organic compounds
4-Methylanilinium 3-carboxy-4-hydroxybenzenesulfonate
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
In the title molecular salt, C7H10N+·C7H5O6S−, the anion is deprotonated at the hydroxy O atom of the sulfonate group. In the anion, an intra-ionic O—H⋯O hydrogen bond generates an S(6) graph-set motif. In the crystal, the inter-ionic N—H⋯O and O—H⋯O hydrogen bonds generate an R24(12) ring-set motif, linking the anions and cations into an infinite three-dimensional framework. The also features C—H⋯π and π–π [centroid-to-centroid distance = 3.5946 (11) Å] interactions.
Keywords: crystal structure; molecular salt; hydrogen bonding.
CCDC reference: 1532573
Structure description
Amino derivatives of benzoic acid are of considerable importance because of their use as anti-inflammatory and anti-cancer agents (Congiu et al., 2005). We herein report the synthesis and the of the title molecular salt (Fig. 1). The contains a 4-methylanilinium cation and a 3-carboxy-4-hydroxybenzenesulfonate anion. The geometric parameters are comparable with those of reported similar structures for 4-methylanilinium (Benali-Cherif et al., 2009) and 3-carboxy-4-hydroxybenzenesulfonate (Hemamalini & Fun, 2010). The cation is protonated at the amine atom N1 and the anion is deprotonated at the hydroxy atom O5. The O1—H1⋯O3 hydrogen bond generates an S(6) graph-set motif (Fig. 1) in the anion.
A pair of inter-ionic N1—H1A⋯O6i and N1—H1B⋯O4ii hydrogen bonds (for symmetry codes, see Table 1) generate an R24(12) ring-set motif (Fig. 2). In the the inter-ionic N—H⋯O and O—H⋯O hydrogen bonds (Table 1 and Fig. 3) link the adjacent anions and cations into an infinite three-dimensional framework. The is also influenced by weak C—H⋯π (Table 1) and π–π [Cg1⋯Cg1(1 − x,1 − y,1 − z) = 3.5946 (11) Å; Cg1 is the centroid of the C8–C13 ring] interactions.
Synthesis and crystallization
The title compound was synthesized from p-methyl aniline and 2-hydroxy-5-sulfobenzoic acid in a stoichiometric ratio and dissolved in a mixed solvent of water and acetone at ambient temperature. The solution was filtered and allowed to evaporate and yielded crystals suitable for X-ray diffraction after two weeks.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1532573
https://doi.org/10.1107/S2414314617002541/bt4043sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002541/bt4043Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617002541/bt4043Isup3.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: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).C7H10N+·C7H5O6S− | F(000) = 680 |
Mr = 325.33 | Dx = 1.489 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5114 (8) Å | Cell parameters from 8665 reflections |
b = 12.3080 (11) Å | θ = 2.3–31.5° |
c = 12.5537 (11) Å | µ = 0.25 mm−1 |
β = 98.962 (3)° | T = 295 K |
V = 1451.7 (2) Å3 | Block, colourless |
Z = 4 | 0.24 × 0.20 × 0.18 mm |
Bruker Kappa APEXII CCD Diffractometer | 3474 reflections with I > 2σ(I) |
