4-[(4-Amino-phen-yl)sulfon-yl]aniline-3,5-dinitro-benzoic acid (1/1).

The title compound, C(7)H(4)N(2)O(6)·C(12)H(12)N(2)O(2)S, is a 1:1 cocrystal of the drug dapsone with 3,5-dinitro-benzoic acid. The dihedral angle between the two aromatic rings of the dapsone mol-ecule is 75.4 (2)°, and the dihedral angles between these rings and that of the 3,5-dinitro-benzoic acid are 64.5 (2) and 68.4 (2)°. A strong inter-molecular carb-oxy-lic acid O-H⋯N(amine) hydrogen bond is found, together with inter-molecular amine N-H⋯O hydrogen-bonding associations with carboxyl, nitro and sulfone O-atom acceptors. In addition, weak π-π inter-actions between one of the dapsone benzene rings and the 3,5-dinitro-benzoic acid ring [ring centroid separation = 3.774 (2) Å] results in a two-dimensional network structure.

Related literature

For drug applications of dapsone, see: Wilson et al. (1991 ▶). For the structures of dapsone and its salts and adducts, see: Dickenson et al. (1970 ▶); Kus’mina et al. (1981 ▶); Smith & Wermuth (2012a ▶,b ▶). For adducts of 3,5-dinitro­benzoic acid, see: Etter & Frankenbach (1989 ▶).

Experimental

Crystal data

C7H4N2O6·C12H12N2O2S

M = 460.43

Monoclinic,

a = 5.8222 (4) Å

b = 15.5982 (10) Å

c = 10.7299 (9) Å

β = 97.693 (6)°

V = 965.68 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.23 mm−1

T = 200 K

0.30 × 0.25 × 0.05 mm

Data collection

Oxfod Diffraction Gemini-S CCD detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.832, T max = 0.990

6257 measured reflections

3774 independent reflections

2643 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.102

S = 0.93

3774 reflections

289 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.43 e Å−3

Absolute structure: Flack (1983 ▶), 1803 Friedel pairs

Flack parameter: 0.07 (11)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812004709/fj2510sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004709/fj2510Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812004709/fj2510Isup3.cml

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

C7H4N2O6·C12H12N2O2S	F(000) = 476
Mr = 460.43	Dx = 1.584 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2802 reflections
a = 5.8222 (4) Å	θ = 3.2–28.7°
b = 15.5982 (10) Å	µ = 0.23 mm−1
c = 10.7299 (9) Å	T = 200 K
β = 97.693 (6)°	Plate, yellow
V = 965.68 (12) Å3	0.30 × 0.25 × 0.05 mm
Z = 2

Oxfod Diffraction Gemini-S CCD detector diffractometer	3774 independent reflections
Radiation source: Enhance (Mo) X-ray source	2643 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −19→19
Tmin = 0.832, Tmax = 0.990	l = −13→10
6257 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0468P)2] where P = (Fo2 + 2Fc2)/3
S = 0.93	(Δ/σ)max = 0.001
3774 reflections	Δρmax = 0.50 e Å−3
289 parameters	Δρmin = −0.43 e Å−3
1 restraint	Absolute structure: Flack (1983), 1803 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.07 (11)

