4-[(4-Amino­phen­yl)sulfon­yl]aniline–3,5-dinitro­benzoic acid (1/1)

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536812004709

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o669

doi:10.1107/S1600536812004709

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4-[(4-Aminophenyl)sulfonyl]aniline–3,5-dinitrobenzoic acid (1/1)

Graham Smith ^a ^* and Urs D. Wermuth ^a

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 17 January 2012; accepted 3 February 2012; online 10 February 2012)

The title compound, C₇H₄N₂O₆·C₁₂H₁₂N₂O₂S, is a 1:1 cocrystal of the drug dapsone with 3,5-dinitrobenzoic acid. The dihedral angle between the two aromatic rings of the dapsone molecule is 75.4 (2)°, and the dihedral angles between these rings and that of the 3,5-dinitrobenzoic acid are 64.5 (2) and 68.4 (2)°. A strong intermolecular carboxylic acid O—H⋯N_amine hydrogen bond is found, together with intermolecular amine N—H⋯O hydrogen-bonding associations with carboxyl, nitro and sulfone O-atom acceptors. In addition, weak π–π interactions between one of the dapsone benzene rings and the 3,5-dinitrobenzoic 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_r = 460.43
Monoclinic, P 2₁
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 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) 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[F² > 2σ(F²)] = 0.056
wR(F²) = 0.102
S = 0.93
3774 reflections
289 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Absolute structure: Flack (1983 ), 1803 Friedel pairs
Flack parameter: 0.07 (11)

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) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812004709/fj2510sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536812004709/fj2510Isup3.cml

checkCIF report

Comment top

Dapsone [4-(4-aminophenylsulfonyl)aniline] is a very weak Lewis base which finds use as an anti-leprotic, anti-malarial and leprostatic drug (Wilson et al., 1991). The structure of the Dapsone 0.33hydrate is known (Kus'mina et al., 1981) but salts or adducts of this compound are not common. We have reported the 1:2 co-crystalline adduct with 1,3,5-trinitrobenzene (Smith & Wermuth, 2012a). Reported here is the structure of the 1:1 cocrystalline adduct of Dapsone with 3,5-dinitrobenzoic acid, C₁₂H₁₂N₂O₂S. C₇H₄N₄O₆ (Fig. 1). This acid has been found to be very useful for the formation of co-crystalline adducts (Etter & Frankenbach, 1989).

A primary intermolecular O—H···O_amine hydrogen bond (Table 1) links the two molecules while N—H···O hydrogen-bond associations with carboxyl, nitro and sulfone O-atom acceptors give a two-dimensional structure (Fig. 2). A weak π–π interaction is also found between one of the Dapsone aromatic ring moieties (C1–C6) and that of the acid molecule (C1A–C6A [minimum ring centroid separation 3.774 (2) Å]. In the Dapsone molecule the inter-ring dihedral angle is 75.4 (2)° which compare with 77.3° in the anhydrous parent Dapsone molecule (Dickenson et al., 1970), 88.1, 75.8 and 74.7° for the three independent Dapsone molecules in the 0.33hydrate structure (Kus'mina et al., 1981) and 77.5° in the 5-nitroisophthalic acid adduct (Smith & Wermuth, 2012b. The 3,5-dinitrobenzoic acid molecule is essentially planar [torsion angles C2A—C1A—C11A—O11A, -171.3 (4)°; C2A—C3A—N31A—O32A, -174.4 (4)°; C4A—C5A—N51A—O52A, -172.2 (4)°].

Related literature top

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 top

The title compound was prepared by the intereaction of 4-(4-aminophenylsulfonyl)aniline (Dapsone) with 3,5-dinitrobenzoic acid by heating together for 15 min under reflux, 1 mmol quantities of the two reagents in 50 ml of 50% ethanol–water. Minor poorly-formed yellow crystal aggregates of the title co-crystal formed after partial room-temperature evaporation of the solvent.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 (Spek, 2009).

Figures top

	Fig. 1. The molecular conformation and atom-numbering scheme for the Dapsone and 3,5-dinitrobenzoic acid molecules in the title co-crystal. Non-H atoms are shown as 50% probability displacement ellipsoids and the inter-species hydrogen bond is shown as a dashed line.
	Fig. 2. The hydrogen-bonding in the title adduct, viewed down the a axial direction of the unit cell. Hydrogen bonds are shown as dashed lines. For symmetry codes see Table 1.

4-[(4-Aminophenyl)sulfonyl]aniline–3,5-dinitrobenzoic acid (1/1) top

Crystal data top

C₇H₄N₂O₆·C₁₂H₁₂N₂O₂S	F(000) = 476
M_r = 460.43	D_x = 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

Data collection top

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	R_int = 0.049
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −19→19
T_min = 0.832, T_max = 0.990	l = −13→10
6257 measured reflections

Refinement top

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(F_o²) + (0.0468P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max = 0.001
3774 reflections	Δρ_max = 0.50 e Å⁻³
289 parameters	Δρ_min = −0.43 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1803 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (11)

Crystal data top

C₇H₄N₂O₆·C₁₂H₁₂N₂O₂S	V = 965.68 (12) Å³
M_r = 460.43	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.8222 (4) Å	µ = 0.23 mm⁻¹
b = 15.5982 (10) Å	T = 200 K
c = 10.7299 (9) Å	0.30 × 0.25 × 0.05 mm
β = 97.693 (6)°

Data collection top

Oxfod Diffraction Gemini-S CCD detector diffractometer	3774 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2643 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.990	R_int = 0.049
6257 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.102	Δρ_max = 0.50 e Å⁻³
S = 0.93	Δρ_min = −0.43 e Å⁻³
3774 reflections	Absolute structure: Flack (1983), 1803 Friedel pairs
289 parameters	Absolute structure parameter: 0.07 (11)
1 restraint

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x−1, y, z; (iii) −x+2, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₄N₂O₆·C₁₂H₁₂N₂O₂S
M_r	460.43
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	200
a, b, c (Å)	5.8222 (4), 15.5982 (10), 10.7299 (9)
β (°)	97.693 (6)
V (Å³)	965.68 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.30 × 0.25 × 0.05

Data collection
Diffractometer	Oxfod Diffraction Gemini-S CCD detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.832, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	6257, 3774, 2643
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.102, 0.93
No. of reflections	3774
No. of parameters	289
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.43
Absolute structure	Flack (1983), 1803 Friedel pairs
Absolute structure parameter	0.07 (11)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+1, y−1/2, −z+1; (ii) x−1, y, z.

Acknowledgements

The authors acknowledge financial support from the Australian Research Committee, the University Library and the Science and Engineering Faculty, Queensland University of Technology.

References

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