organic compounds
4-Nitroanilinium p-toluenesulfonate
aDepartment of Physics, MNM Jain Engineering College, Chennai 600 097, India, bDepartment of Physics, Presidency College, Chennai 600 005, India, and cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, mohan66@hotmail.com
In the cation of the title salt, C6H7N2O2+·C7H7O3S−, the benzene ring makes a dihedral angle of 10.2 (2)° with the nitro group. In the crystal, the cations and anions are linked by weak N—H⋯O hydrogen bonds, forming a layer parallel to the ac plane. A weak C—H⋯O interaction and π–π interactions [centroid–centroid distances of 3.738 (3) and 3.748 (3) Å] also observed within the layer.
Related literature
For related structures of 4-toluenesulfonate salts, see: Koshima et al. (2004); Biradha & Mahata (2005). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
|
Refinement
|
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
https://doi.org/10.1107/S1600536812040664/is5199sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040664/is5199Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812040664/is5199Isup3.cml
The title compound was formed from a mixture of 4-nitroaniline (2.15 g, 1 mmol) and p-toluenesulfonic acid (2.52 g, 1 mmol) in ethanol, which was stirred two hours at room temperature, giving a clear solution. After slow evaporation of ethanol for few days, single crystals suitable for X-ray diffraction were obtained.
H atoms were positioned geometrically and refined using riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3, and N—H = 0.89 Å and Uiso(H) = 1.5Ueq(N).
The π–π interactions. [Cg1···Cg2 (x, y, 1 + z) distance of 3.748 (3) Å; Cg2···Cg1 (x, y, -1 + z) distance of 3.748 (3) Å; Cg1···Cg2 (1/2 + x, 1/2 - y, 1/2 + z) distance of 3.738 (3) Å; Cg1 and Cg2 are the centroids of the rings (C1–C6) and (C8–C13), respectively.]
of the title compound (Fig. 1) contains one C6H7N2O2+ cation and one C7H7O3S- anion. The bond lengths and angles in both anion and cation are within normal range (Allen et al., 1987) and those in the anion are comparable to those in other 4-toluenesulfonate salts (Koshima et al., 2004; Biradha & Mahata, 2005). The exhibit weak intermolecular N—H···O and C—H···O hydrogen bonds (Table 1 & Fig. 2) andFor related structures of 4-toluenesulfonate salts, see: Koshima et al. (2004); Biradha & Mahata (2005). For bond-length data, see: Allen et al. (1987).
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).C6H7N2O2+·C7H7O3S− | F(000) = 648 |
Mr = 310.32 | Dx = 1.471 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4052 reflections |
a = 6.216 (5) Å | θ = 1.8–28.3° |
b = 30.674 (4) Å | µ = 0.26 mm−1 |
c = 7.405 (5) Å | T = 295 K |
β = 97.048 (5)° | Block, colourless |
V = 1401.2 (15) Å3 | 0.30 × 0.24 × 0.20 mm |
Z = 4 |
Bruker Kappa APEXII diffractometer | 3509 independent reflections |
Radiation source: fine-focus sealed tube | 3232 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω and φ scans | θmax = 28.4°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.928, Tmax = 0.951 | k = −41→35 |
13942 measured reflections | l = −9→8 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.22 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.984P] where P = (Fo2 + 2Fc2)/3 |