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	0.93142 (16)	0.26625 (7)	0.65868 (10)	0.0211 (3)
O1	1.1787 (4)	0.25679 (19)	0.6593 (2)	0.0277 (9)
O11	0.7823 (5)	0.19588 (17)	0.6150 (3)	0.0281 (10)
N4	0.8049 (6)	0.3557 (2)	1.1801 (3)	0.0372 (14)
N41	0.6306 (6)	0.5772 (2)	0.3593 (3)	0.0297 (12)
C1	0.8876 (6)	0.2919 (2)	0.8133 (4)	0.0198 (12)
C2	1.0600 (7)	0.3366 (2)	0.8888 (4)	0.0214 (14)
C3	1.0320 (7)	0.3575 (3)	1.0091 (4)	0.0234 (14)
C4	0.8282 (7)	0.3357 (3)	1.0594 (4)	0.0244 (14)
C5	0.6570 (6)	0.2913 (2)	0.9813 (4)	0.0250 (16)
C6	0.6843 (6)	0.2705 (3)	0.8600 (4)	0.0232 (14)
C11	0.8420 (6)	0.3568 (2)	0.5669 (4)	0.0179 (12)
C21	0.9984 (6)	0.4232 (2)	0.5568 (4)	0.0216 (14)
C31	0.9285 (7)	0.4947 (3)	0.4881 (4)	0.0239 (16)
C41	0.6997 (7)	0.5020 (3)	0.4281 (4)	0.0223 (14)
C51	0.5478 (6)	0.4342 (3)	0.4358 (4)	0.0222 (16)
C61	0.6189 (6)	0.3623 (3)	0.5057 (4)	0.0202 (14)
O11A	1.1135 (5)	0.52662 (18)	0.1963 (3)	0.0307 (11)
O12A	0.7721 (5)	0.59140 (19)	0.1352 (3)	0.0338 (11)
O31A	0.6393 (5)	0.7561 (2)	−0.2381 (3)	0.0411 (11)
O32A	0.8367 (5)	0.7329 (2)	−0.3913 (3)	0.0568 (14)
O51A	1.5248 (5)	0.5584 (2)	−0.3210 (3)	0.0452 (11)
O52A	1.5821 (5)	0.4790 (2)	−0.1557 (4)	0.0518 (14)
N31A	0.7989 (6)	0.7217 (2)	−0.2837 (4)	0.0304 (12)
N51A	1.4771 (6)	0.5348 (2)	−0.2196 (4)	0.0302 (14)
C1A	1.0392 (6)	0.5909 (2)	−0.0076 (4)	0.0202 (14)
C2A	0.8998 (7)	0.6454 (3)	−0.0849 (4)	0.0227 (14)
C3A	0.9516 (6)	0.6645 (3)	−0.2025 (4)	0.0228 (14)
C4A	1.1434 (7)	0.6304 (3)	−0.2487 (4)	0.0237 (14)
C5A	1.2790 (6)	0.5752 (3)	−0.1701 (4)	0.0205 (14)
C6A	1.2350 (6)	0.5561 (3)	−0.0500 (4)	0.0234 (14)
C11A	0.9811 (7)	0.5666 (3)	0.1197 (4)	0.0267 (17)
H2	1.19500	0.35230	0.85710	0.0260*
H3	1.14970	0.38670	1.05900	0.0280*
H5	0.52150	0.27540	1.01240	0.0300*
H6	0.56660	0.24200	0.80910	0.0280*
H21	1.15000	0.41890	0.59660	0.0260*
H31	1.03330	0.53890	0.48110	0.0290*
H51	0.39760	0.43720	0.39380	0.0270*
H61	0.51570	0.31740	0.51140	0.0240*
H411	0.92050	0.36670	1.23450	0.0450*
H412	0.65340	0.36650	1.20020	0.0450*
H413	0.48370	0.57210	0.32450	0.0360*
H414	0.64420	0.62220	0.41090	0.0360*
H2A	0.76960	0.66950	−0.05720	0.0280*
H4A	1.17850	0.64400	−0.32840	0.0280*
H6A	1.33460	0.52070	0.00190	0.0270*
H12A	0.73000	0.58250	0.21450	0.0510*

