4-(4-Amino-phenyl-sulfon-yl)anilinium toluene-4-sulfonate.

In the title p-toluene-sulfonate salt of the drug dapsone, C12H13N2O2S(+)·C7H7O3S(-), the dihedral angle between the two aromatic rings of the dapsone monocation is 70.19 (17)° and those between these rings and that of the p-toluene-sulfonate anion are 72.34 (17) and 46.43 (17)°. All amine and aminium H atoms are involved in inter-molecular N-H⋯O hydrogen-bonding associations with sulfonyl O-atom acceptors as well as one of the sulfone O atoms, giving a three-dimensional structure.

Related literature

For drug applications of dapsone, see: Wilson et al. (1991 ▶). For the structures of dapsone solvates, see: Kus’mina et al. (1981 ▶); Lemmer et al. (2012 ▶). For the structures of adducts and a salt of dapsone, see: Smith & Wermuth (2012a ▶,b ▶, 2013 ▶).

Experimental

Crystal data

C12H13N2O2S+·C7H7O3S−

M = 420.49

Monoclinic,

a = 5.9516 (9) Å

b = 25.147 (3) Å

c = 12.4506 (15) Å

β = 94.908 (11)°

V = 1856.6 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 200 K

0.25 × 0.12 × 0.12 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T min = 0.935, T max = 0.980

6908 measured reflections

3650 independent reflections

2653 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.161

S = 1.02

3650 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.39 e Å−3

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813033023/sj5377sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033023/sj5377Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813033023/sj5377Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H13N2O2S+·C7H7O3S−	F(000) = 880
Mr = 420.49	Dx = 1.504 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1570 reflections
a = 5.9516 (9) Å	θ = 3.6–27.2°
b = 25.147 (3) Å	µ = 0.32 mm−1
c = 12.4506 (15) Å	T = 200 K
β = 94.908 (11)°	Prism, colourless
V = 1856.6 (4) Å3	0.25 × 0.12 × 0.12 mm
Z = 4

Oxford Diffraction Gemini-S CCD-detector diffractometer	3650 independent reflections
Radiation source: Enhance (Mo) X-ray source	2653 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −31→19
Tmin = 0.935, Tmax = 0.980	l = −7→15
6908 measured reflections

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0672P)2 + 0.6392P] where P = (Fo2 + 2Fc2)/3
3650 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > σ(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
S1	0.31318 (17)	0.24657 (3)	0.40362 (7)	0.0267 (3)
O11	0.5538 (5)	0.25511 (10)	0.4069 (2)	0.0372 (9)
O12	0.1671 (5)	0.29205 (9)	0.3968 (2)	0.0377 (9)
N4	0.1704 (5)	0.13828 (12)	0.8172 (2)	0.0243 (9)
N41	0.0383 (6)	0.10417 (12)	0.0404 (3)	0.0344 (10)
C1	0.2645 (6)	0.21160 (12)	0.5225 (3)	0.0205 (10)
C2	0.4324 (6)	0.17907 (14)	0.5693 (3)	0.0245 (11)
C3	0.4005 (6)	0.15377 (14)	0.6663 (3)	0.0247 (11)
C4	0.2020 (6)	0.16202 (12)	0.7128 (3)	0.0189 (10)
C5	0.0323 (6)	0.19321 (13)	0.6645 (3)	0.0214 (10)
C6	0.0637 (6)	0.21865 (13)	0.5689 (3)	0.0230 (11)
C11	0.2346 (6)	0.20430 (13)	0.2959 (3)	0.0205 (10)
C21	0.0160 (6)	0.20665 (14)	0.2470 (3)	0.0250 (11)
C31	−0.0465 (6)	0.17356 (13)	0.1623 (3)	0.0241 (11)
C41	0.1045 (7)	0.13691 (13)	0.1250 (3)	0.0254 (11)
C51	0.3230 (6)	0.13441 (14)	0.1764 (3)	0.0275 (11)
C61	0.3863 (6)	0.16748 (14)	0.2607 (3)	0.0261 (12)
S1A	0.33152 (15)	−0.04463 (3)	0.14993 (8)	0.0244 (3)
O11A	0.1942 (4)	−0.07383 (10)	0.2210 (2)	0.0339 (9)
O12A	0.2028 (4)	−0.00796 (10)	0.0801 (2)	0.0331 (9)
O13A	0.4701 (4)	−0.08006 (10)	0.0909 (2)	0.0314 (8)
C1A	0.5187 (6)	−0.00617 (13)	0.2370 (3)	0.0238 (11)
C2A	0.4538 (6)	0.00940 (15)	0.3363 (3)	0.0306 (12)
C3A	0.5965 (7)	0.04085 (15)	0.4021 (3)	0.0329 (12)
C4A	0.8047 (7)	0.05602 (15)	0.3713 (3)	0.0340 (12)
C5A	0.8647 (6)	0.04020 (15)	0.2715 (3)	0.0315 (12)
C6A	0.7228 (6)	0.00919 (14)	0.2039 (3)	0.0275 (11)
C41A	0.9617 (8)	0.08898 (19)	0.4466 (4)	0.0532 (17)
H2	0.56820	0.17400	0.53570	0.0290*
H3	0.51380	0.13120	0.69970	0.0290*
H5	−0.10570	0.19720	0.69680	0.0260*
H6	−0.05120	0.24080	0.53540	0.0280*
H21	−0.08940	0.23110	0.27220	0.0300*
H31	−0.19530	0.17560	0.12830	0.0290*
H41	0.29640	0.12250	0.83680	0.0290*
H42	0.14260	0.16160	0.86140	0.0290*
H43	0.06360	0.11530	0.82050	0.0290*
H51	0.42800	0.10950	0.15240	0.0330*
H61	0.53450	0.16530	0.29540	0.0320*
H411	0.11190	0.07320	0.03200	0.0410*
H412	−0.11720	0.10820	0.01020	0.0410*
H2A	0.31240	−0.00140	0.35880	0.0370*
H3A	0.55110	0.05230	0.46970	0.0400*
H5A	1.00640	0.05080	0.24890	0.0380*
H6A	0.76610	−0.00130	0.13530	0.0330*
H41A	1.09020	0.10080	0.40850	0.0800*
H42A	1.01600	0.06740	0.50910	0.0800*
H43A	0.88040	0.12000	0.47090	0.0800*