3509 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C6H7N2O2+·C7H7O3S− | V = 1401.2 (15) Å3 |
Mr = 310.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.216 (5) Å | µ = 0.26 mm−1 |
b = 30.674 (4) Å | T = 295 K |
c = 7.405 (5) Å | 0.30 × 0.24 × 0.20 mm |
β = 97.048 (5)° |
Bruker Kappa APEXII diffractometer | 3509 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3232 reflections with I > 2σ(I) |
Tmin = 0.928, Tmax = 0.951 | Rint = 0.024 |
13942 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.22 | Δρmax = 0.28 e Å−3 |
3509 reflections | Δρmin = −0.54 e Å−3 |
192 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. |
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 | 0.4464 (3) | 0.15687 (6) | 1.0932 (3) | 0.0291 (4) | |
C2 | 0.3478 (4) | 0.11695 (7) | 1.0557 (3) | 0.0413 (5) | |
H2 | 0.2032 | 0.1156 | 1.0056 | 0.050* | |
C3 | 0.4649 (5) | 0.07893 (8) | 1.0928 (4) | 0.0526 (6) | |
H3 | 0.3974 | 0.0522 | 1.0676 | 0.063* | |
C4 | 0.6802 (5) | 0.07991 (9) | 1.1666 (4) | 0.0513 (6) | |
C5 | 0.7754 (4) | 0.11997 (9) | 1.2045 (4) | 0.0508 (6) | |
H5 | 0.9198 | 0.1212 | 1.2550 | 0.061* | |
C6 | 0.6614 (3) | 0.15854 (8) | 1.1694 (3) | 0.0410 (5) | |
H6 | 0.7286 | 0.1852 | 1.1966 | 0.049* | |
C7 | 0.8092 (6) | 0.03827 (11) | 1.2035 (5) | 0.0829 (11) | |
H7A | 0.8506 | 0.0272 | 1.0914 | 0.124* | |
H7B | 0.7220 | 0.0170 | 1.2558 | 0.124* | |
H7C | 0.9369 | 0.0442 | 1.2866 | 0.124* | |
C8 | 0.4640 (3) | 0.17612 (6) | 0.6035 (2) | 0.0287 (4) | |
C9 | 0.3447 (4) | 0.13903 (8) | 0.5530 (3) | 0.0415 (5) | |
H9 | 0.2015 | 0.1413 | 0.5002 | 0.050* | |
C10 | 0.4402 (4) | 0.09860 (8) | 0.5817 (4) | 0.0480 (6) | |
H10 | 0.3627 | 0.0732 | 0.5504 | 0.058* | |
C11 | 0.6539 (4) | 0.09694 (7) | 0.6584 (3) | 0.0411 (5) | |
C12 | 0.7739 (4) | 0.13364 (7) | 0.7077 (3) | 0.0400 (5) | |
H12 | 0.9177 | 0.1313 | 0.7590 | 0.048* | |
C13 | 0.6768 (3) | 0.17402 (7) | 0.6797 (3) | 0.0345 (4) | |
H13 | 0.7543 | 0.1994 | 0.7118 | 0.041* | |
N2 | 0.3582 (3) | 0.21852 (6) | 0.5788 (2) | 0.0328 (4) | |
H14A | 0.4535 | 0.2395 | 0.6133 | 0.049* | |
H14B | 0.2490 | 0.2198 | 0.6459 | 0.049* | |
H14C | 0.3074 | 0.2221 | 0.4620 | 0.049* | |
N1 | 0.7608 (5) | 0.05441 (7) | 0.6924 (4) | 0.0669 (7) | |
O1 | 0.4582 (3) | 0.23868 (5) | 1.0129 (3) | 0.0461 (4) | |
O2 | 0.1910 (3) | 0.21560 (5) | 1.20530 (19) | 0.0384 (3) | |
O3 | 0.1435 (2) | 0.19798 (5) | 0.8876 (2) | 0.0379 (3) | |
O4 | 0.9550 (4) | 0.05402 (8) | 0.7374 (5) | 0.1119 (12) | |
O5 | 0.6501 (5) | 0.02194 (7) | 0.6748 (5) | 0.1009 (10) | |
S1 | 0.30084 (7) | 0.205912 (15) | 1.04561 (6) | 0.02737 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0279 (9) | 0.0332 (9) | 0.0263 (8) | 0.0032 (7) | 0.0039 (7) | 0.0001 (7) |
C2 | 0.0390 (11) | 0.0364 (11) | 0.0463 (12) | −0.0012 (9) | −0.0033 (9) | −0.0008 (9) |
C3 | 0.0632 (16) | 0.0345 (11) | 0.0586 (15) | 0.0043 (11) | 0.0014 (12) | −0.0016 (10) |
C4 | 0.0590 (15) | 0.0487 (14) | 0.0465 (13) | 0.0220 (11) | 0.0077 (11) | 0.0053 (11) |
C5 | 0.0343 (11) | 0.0656 (16) | 0.0509 (14) | 0.0147 (11) | −0.0004 (10) | 0.0083 (12) |
C6 | 0.0308 (10) | 0.0471 (12) | 0.0436 (12) | −0.0005 (9) | −0.0018 (9) | 0.0015 (9) |
C7 | 0.091 (3) | 0.066 (2) | 0.091 (3) | 0.0408 (19) | 0.009 (2) | 0.0157 (18) |