	U11	U22	U33	U12	U13	U23
S1	0.0254 (5)	0.0146 (5)	0.0240 (6)	0.0027 (5)	0.0059 (4)	0.0007 (5)
O1	0.0231 (14)	0.0290 (17)	0.0322 (17)	0.0077 (14)	0.0084 (11)	0.0032 (15)
O11	0.0409 (17)	0.0127 (15)	0.0319 (18)	−0.0020 (13)	0.0091 (13)	−0.0017 (13)
N4	0.043 (2)	0.045 (3)	0.027 (2)	−0.0099 (19)	0.0168 (18)	−0.005 (2)
N41	0.027 (2)	0.035 (2)	0.030 (2)	0.0116 (16)	0.0147 (16)	0.0147 (18)
C1	0.024 (2)	0.015 (2)	0.021 (2)	0.0046 (16)	0.0057 (17)	0.0073 (17)
C2	0.019 (2)	0.018 (2)	0.028 (3)	−0.0006 (17)	0.0062 (18)	0.0050 (19)
C3	0.024 (2)	0.021 (2)	0.026 (3)	−0.0070 (18)	0.0063 (18)	0.002 (2)
C4	0.031 (2)	0.014 (2)	0.029 (3)	0.0027 (19)	0.0075 (19)	0.005 (2)
C5	0.019 (2)	0.028 (3)	0.029 (3)	0.0011 (17)	0.0065 (18)	0.006 (2)
C6	0.020 (2)	0.022 (2)	0.027 (3)	−0.001 (2)	0.0008 (16)	0.002 (2)
C11	0.020 (2)	0.017 (2)	0.018 (2)	0.0024 (17)	0.0071 (17)	−0.0014 (18)
C21	0.019 (2)	0.019 (2)	0.027 (3)	0.0022 (18)	0.0036 (17)	−0.002 (2)
C31	0.027 (3)	0.015 (2)	0.032 (3)	−0.0054 (18)	0.0119 (19)	−0.002 (2)
C41	0.028 (2)	0.022 (2)	0.020 (3)	0.0052 (19)	0.0144 (18)	0.0014 (19)
C51	0.013 (2)	0.034 (3)	0.020 (3)	−0.0010 (19)	0.0037 (16)	0.001 (2)
C61	0.018 (2)	0.016 (2)	0.027 (3)	−0.0033 (17)	0.0043 (17)	0.0019 (19)
O11A	0.0358 (18)	0.032 (2)	0.0237 (19)	0.0036 (15)	0.0015 (14)	0.0046 (15)
O12A	0.0348 (18)	0.043 (2)	0.0270 (19)	0.0126 (15)	0.0162 (14)	0.0109 (16)
O31A	0.0382 (17)	0.051 (2)	0.036 (2)	0.0219 (18)	0.0123 (14)	0.0015 (19)
O32A	0.050 (2)	0.094 (3)	0.029 (2)	0.0285 (19)	0.0145 (16)	0.023 (2)
O51A	0.0420 (19)	0.058 (2)	0.040 (2)	0.0061 (16)	0.0217 (16)	−0.0068 (17)
O52A	0.040 (2)	0.038 (2)	0.081 (3)	0.0210 (18)	0.0219 (18)	0.011 (2)
N31A	0.032 (2)	0.035 (2)	0.025 (2)	0.0044 (17)	0.0070 (18)	0.0080 (19)
N51A	0.023 (2)	0.025 (2)	0.044 (3)	0.0027 (17)	0.0102 (18)	−0.011 (2)
C1A	0.026 (2)	0.007 (2)	0.028 (3)	−0.0041 (17)	0.0047 (18)	−0.0044 (19)
C2A	0.020 (2)	0.016 (2)	0.031 (3)	−0.0019 (17)	−0.0003 (18)	−0.0017 (19)
C3A	0.019 (2)	0.020 (2)	0.030 (3)	−0.0012 (17)	0.0058 (18)	−0.006 (2)
C4A	0.028 (2)	0.023 (2)	0.021 (3)	−0.0062 (19)	0.0071 (19)	−0.0041 (19)
C5A	0.022 (2)	0.018 (2)	0.022 (3)	0.0016 (17)	0.0050 (17)	−0.0022 (19)
C6A	0.024 (2)	0.016 (2)	0.031 (3)	−0.0009 (19)	0.0068 (19)	−0.002 (2)
C11A	0.033 (3)	0.020 (3)	0.027 (3)	−0.004 (2)	0.004 (2)	−0.002 (2)

