) | C7—C11—H11 | 120.1 |
C3—C4—N1 | 119.62 (11) | C10—C11—H11 | 120.1 |
C5—C4—N1 | 119.18 (12) | O4—C12—O5 | 127.49 (12) |
C6—C5—C4 | 119.40 (12) | O4—C12—C7 | 116.64 (11) |
C6—C5—H5 | 120.3 | O5—C12—C7 | 115.84 (11) |
C4—C5—H5 | 120.3 | O2—N1—O3 | 122.83 (12) |
C5—C6—C1 | 120.31 (12) | O2—N1—C4 | 118.51 (12) |
C5—C6—H6 | 119.8 | O3—N1—C4 | 118.65 (11) |
C1—C6—H6 | 119.8 | C8—N2—C7 | 123.02 (11) |
N2—C7—C11 | 118.38 (11) | C8—N2—H2 | 117.9 (11) |
N2—C7—C12 | 116.75 (11) | C7—N2—H2 | 119.0 (11) |
C11—C7—C12 | 124.87 (12) | C1—O1—H1 | 109.5 (14) |
N2—C8—C9 | 119.78 (13) | ||
O1—C1—C2—C3 | 177.46 (13) | C12—C7—C11—C10 | 179.96 (13) |
C6—C1—C2—C3 | −1.60 (19) | C9—C10—C11—C7 | 0.2 (2) |
C1—C2—C3—C4 | 0.5 (2) | N2—C7—C12—O4 | −1.96 (19) |
C2—C3—C4—C5 | 0.09 (19) | C11—C7—C12—O4 | 178.60 (14) |
C2—C3—C4—N1 | −179.33 (11) | N2—C7—C12—O5 | 176.51 (12) |
C3—C4—C5—C6 | 0.42 (19) | C11—C7—C12—O5 | −2.9 (2) |
N1—C4—C5—C6 | 179.84 (11) | C3—C4—N1—O2 | 1.36 (18) |
C4—C5—C6—C1 | −1.53 (19) | C5—C4—N1—O2 | −178.07 (11) |
O1—C1—C6—C5 | −176.89 (12) | C3—C4—N1—O3 | −178.10 (12) |
C2—C1—C6—C5 | 2.11 (19) | C5—C4—N1—O3 | 2.47 (18) |
N2—C8—C9—C10 | 0.7 (2) | C9—C8—N2—C7 | 0.0 (2) |
C8—C9—C10—C11 | −0.8 (2) | C11—C7—N2—C8 | −0.6 (2) |
N2—C7—C11—C10 | 0.5 (2) | C12—C7—N2—C8 | 179.91 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5i | 0.84 (1) | 1.77 (1) | 2.5929 (15) | 165 (2) |
N2—H2···O4ii | 0.87 (1) | 1.88 (1) | 2.6693 (15) | 151 (2) |
C5—H5···O3iii | 0.93 | 2.56 | 3.3570 (17) | 143 |
C9—H9···O2iv | 0.93 | 2.57 | 3.2009 (18) | 126 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+2, −y+1, −z; (iv) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5i | 0.838 (9) | 1.773 (11) | 2.5929 (15) | 165 (2) |
N2—H2···O4ii | 0.866 (9) | 1.880 (12) | 2.6693 (15) | 151 (2) |
C5—H5···O3iii | 0.93 | 2.56 | 3.3570 (17) | 143 |
C9—H9···O2iv | 0.93 | 2.57 | 3.2009 (18) | 126 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+2, −y+1, −z; (iv) −x, −y, −z. |
Acknowledgements
The authors thank the SAIF, IIT, Madras, for the data collection.
References
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Pandi, P., Peramaiyan, G., Akilan, R., Chakkaravarthi, G. & Mohankumar, R. (2012). Acta Cryst. E68, o3081. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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We herin report the crystal structure of (I), (Fig. 1). The bond lengths are comparable with those in a similar structure (Pandi et al., 2012).
The pyridine ring is almost planar, with the maximum deviation of 0.005 (2) Å. The carboxy group is twisted at an angle of 2.9 (1)° with the pyridine ring. The nitro group is oriented at an angle of 1.8 (1)° with the benzene ring. The crystal structure features O—H···O, N—H···O and C—H···O (Fig. 2 & Table 1) interactions to form a three dimensional network.