C8 | 0.0280 (9) | 0.0348 (9) | 0.0230 (8) | 0.0016 (7) | 0.0020 (7) | 0.0026 (7) |
C9 | 0.0308 (10) | 0.0482 (12) | 0.0434 (12) | −0.0059 (9) | −0.0039 (9) | −0.0025 (10) |
C10 | 0.0478 (13) | 0.0388 (12) | 0.0562 (14) | −0.0112 (10) | 0.0016 (11) | −0.0054 (10) |
C11 | 0.0472 (12) | 0.0325 (10) | 0.0434 (12) | 0.0047 (9) | 0.0053 (10) | 0.0030 (9) |
C12 | 0.0336 (10) | 0.0402 (11) | 0.0444 (12) | 0.0040 (8) | −0.0032 (9) | 0.0009 (9) |
C13 | 0.0300 (9) | 0.0341 (10) | 0.0374 (10) | −0.0007 (8) | −0.0041 (8) | −0.0003 (8) |
N2 | 0.0288 (8) | 0.0389 (9) | 0.0303 (8) | 0.0044 (7) | 0.0026 (6) | 0.0028 (7) |
N1 | 0.0780 (18) | 0.0361 (11) | 0.0860 (19) | 0.0084 (11) | 0.0073 (14) | 0.0039 (11) |
O1 | 0.0391 (8) | 0.0369 (8) | 0.0628 (11) | −0.0085 (6) | 0.0081 (7) | 0.0031 (7) |
O2 | 0.0421 (8) | 0.0455 (8) | 0.0283 (7) | 0.0105 (6) | 0.0072 (6) | −0.0024 (6) |
O3 | 0.0338 (7) | 0.0469 (8) | 0.0307 (7) | 0.0050 (6) | −0.0053 (6) | 0.0016 (6) |
O4 | 0.0718 (17) | 0.0540 (14) | 0.203 (4) | 0.0273 (12) | −0.0121 (19) | 0.0111 (17) |
O5 | 0.107 (2) | 0.0358 (11) | 0.156 (3) | −0.0028 (12) | 0.0016 (19) | 0.0068 (14) |
S1 | 0.0253 (2) | 0.0303 (2) | 0.0264 (2) | −0.00042 (16) | 0.00236 (16) | −0.00106 (16) |
C1—C2 | 1.382 (3) | C9—C10 | 1.380 (3) |
C1—C6 | 1.387 (3) | C9—H9 | 0.9300 |
C1—S1 | 1.768 (2) | C10—C11 | 1.380 (4) |
C2—C3 | 1.384 (3) | C10—H10 | 0.9300 |
C2—H2 | 0.9300 | C11—C12 | 1.375 (3) |
C3—C4 | 1.383 (4) | C11—N1 | 1.472 (3) |
C3—H3 | 0.9300 | C12—C13 | 1.382 (3) |
C4—C5 | 1.377 (4) | C12—H12 | 0.9300 |
C4—C7 | 1.515 (4) | C13—H13 | 0.9300 |
C5—C6 | 1.387 (3) | N2—H14A | 0.8900 |
C5—H5 | 0.9300 | N2—H14B | 0.8900 |
C6—H6 | 0.9300 | N2—H14C | 0.8900 |
C7—H7A | 0.9600 | N1—O5 | 1.209 (3) |
C7—H7B | 0.9600 | N1—O4 | 1.212 (4) |
C7—H7C | 0.9600 | O1—S1 | 1.4436 (16) |
C8—C13 | 1.374 (3) | O2—S1 | 1.4665 (16) |
C8—C9 | 1.385 (3) | O3—S1 | 1.4507 (16) |
C8—N2 | 1.459 (2) | ||
C2—C1—C6 | 119.73 (19) | C8—C9—H9 | 120.3 |
C2—C1—S1 | 120.68 (16) | C9—C10—C11 | 118.1 (2) |
C6—C1—S1 | 119.59 (16) | C9—C10—H10 | 121.0 |
C1—C2—C3 | 119.8 (2) | C11—C10—H10 | 121.0 |
C1—C2—H2 | 120.1 | C12—C11—C10 | 122.9 (2) |
C3—C2—H2 | 120.1 | C12—C11—N1 | 117.5 (2) |
C4—C3—C2 | 121.3 (2) | C10—C11—N1 | 119.7 (2) |
C4—C3—H3 | 119.3 | C11—C12—C13 | 118.8 (2) |
C2—C3—H3 | 119.3 | C11—C12—H12 | 120.6 |
C5—C4—C3 | 118.1 (2) | C13—C12—H12 | 120.6 |
C5—C4—C7 | 120.7 (3) | C8—C13—C12 | 118.96 (19) |
C3—C4—C7 | 121.2 (3) | C8—C13—H13 | 120.5 |
C4—C5—C6 | 121.7 (2) | C12—C13—H13 | 120.5 |
C4—C5—H5 | 119.1 | C8—N2—H14A | 109.5 |
C6—C5—H5 | 119.1 | C8—N2—H14B | 109.5 |
C1—C6—C5 | 119.3 (2) | H14A—N2—H14B | 109.5 |
C1—C6—H6 | 120.3 | C8—N2—H14C | 109.5 |
C5—C6—H6 | 120.3 | H14A—N2—H14C | 109.5 |
C4—C7—H7A | 109.5 | H14B—N2—H14C | 109.5 |
C4—C7—H7B | 109.5 | O5—N1—O4 | 123.8 (3) |
H7A—C7—H7B | 109.5 | O5—N1—C11 | 118.2 (3) |
C4—C7—H7C | 109.5 | O4—N1—C11 | 118.0 (2) |
H7A—C7—H7C | 109.5 | O1—S1—O3 | 112.65 (11) |
H7B—C7—H7C | 109.5 | O1—S1—O2 | 112.71 (10) |
C13—C8—C9 | 121.95 (19) | O3—S1—O2 | 110.50 (11) |
C13—C8—N2 | 119.34 (17) | O1—S1—C1 | 106.57 (10) |
C9—C8—N2 | 118.70 (18) | O3—S1—C1 | 107.22 (9) |
C10—C9—C8 | 119.4 (2) | O2—S1—C1 | 106.79 (9) |
C10—C9—H9 | 120.3 | ||
C6—C1—C2—C3 | −0.6 (3) | C10—C11—C12—C13 | 0.0 (4) |