	U11	U22	U33	U12	U13	U23
S1	0.0384 (6)	0.0232 (5)	0.0178 (5)	−0.0097 (4)	−0.0024 (4)	0.0024 (4)
O11	0.0397 (17)	0.0460 (17)	0.0256 (15)	−0.0258 (14)	0.0008 (13)	0.0054 (13)
O12	0.067 (2)	0.0179 (13)	0.0270 (15)	0.0014 (13)	−0.0020 (14)	0.0015 (12)
N4	0.0212 (16)	0.0297 (16)	0.0225 (16)	−0.0006 (13)	0.0051 (13)	−0.0015 (14)
N41	0.053 (2)	0.0245 (16)	0.0255 (17)	0.0009 (15)	0.0028 (16)	−0.0072 (14)
C1	0.033 (2)	0.0158 (16)	0.0127 (17)	−0.0093 (15)	0.0012 (15)	−0.0047 (14)
C2	0.0224 (19)	0.032 (2)	0.0196 (18)	−0.0037 (16)	0.0056 (16)	0.0030 (16)
C3	0.0213 (19)	0.0253 (18)	0.027 (2)	0.0029 (15)	−0.0001 (16)	−0.0011 (16)
C4	0.0245 (19)	0.0162 (16)	0.0162 (17)	−0.0054 (15)	0.0027 (15)	0.0006 (14)
C5	0.0185 (18)	0.0260 (18)	0.0195 (18)	−0.0032 (15)	0.0010 (15)	−0.0039 (16)
C6	0.025 (2)	0.0253 (18)	0.0181 (18)	0.0033 (16)	−0.0014 (16)	−0.0012 (16)
C11	0.0280 (19)	0.0205 (17)	0.0128 (16)	−0.0046 (15)	0.0015 (15)	0.0005 (15)
C21	0.030 (2)	0.0215 (17)	0.0234 (19)	0.0017 (16)	0.0011 (16)	0.0011 (16)
C31	0.026 (2)	0.0237 (18)	0.0213 (18)	−0.0031 (16)	−0.0048 (16)	0.0011 (16)
C41	0.039 (2)	0.0172 (17)	0.0200 (18)	−0.0057 (16)	0.0033 (17)	0.0031 (15)
C51	0.029 (2)	0.0234 (18)	0.031 (2)	0.0055 (16)	0.0073 (18)	−0.0014 (17)
C61	0.024 (2)	0.029 (2)	0.025 (2)	−0.0019 (16)	0.0003 (16)	0.0029 (17)
S1A	0.0234 (5)	0.0236 (5)	0.0251 (5)	−0.0014 (4)	−0.0042 (4)	0.0005 (4)
O11A	0.0294 (15)	0.0369 (15)	0.0349 (16)	−0.0134 (12)	−0.0001 (12)	0.0049 (13)
O12A	0.0332 (16)	0.0354 (15)	0.0290 (15)	0.0083 (12)	−0.0075 (12)	0.0059 (13)
O13A	0.0323 (15)	0.0293 (13)	0.0316 (15)	0.0037 (12)	−0.0027 (12)	−0.0059 (12)
C1A	0.0204 (19)	0.0224 (18)	0.028 (2)	−0.0016 (15)	−0.0006 (16)	0.0029 (16)
C2A	0.024 (2)	0.039 (2)	0.029 (2)	−0.0027 (18)	0.0030 (17)	0.0007 (19)
C3A	0.038 (2)	0.039 (2)	0.022 (2)	−0.0068 (19)	0.0050 (18)	−0.0029 (18)
C4A	0.036 (2)	0.026 (2)	0.038 (2)	−0.0029 (18)	−0.0075 (19)	−0.0020 (19)
C5A	0.025 (2)	0.033 (2)	0.037 (2)	−0.0086 (17)	0.0053 (18)	−0.0017 (19)
C6A	0.030 (2)	0.0265 (19)	0.026 (2)	−0.0020 (17)	0.0023 (17)	−0.0014 (17)
C41A	0.053 (3)	0.052 (3)	0.053 (3)	−0.018 (2)	−0.005 (3)	−0.020 (3)