S1—O1	1.446 (3)	C11—C61	1.378 (5)
S1—O11	1.439 (3)	C11—C21	1.393 (5)
S1—C1	1.758 (4)	C21—C31	1.368 (6)
S1—C11	1.760 (4)	C31—C41	1.404 (6)
O11A—C11A	1.220 (5)	C41—C51	1.388 (6)
O12A—C11A	1.309 (5)	C51—C61	1.382 (6)
O31A—N31A	1.230 (5)	C2—H2	0.9300
O32A—N31A	1.217 (5)	C3—H3	0.9300
O51A—N51A	1.215 (5)	C5—H5	0.9300
O52A—N51A	1.220 (5)	C6—H6	0.9300
O12A—H12A	0.9300	C21—H21	0.9300
N4—C4	1.357 (5)	C31—H31	0.9300
N41—C41	1.415 (6)	C51—H51	0.9300
N4—H412	0.9500	C61—H61	0.9300
N4—H411	0.8500	C1A—C6A	1.393 (5)
N41—H413	0.8900	C1A—C11A	1.499 (6)
N41—H414	0.8900	C1A—C2A	1.374 (6)
N31A—C3A	1.462 (6)	C2A—C3A	1.369 (6)
N51A—C5A	1.474 (5)	C3A—C4A	1.387 (6)
C1—C2	1.390 (5)	C4A—C5A	1.378 (6)
C1—C6	1.387 (5)	C5A—C6A	1.380 (6)
C2—C3	1.362 (6)	C2A—H2A	0.9300
C3—C4	1.409 (6)	C4A—H4A	0.9300
C4—C5	1.397 (6)	C6A—H6A	0.9300
C5—C6	1.371 (6)
O1—S1—O11	118.73 (18)	C11—C61—C51	120.3 (4)
O1—S1—C1	106.80 (16)	C1—C2—H2	120.00
O1—S1—C11	107.70 (17)	C3—C2—H2	120.00
O11—S1—C1	108.88 (18)	C4—C3—H3	119.00
O11—S1—C11	108.03 (18)	C2—C3—H3	119.00
C1—S1—C11	106.02 (18)	C4—C5—H5	119.00
C11A—O12A—H12A	116.00	C6—C5—H5	119.00
H411—N4—H412	119.00	C1—C6—H6	120.00
C4—N4—H411	122.00	C5—C6—H6	120.00
C4—N4—H412	118.00	C11—C21—H21	120.00
C41—N41—H413	110.00	C31—C21—H21	120.00
C41—N41—H414	109.00	C21—C31—H31	120.00
H413—N41—H414	109.00	C41—C31—H31	120.00
O31A—N31A—O32A	123.9 (4)	C41—C51—H51	120.00
O31A—N31A—C3A	117.4 (4)	C61—C51—H51	120.00
O32A—N31A—C3A	118.7 (3)	C11—C61—H61	120.00
O52A—N51A—C5A	117.4 (4)	C51—C61—H61	120.00
O51A—N51A—O52A	124.2 (4)	C2A—C1A—C11A	121.3 (3)
O51A—N51A—C5A	118.5 (3)	C6A—C1A—C11A	119.6 (3)
S1—C1—C2	118.7 (3)	C2A—C1A—C6A	119.1 (4)
C2—C1—C6	119.7 (4)	C1A—C2A—C3A	120.4 (4)
S1—C1—C6	121.7 (3)	N31A—C3A—C2A	119.4 (4)
C1—C2—C3	120.2 (4)	C2A—C3A—C4A	122.2 (4)
C2—C3—C4	121.3 (4)	N31A—C3A—C4A	118.4 (4)
N4—C4—C5	122.2 (4)	C3A—C4A—C5A	116.3 (4)
C3—C4—C5	117.4 (4)	N51A—C5A—C6A	119.8 (4)
N4—C4—C3	120.5 (4)	C4A—C5A—C6A	123.0 (4)
C4—C5—C6	121.5 (4)	N51A—C5A—C4A	117.3 (4)
C1—C6—C5	119.9 (4)	C1A—C6A—C5A	118.9 (4)
C21—C11—C61	120.1 (4)	O11A—C11A—C1A	122.9 (4)
S1—C11—C21	119.5 (3)	O12A—C11A—C1A	111.6 (4)