ω and φ scan | Rint = 0.040 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | θmax = 31.6°, θmin = 2.3° |
Tmin = 0.609, Tmax = 0.746 | h = −14→13 |
26625 measured reflections | k = −17→17 |
4730 independent reflections | l = −18→18 |
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)] = 0.051 | w = 1/[σ2(Fo2) + (0.0514P)2 + 0.973P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.142 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.40 e Å−3 |
4730 reflections | Δρmin = −0.76 e Å−3 |
208 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2016), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.030 (2) |
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 | 0.41299 (18) | 1.08104 (15) | 0.28078 (14) | 0.0309 (4) | |
C2 | 0.3200 (2) | 1.16342 (16) | 0.29414 (16) | 0.0352 (4) | |
H2 | 0.311647 | 1.223576 | 0.248763 | 0.042* | |
C3 | 0.2388 (2) | 1.15537 (17) | 0.37648 (16) | 0.0387 (4) | |
H3 | 0.175095 | 1.210620 | 0.385736 | 0.046* | |
C4 | 0.2507 (2) | 1.06667 (18) | 0.44518 (15) | 0.0385 (4) | |
C5 | 0.3410 (2) | 0.98278 (19) | 0.42574 (17) | 0.0438 (5) | |
H5 | 0.346720 | 0.920894 | 0.468705 | 0.053* | |
C6 | 0.4227 (2) | 0.98922 (18) | 0.34377 (17) | 0.0403 (4) | |
H6 | 0.482924 | 0.932553 | 0.331607 | 0.048* | |
C7 | 0.1721 (3) | 1.0633 (2) | 0.54056 (19) | 0.0593 (7) | |
H7A | 0.230980 | 1.093739 | 0.602444 | 0.089* | |
H7B | 0.149500 | 0.989370 | 0.555340 | 0.089* | |
H7C | 0.085869 | 1.104711 | 0.524619 | 0.089* | |
C8 | 0.36092 (18) | 0.65002 (14) | 0.58334 (13) | 0.0283 (3) | |
C9 | 0.4344 (2) | 0.59570 (16) | 0.67204 (14) | 0.0344 (4) | |
H9 | 0.389513 | 0.581016 | 0.731168 | 0.041* | |
C10 | 0.5734 (2) | 0.56345 (16) | 0.67298 (14) | 0.0357 (4) | |
H10 | 0.621603 | 0.526240 | 0.732126 | 0.043* | |
C11 | 0.64165 (18) | 0.58672 (15) | 0.58512 (14) | 0.0298 (3) | |
C12 | 0.56786 (17) | 0.64118 (13) | 0.49562 (12) | 0.0250 (3) | |
C13 | 0.42673 (17) | 0.67244 (14) | 0.49550 (13) | 0.0264 (3) | |
H13 | 0.377117 | 0.708411 | 0.436115 | 0.032* | |
C14 | 0.63914 (18) | 0.66439 (15) | 0.40202 (14) | 0.0290 (3) | |
N1 | 0.50396 (18) | 1.09139 (15) | 0.19685 (14) | 0.0400 (4) | |
H1A | 0.457317 | 1.127520 | 0.140822 | 0.060* | |
H1B | 0.526763 | 1.025568 | 0.175674 | 0.060* | |
H1C | 0.582911 | 1.127370 | 0.223231 | 0.060* | |
O1 | 0.77811 (15) | 0.55499 (14) | 0.58997 (12) | 0.0447 (4) | |
O2 | 0.55929 (15) | 0.71141 (14) | 0.32111 (11) | 0.0442 (4) | |
O3 | 0.76397 (14) | 0.64117 (14) | 0.40068 (12) | 0.0438 (4) | |
O4 | 0.11033 (19) | 0.60551 (15) | 0.62629 (18) | 0.0701 (6) | |
O5 | 0.1984 (2) | 0.78754 (13) | 0.65703 (13) | 0.0531 (4) | |
O6 | 0.12809 (16) | 0.72387 (15) | 0.47508 (13) | 0.0517 (4) | |
S1 | 0.18523 (5) | 0.69380 (4) | 0.58472 (4) | 0.03677 (15) | |
H1 | 0.804 (3) | 0.576 (2) | 0.5332 (13) | 0.055* | |
H2A | 0.601 (3) | 0.715 (2) | 0.2685 (15) | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0271 (8) | 0.0397 (9) | 0.0268 (8) | −0.0058 (7) | 0.0066 (6) | −0.0079 (7) |
C2 | 0.0398 (10) | 0.0326 (9) | 0.0351 (9) | −0.0034 (7) | 0.0115 (8) | −0.0064 (7) |
C3 | 0.0365 (9) | 0.0413 (10) | 0.0403 (10) | −0.0034 (8) | 0.0121 (8) | −0.0140 (8) |
C4 | 0.0346 (9) | 0.0506 (11) | 0.0315 (9) | −0.0148 (8) | 0.0090 (7) | −0.0103 (8) |
C5 | 0.0491 (12) | 0.0487 (12) | 0.0340 (10) | −0.0033 (9) | 0.0072 (9) | 0.0055 (9) |
C6 | 0.0375 (10) | 0.0463 (11) | 0.0371 (10) | 0.0067 (8) | 0.0059 (8) | −0.0023 (8) |
C7 | 0.0565 (14) | 0.0821 (18) | 0.0453 (13) | −0.0183 (13) | 0.0266 (11) | −0.0090 (12) |
C8 | 0.0302 (8) | 0.0322 (8) | 0.0250 (8) | −0.0026 (7) | 0.0121 (6) | −0.0036 (6) |
C9 | 0.0424 (10) | 0.0411 (10) | 0.0222 (8) | −0.0052 (8) | 0.0122 (7) | 0.0010 (7) |
C10 | 0.0405 (10) | 0.0416 (10) | 0.0243 (8) | −0.0006 (8) | 0.0034 (7) | 0.0076 (7) |
C11 | 0.0285 (8) | 0.0321 (8) | 0.0286 (8) | −0.0014 (7) | 0.0041 (6) | 0.0030 (7) |
C12 | 0.0260 (7) | 0.0284 (8) | 0.0218 (7) | −0.0017 (6) | 0.0077 (6) | −0.0006 (6) |
C13 | 0.0276 (7) | 0.0312 (8) | 0.0216 (7) | 0.0006 (6) | 0.0081 (6) | 0.0013 (6) |
C14 | 0.0271 (7) | 0.0343 (8) | 0.0277 (8) | −0.0008 (6) | 0.0107 (6) | 0.0018 (7) |
N1 | 0.0364 (8) | 0.0490 (10) | 0.0380 (9) | −0.0026 (7) | 0.0170 (7) | −0.0066 (7) |
O1 | 0.0306 (7) | 0.0602 (10) | 0.0437 (8) | 0.0088 (6) | 0.0067 (6) | 0.0175 (7) |
O2 | 0.0345 (7) | 0.0713 (10) | 0.0301 (7) | 0.0101 (7) | 0.0157 (5) | 0.0189 (7) |
O3 | 0.0292 (6) | 0.0624 (10) | 0.0435 (8) | 0.0085 (6) | 0.0170 (6) | 0.0121 (7) |
O4 | 0.0482 (9) | 0.0539 (10) | 0.1196 (17) | −0.0002 (8) | 0.0485 (10) | 0.0197 (11) |
O5 | 0.0716 (11) | 0.0506 (9) | 0.0456 (9) | 0.0087 (8) | 0.0357 (8) | −0.0088 (7) |
O6 | 0.0382 (8) | 0.0744 (11) | 0.0441 (9) | 0.0165 (8) | 0.0111 (6) | −0.0048 (8) |
S1 | 0.0362 (2) | 0.0396 (3) | 0.0400 (3) | 0.00331 (19) | 0.02343 (19) | −0.00040 (19) |
C1—C2 | 1.373 (3) | C9—H9 | 0.9300 |
C1—C6 | 1.374 (3) | C10—C11 | 1.394 (2) |
C1—N1 | 1.469 (2) | C10—H10 | 0.9300 |
C2—C3 | 1.387 (3) | C11—O1 | 1.348 (2) |
C2—H2 | 0.9300 | C11—C12 | 1.400 (2) |
C3—C4 | 1.385 (3) | C12—C13 | 1.396 (2) |
C3—H3 | 0.9300 | C12—C14 | 1.473 (2) |
C4—C5 | 1.389 (3) | C13—H13 | 0.9300 |
C4—C7 | 1.508 (3) | C14—O3 | 1.224 (2) |
C5—C6 | 1.385 (3) | C14—O2 | 1.305 (2) |
C5—H5 | 0.9300 | N1—H1A | 0.8900 |
C6—H6 | 0.9300 | N1—H1B | 0.8900 |
C7—H7A | 0.9600 | N1—H1C | 0.8900 |
C7—H7B | 0.9600 | O1—H1 | 0.829 (10) |
C7—H7C | 0.9600 | O2—H2A | 0.824 (10) |
C8—C13 | 1.378 (2) | O4—S1 | 1.4411 (17) |
C8—C9 | 1.390 (3) | O5—S1 | 1.4612 (16) |
C8—S1 | 1.7585 (17) | O6—S1 | 1.4470 (17) |
C9—C10 | 1.379 (3) | ||
C2—C1—C6 | 121.61 (17) | C9—C10—C11 | 119.87 (17) |
C2—C1—N1 | 119.08 (17) | C9—C10—H10 | 120.1 |
C6—C1—N1 | 119.32 (17) | C11—C10—H10 | 120.1 |
C1—C2—C3 | 118.85 (19) | O1—C11—C10 | 117.93 (16) |
C1—C2—H2 | 120.6 | O1—C11—C12 | 122.28 (15) |
C3—C2—H2 | 120.6 | C10—C11—C12 | 119.78 (16) |
C4—C3—C2 | 121.28 (19) | C13—C12—C11 | 119.65 (14) |
C4—C3—H3 | 119.4 | C13—C12—C14 | 120.50 (15) |