S1—O11	1.445 (3)	C41—C51	1.401 (5)
S1—O12	1.435 (3)	C51—C61	1.367 (5)
S1—C1	1.767 (4)	C2—H2	0.9500
S1—C11	1.744 (4)	C3—H3	0.9500
S1A—C1A	1.773 (4)	C5—H5	0.9500
S1A—O13A	1.455 (3)	C6—H6	0.9500
S1A—O11A	1.454 (3)	C21—H21	0.9500
S1A—O12A	1.442 (3)	C31—H31	0.9500
N4—C4	1.457 (4)	C51—H51	0.9500
N41—C41	1.368 (5)	C61—H61	0.9500
N4—H42	0.8300	C1A—C2A	1.383 (5)
N4—H43	0.8600	C1A—C6A	1.371 (5)
N4—H41	0.8600	C2A—C3A	1.378 (5)
N41—H411	0.9000	C3A—C4A	1.382 (6)
N41—H412	0.9700	C4A—C5A	1.381 (5)
C1—C6	1.383 (5)	C4A—C41A	1.513 (6)
C1—C2	1.381 (5)	C5A—C6A	1.381 (5)
C2—C3	1.392 (5)	C2A—H2A	0.9500
C3—C4	1.375 (5)	C3A—H3A	0.9500
C4—C5	1.376 (5)	C5A—H5A	0.9500
C5—C6	1.378 (5)	C6A—H6A	0.9500
C11—C61	1.390 (5)	C41A—H41A	0.9800
C11—C21	1.390 (5)	C41A—H42A	0.9800
C21—C31	1.370 (5)	C41A—H43A	0.9800
C31—C41	1.394 (5)
O11—S1—O12	118.50 (16)	C1—C2—H2	120.00
O11—S1—C1	106.46 (16)	C3—C2—H2	120.00
O11—S1—C11	108.20 (16)	C2—C3—H3	121.00
O12—S1—C1	107.72 (16)	C4—C3—H3	121.00
O12—S1—C11	108.61 (16)	C6—C5—H5	120.00
C1—S1—C11	106.77 (16)	C4—C5—H5	120.00
O11A—S1A—O13A	111.75 (15)	C1—C6—H6	120.00
O11A—S1A—C1A	105.06 (16)	C5—C6—H6	120.00
O12A—S1A—O13A	112.45 (15)	C11—C21—H21	120.00
O12A—S1A—C1A	107.06 (15)	C31—C21—H21	120.00
O13A—S1A—C1A	106.80 (16)	C41—C31—H31	119.00
O11A—S1A—O12A	113.12 (15)	C21—C31—H31	119.00
C4—N4—H41	105.00	C41—C51—H51	120.00
C4—N4—H42	110.00	C61—C51—H51	120.00
H41—N4—H42	111.00	C51—C61—H61	120.00
H41—N4—H43	108.00	C11—C61—H61	120.00
H42—N4—H43	105.00	S1A—C1A—C2A	119.5 (3)
C4—N4—H43	118.00	S1A—C1A—C6A	119.8 (3)
C41—N41—H412	116.00	C2A—C1A—C6A	120.8 (3)
H411—N41—H412	120.00	C1A—C2A—C3A	119.3 (3)
C41—N41—H411	120.00	C2A—C3A—C4A	121.0 (3)
S1—C1—C2	118.9 (3)	C3A—C4A—C5A	118.5 (4)
S1—C1—C6	119.7 (3)	C3A—C4A—C41A	120.0 (4)
C2—C1—C6	121.3 (3)	C5A—C4A—C41A	121.5 (4)
C1—C2—C3	119.3 (3)	C4A—C5A—C6A	121.3 (3)
C2—C3—C4	118.8 (3)	C1A—C6A—C5A	119.2 (3)
N4—C4—C3	119.7 (3)	C1A—C2A—H2A	120.00
N4—C4—C5	118.5 (3)	C3A—C2A—H2A	120.00
C3—C4—C5	121.8 (3)	C2A—C3A—H3A	120.00
C4—C5—C6	119.6 (3)	C4A—C3A—H3A	119.00
C1—C6—C5	119.2 (3)	C4A—C5A—H5A	119.00
S1—C11—C21	119.4 (3)	C6A—C5A—H5A	119.00
S1—C11—C61	120.7 (3)	C1A—C6A—H6A	120.00
C21—C11—C61	120.0 (3)	C5A—C6A—H6A	120.00