S1—C1—C2—C3 | 179.55 (19) | N1—C11—C12—C13 | −179.1 (2) |
C1—C2—C3—C4 | −0.2 (4) | C9—C8—C13—C12 | −0.5 (3) |
C2—C3—C4—C5 | 0.8 (4) | N2—C8—C13—C12 | 178.06 (18) |
C2—C3—C4—C7 | −178.8 (3) | C11—C12—C13—C8 | 0.0 (3) |
C3—C4—C5—C6 | −0.5 (4) | C12—C11—N1—O5 | 169.4 (3) |
C7—C4—C5—C6 | 179.0 (3) | C10—C11—N1—O5 | −9.8 (4) |
C2—C1—C6—C5 | 0.8 (3) | C12—C11—N1—O4 | −10.3 (4) |
S1—C1—C6—C5 | −179.28 (18) | C10—C11—N1—O4 | 170.6 (3) |
C4—C5—C6—C1 | −0.3 (4) | C2—C1—S1—O1 | −152.38 (18) |
C13—C8—C9—C10 | 0.9 (3) | C6—C1—S1—O1 | 27.7 (2) |
N2—C8—C9—C10 | −177.6 (2) | C2—C1—S1—O3 | −31.5 (2) |
C8—C9—C10—C11 | −0.8 (4) | C6—C1—S1—O3 | 148.59 (17) |
C9—C10—C11—C12 | 0.4 (4) | C2—C1—S1—O2 | 86.92 (19) |
C9—C10—C11—N1 | 179.5 (2) | C6—C1—S1—O2 | −92.96 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H14B···O3 | 0.89 | 2.09 | 2.856 (3) | 144 |
N2—H14A···O2i | 0.89 | 2.07 | 2.961 (3) | 175 |
N2—H14B···O1ii | 0.89 | 2.33 | 2.801 (3) | 113 |
N2—H14C···O2iii | 0.89 | 1.96 | 2.834 (3) | 167 |
C12—H12···O3iv | 0.93 | 2.59 | 3.193 (3) | 123 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, y, z−1; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C6H7N2O2+·C7H7O3S− |
Mr | 310.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 6.216 (5), 30.674 (4), 7.405 (5) |
β (°) | 97.048 (5) |
V (Å3) | 1401.2 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.30 × 0.24 × 0.20 |
Data collection | |
Diffractometer | Bruker Kappa APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.928, 0.951 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13942, 3509, 3232 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.134, 1.22 |
No. of reflections | 3509 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.54 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H14B···O3 | 0.89 | 2.09 | 2.856 (3) | 144 |
N2—H14A···O2i | 0.89 | 2.07 | 2.961 (3) | 175 |
N2—H14B···O1ii | 0.89 | 2.33 | 2.801 (3) | 113 |
N2—H14C···O2iii | 0.89 | 1.96 | 2.834 (3) | 167 |
C12—H12···O3iv | 0.93 | 2.59 | 3.193 (3) | 123 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, y, z−1; (iv) x+1, y, z. |
Acknowledgements
The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Biradha, K. & Mahata, G. (2005). Cryst. Growth Des. 5, 49–51. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Koshima, H., Miyamoto, H., Yagi, I. & Uosaki, K. (2004). Cryst. Growth Des. 4, 807–811. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany. 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
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.
The asymmetric unit of the title compound (Fig. 1) contains one C6H7N2O2+ cation and one C7H7O3S- anion. The bond lengths and angles in both anion and cation are within normal range (Allen et al., 1987) and those in the anion are comparable to those in other 4-toluenesulfonate salts (Koshima et al., 2004; Biradha & Mahata, 2005). The crystal structure exhibit weak intermolecular N—H···O and C—H···O hydrogen bonds (Table 1 & Fig. 2) and π–π interactions. [Cg1···Cg2 (x, y, 1 + z) distance of 3.748 (3) Å; Cg2···Cg1 (x, y, -1 + z) distance of 3.748 (3) Å; Cg1···Cg2 (1/2 + x, 1/2 - y, 1/2 + z) distance of 3.738 (3) Å; Cg1 and Cg2 are the centroids of the rings (C1–C6) and (C8–C13), respectively.]