C2—C3—H3 | 119.4 | C11—C12—C14 | 119.84 (15) |
C3—C4—C5 | 118.01 (17) | C8—C13—C12 | 120.03 (16) |
C3—C4—C7 | 120.9 (2) | C8—C13—H13 | 120.0 |
C5—C4—C7 | 121.1 (2) | C12—C13—H13 | 120.0 |
C6—C5—C4 | 121.5 (2) | O3—C14—O2 | 122.76 (15) |
C6—C5—H5 | 119.3 | O3—C14—C12 | 122.26 (16) |
C4—C5—H5 | 119.3 | O2—C14—C12 | 114.99 (14) |
C1—C6—C5 | 118.64 (19) | C1—N1—H1A | 109.5 |
C1—C6—H6 | 120.7 | C1—N1—H1B | 109.5 |
C5—C6—H6 | 120.7 | H1A—N1—H1B | 109.5 |
C4—C7—H7A | 109.5 | C1—N1—H1C | 109.5 |
C4—C7—H7B | 109.5 | H1A—N1—H1C | 109.5 |
H7A—C7—H7B | 109.5 | H1B—N1—H1C | 109.5 |
C4—C7—H7C | 109.5 | C11—O1—H1 | 106.3 (19) |
H7A—C7—H7C | 109.5 | C14—O2—H2A | 110.5 (19) |
H7B—C7—H7C | 109.5 | O4—S1—O6 | 113.81 (13) |
C13—C8—C9 | 120.18 (16) | O4—S1—O5 | 111.70 (11) |
C13—C8—S1 | 119.83 (14) | O6—S1—O5 | 111.85 (10) |
C9—C8—S1 | 119.97 (12) | O4—S1—C8 | 107.26 (10) |
C10—C9—C8 | 120.47 (15) | O6—S1—C8 | 106.60 (8) |
C10—C9—H9 | 119.8 | O5—S1—C8 | 104.98 (10) |
C8—C9—H9 | 119.8 | ||
C6—C1—C2—C3 | 2.9 (3) | O1—C11—C12—C14 | 0.7 (3) |
N1—C1—C2—C3 | −177.26 (17) | C10—C11—C12—C14 | −179.09 (17) |
C1—C2—C3—C4 | 0.4 (3) | C9—C8—C13—C12 | −0.4 (3) |
C2—C3—C4—C5 | −3.4 (3) | S1—C8—C13—C12 | 177.76 (13) |
C2—C3—C4—C7 | 174.4 (2) | C11—C12—C13—C8 | 0.2 (3) |
C3—C4—C5—C6 | 3.3 (3) | C14—C12—C13—C8 | 179.79 (16) |
C7—C4—C5—C6 | −174.5 (2) | C13—C12—C14—O3 | 177.70 (18) |
C2—C1—C6—C5 | −3.0 (3) | C11—C12—C14—O3 | −2.7 (3) |
N1—C1—C6—C5 | 177.11 (18) | C13—C12—C14—O2 | −2.3 (3) |
C4—C5—C6—C1 | −0.1 (3) | C11—C12—C14—O2 | 177.28 (17) |
C13—C8—C9—C10 | −0.2 (3) | C13—C8—S1—O4 | 136.91 (17) |
S1—C8—C9—C10 | −178.34 (15) | C9—C8—S1—O4 | −44.95 (19) |
C8—C9—C10—C11 | 0.9 (3) | C13—C8—S1—O6 | 14.65 (18) |
C9—C10—C11—O1 | 179.15 (18) | C9—C8—S1—O6 | −167.20 (16) |
C9—C10—C11—C12 | −1.0 (3) | C13—C8—S1—O5 | −104.14 (15) |
O1—C11—C12—C13 | −179.73 (17) | C9—C8—S1—O5 | 74.00 (17) |
C10—C11—C12—C13 | 0.5 (3) |
Cg2 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.83 (1) | 1.83 (2) | 2.587 (2) | 150 (3) |
N1—H1A···O6i | 0.89 | 1.95 | 2.837 (3) | 172 |
N1—H1B···O4ii | 0.89 | 1.94 | 2.821 (2) | 169 |
O2—H2A···O5ii | 0.82 (1) | 1.79 (1) | 2.6159 (19) | 176 (3) |
N1—H1C···O3iii | 0.89 | 2.30 | 2.7548 (19) | 112 |
N1—H1C···O5iv | 0.89 | 2.59 | 3.461 (3) | 166 |
C10—H10···Cg2v | 0.93 | 2.66 | 3.549 (2) | 160 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1, −y+2, −z+1; (v) x+1/2, −y+3/2, z+1/2. |
Acknowledgements
The authors acknowledge the SAIF, IIT, Madras, for the data collection.
References
Benali-Cherif, N., Boussekine, H., Boutobba, Z. & Dadda, N. (2009). Acta Cryst. E65, o2744. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Congiu, C., Cocco, M. T., Lilliu, V. & Onnis, V. (2005). J. Med. Chem. 48, 8245–8252. Web of Science CrossRef PubMed CAS Google Scholar
Hemamalini, M. & Fun, H.-K. (2010). Acta Cryst. E66, o2153–o2154. 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
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.