C11—C21—C31	119.6 (3)	C4A—C41A—H41A	109.00
C21—C31—C41	121.2 (3)	C4A—C41A—H42A	109.00
N41—C41—C51	121.3 (3)	C4A—C41A—H43A	109.00
N41—C41—C31	120.2 (4)	H41A—C41A—H42A	110.00
C31—C41—C51	118.5 (3)	H41A—C41A—H43A	110.00
C41—C51—C61	120.5 (3)	H42A—C41A—H43A	109.00
C11—C61—C51	120.2 (3)
O11—S1—C1—C2	−28.1 (3)	C2—C3—C4—N4	−176.6 (3)
O11—S1—C1—C6	149.6 (3)	N4—C4—C5—C6	176.2 (3)
O12—S1—C1—C2	−156.2 (3)	C3—C4—C5—C6	−2.5 (5)
O12—S1—C1—C6	21.5 (3)	C4—C5—C6—C1	1.0 (5)
C11—S1—C1—C2	87.3 (3)	S1—C11—C61—C51	179.8 (3)
C11—S1—C1—C6	−95.0 (3)	C61—C11—C21—C31	−1.8 (5)
O11—S1—C11—C21	−153.5 (3)	S1—C11—C21—C31	180.0 (3)
O11—S1—C11—C61	28.2 (3)	C21—C11—C61—C51	1.6 (5)
O12—S1—C11—C21	−23.7 (3)	C11—C21—C31—C41	0.9 (5)
O12—S1—C11—C61	158.1 (3)	C21—C31—C41—N41	179.9 (3)
C1—S1—C11—C21	92.2 (3)	C21—C31—C41—C51	0.2 (5)
C1—S1—C11—C61	−86.0 (3)	C31—C41—C51—C61	−0.4 (5)
O12A—S1A—C1A—C2A	92.7 (3)	N41—C41—C51—C61	179.9 (3)
O12A—S1A—C1A—C6A	−85.3 (3)	C41—C51—C61—C11	−0.5 (5)
O13A—S1A—C1A—C2A	−146.7 (3)	S1A—C1A—C2A—C3A	−177.7 (3)
O13A—S1A—C1A—C6A	35.4 (3)	C6A—C1A—C2A—C3A	0.2 (5)
O11A—S1A—C1A—C2A	−27.8 (3)	S1A—C1A—C6A—C5A	178.5 (3)
O11A—S1A—C1A—C6A	154.2 (3)	C2A—C1A—C6A—C5A	0.5 (5)
S1—C1—C2—C3	176.3 (3)	C1A—C2A—C3A—C4A	−1.4 (6)
C2—C1—C6—C5	0.9 (5)	C2A—C3A—C4A—C5A	1.8 (6)
C6—C1—C2—C3	−1.4 (5)	C2A—C3A—C4A—C41A	−177.9 (4)
S1—C1—C6—C5	−176.8 (3)	C3A—C4A—C5A—C6A	−1.0 (6)
C1—C2—C3—C4	−0.1 (5)	C41A—C4A—C5A—C6A	178.7 (4)
C2—C3—C4—C5	2.0 (5)	C4A—C5A—C6A—C1A	−0.1 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···O13Ai	0.86	1.91	2.759 (4)	165
N4—H42···O11ii	0.83	2.24	3.008 (4)	153
N4—H43···O11Aiii	0.86	1.89	2.718 (4)	160
N41—H411···O12A	0.90	2.18	3.012 (4)	152
N41—H412···O13Aiv	0.97	2.46	3.369 (4)	155
C2—H2···O11	0.95	2.59	2.918 (4)	101
C2A—H2A···O11A	0.95	2.56	2.907 (4)	102
C6—H6···O12	0.95	2.59	2.933 (4)	102
C21—H21···O12	0.95	2.58	2.935 (4)	102

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯O13A i	0.86	1.91	2.759 (4)	165
N4—H42⋯O11ii	0.83	2.24	3.008 (4)	153
N4—H43⋯O11A iii	0.86	1.89	2.718 (4)	160
N41—H411⋯O12A	0.90	2.18	3.012 (4)	152
N41—H412⋯O13A iv	0.97	2.46	3.369 (4)	155

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .