4-Nitro-anilinium p-toluene-sulfonate.

In the cation of the title salt, C(6)H(7)N(2)O(2) (+)·C(7)H(7)O(3)S(-), 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 inter-action and π-π inter-actions [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

C6H7N2O2 +·C7H7O3S−

M = 310.32

Monoclinic,

a = 6.216 (5) Å

b = 30.674 (4) Å

c = 7.405 (5) Å

β = 97.048 (5)°

V = 1401.2 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 295 K

0.30 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.928, T max = 0.951

13942 measured reflections

3509 independent reflections

3232 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.134

S = 1.22

3509 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812040664/is5199sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812040664/is5199Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812040664/is5199Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

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

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) ; (iii) ; (iv) .