S1—C11—C61	120.4 (3)	O11A—C11A—O12A	125.4 (4)
C11—C21—C31	119.8 (4)	C1A—C2A—H2A	120.00
C21—C31—C41	120.6 (4)	C3A—C2A—H2A	120.00
N41—C41—C51	121.6 (4)	C3A—C4A—H4A	122.00
C31—C41—C51	118.9 (4)	C5A—C4A—H4A	122.00
N41—C41—C31	119.5 (4)	C1A—C6A—H6A	121.00
C41—C51—C61	120.3 (4)	C5A—C6A—H6A	121.00
O1—S1—C1—C2	29.6 (3)	C3—C4—C5—C6	−0.7 (6)
O1—S1—C1—C6	−152.0 (3)	C4—C5—C6—C1	1.5 (6)
O11—S1—C1—C2	158.9 (3)	S1—C11—C21—C31	−178.4 (3)
O11—S1—C1—C6	−22.7 (4)	C61—C11—C21—C31	1.4 (6)
C11—S1—C1—C2	−85.1 (3)	C21—C11—C61—C51	−1.1 (6)
C11—S1—C1—C6	93.3 (3)	S1—C11—C61—C51	178.7 (3)
O1—S1—C11—C21	−27.7 (4)	C11—C21—C31—C41	0.4 (6)
O1—S1—C11—C61	152.6 (3)	C21—C31—C41—N41	179.0 (4)
O11—S1—C11—C21	−157.0 (3)	C21—C31—C41—C51	−2.3 (6)
O11—S1—C11—C61	23.2 (4)	C31—C41—C51—C61	2.6 (6)
C1—S1—C11—C21	86.4 (3)	N41—C41—C51—C61	−178.7 (4)
C1—S1—C11—C61	−93.4 (4)	C41—C51—C61—C11	−0.9 (6)
O32A—N31A—C3A—C2A	−174.4 (4)	C6A—C1A—C2A—C3A	0.7 (6)
O32A—N31A—C3A—C4A	4.7 (6)	C11A—C1A—C2A—C3A	−177.8 (4)
O31A—N31A—C3A—C2A	6.0 (6)	C2A—C1A—C6A—C5A	−2.1 (6)
O31A—N31A—C3A—C4A	−175.0 (4)	C11A—C1A—C6A—C5A	176.3 (4)
O52A—N51A—C5A—C4A	−172.2 (4)	C2A—C1A—C11A—O11A	−171.3 (4)
O51A—N51A—C5A—C4A	7.3 (6)	C2A—C1A—C11A—O12A	10.5 (6)
O51A—N51A—C5A—C6A	−173.5 (4)	C6A—C1A—C11A—O11A	10.3 (6)
O52A—N51A—C5A—C6A	7.0 (6)	C6A—C1A—C11A—O12A	−167.9 (4)
S1—C1—C2—C3	−180.0 (3)	C1A—C2A—C3A—N31A	179.2 (4)
C6—C1—C2—C3	1.6 (6)	C1A—C2A—C3A—C4A	0.1 (7)
C2—C1—C6—C5	−1.9 (6)	N31A—C3A—C4A—C5A	−178.4 (4)
S1—C1—C6—C5	179.7 (3)	C2A—C3A—C4A—C5A	0.6 (7)
C1—C2—C3—C4	−0.9 (6)	C3A—C4A—C5A—N51A	177.0 (4)
C2—C3—C4—N4	178.9 (4)	C3A—C4A—C5A—C6A	−2.2 (7)
C2—C3—C4—C5	0.5 (6)	N51A—C5A—C6A—C1A	−176.2 (4)
N4—C4—C5—C6	−179.1 (4)	C4A—C5A—C6A—C1A	3.0 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O12A—H12A···N41	0.93	1.73	2.653 (5)	173
N4—H412···O31Ai	0.95	2.49	3.150 (5)	126
N41—H413···O11Aii	0.89	2.50	3.367 (5)	165
N41—H414···O1iii	0.89	2.50	3.030 (4)	119
C2—H2···O1	0.93	2.58	2.924 (5)	102

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12A—H12A⋯N41	0.93	1.73	2.653 (5)	173
N4—H412⋯O31Ai	0.95	2.49	3.150 (5)	126
N41—H413⋯O11Aii	0.89	2.50	3.367 (5)	165

Symmetry codes: (i) ; (ii) .