3-Nitro-N,N-bis­(p-tolyl­sulfon­yl)aniline

In the title compound, C₂₀H₁₈N₂O₆S₂, all bond lengths and angles are within normal ranges. The configuration around central N atom is almost planar; the r.m.s. deviation for the fitted atoms is 0.0218 Å. The electron-withdrawing effect of the S atom is observed in this structure, i.e. the ortho-meta-para C-C-C angles in the attached rings are greater than 120°.

Key indicators

• Single-crystal X-ray study
• T = 278 K
• Mean [sigma](C-C)= 0.004 Å
• R factor = 0.054
• wR factor = 0.135
• Data-to-parameter ratio = 13.2

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S1. Comment

The sulfonamide group is present in many bioactive compounds and be used as protecting group (Krishnaiah et al., 1995; Patani & Lavoie, 1996). Some crystal structures involving sulfonamide groups have been published, including a recent report from our labratory (Yan, et al., 2007). As an extension of this research, we report the synthesis and the crystal structure of C₂₀H₁₈N₂O₆S₂ (I), namely N,N-bis(toluene-4-sulfonylamino)-3-nitroaniline.

In (I) (Fig. 1), all bond lengths and angles show normal values (Allen et al., 1987) and are unremarkable when compared with those found in our previous report (Yan, et al., 2007). The three independent benzene rings C2—C7 (P₁), C9—C14 (P₂) and C15—C20 (P₃) are essentially planar with r.m.s. deviation of 0.0029 Å, 0.0091 Å and 0.0041 Å, respectively. The dihedral angles P1/P2, P1/P3 and P2/P3 are 41.74 (14), 31.82 (14) and 19.50 (14)°, respectively. The bond angles of C4—C3—C2 and C6—C7—C2 should be more than 120°. The experimental results are 121.1 (3)° and 121.6 (3)°, respectively. It shows that the S atoms introduce electron-withdrawing effect (Kazak et al., 2000).

Related literature

For related literature, see: Allen et al. (1987); Krishnaiah et al. (1995); Patani & Lavoie (1996); Yan et al. (2007); Creaser et al. (2001); Kazak et al. (2000); Yu (2006).

S2. Experimental

Aqueous NaOH (20 ml, 10%) was added dropwise to a mixture of 4-methylbenzene-1-sulfonyl chloride (10 mmol, 1.905 g) and 3-nitroaniline (5 mmol, 1.38 g) with constant stirring for 4 h. After column chromatography separation with the silica stationary phase and the eluent of petroleum ether and acetic ester with relative proportions (v/v, 5/1), the purified product was dissolved in ethanol and allowed to stand for approximately 8 d until single crystals formed.

S3. Refinement

The all H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of Csp²—H = 0.93 Å with U_iso = 1.2U_eq(parent atom), Csp³—H = 0.96 Å with U_iso = 1.5U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids and the atomic numbering.

3-Nitro-N,N-bis(p-tolylsulfonyl)aniline

Crystal data

C20H18N2O6S2	F(000) = 1856
Mr = 446.48	Dx = 1.457 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3381 reflections
a = 25.7789 (9) Å	θ = 2.5–25.0°
b = 9.7238 (7) Å	µ = 0.30 mm^−1
c = 16.4653 (8) Å	T = 278 K
β = 99.507 (1)°	Blcok, colourless
V = 4070.7 (4) Å^3	0.41 × 0.29 × 0.26 mm
Z = 8

Data collection

Bruker APEX area-detector diffractometer	3607 independent reflections
Radiation source: fine-focus sealed tube	3249 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −30→28
Tmin = 0.886, Tmax = 0.926	k = −11→11
10446 measured reflections	l = −13→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.057P)^2 + 4.9858P] where P = (Fo^2 + 2Fc^2)/3
3607 reflections	(Δ/σ)max = 0.001
273 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.34132 (3)	0.03077 (7)	0.05542 (4)	0.0478 (2)
S2	0.29039 (3)	0.01230 (7)	0.20435 (4)	0.0471 (2)
O1	0.31699 (8)	−0.0994 (2)	0.04417 (15)	0.0689 (6)
O2	0.33162 (8)	0.1314 (2)	−0.00784 (12)	0.0633 (6)
O3	0.31436 (8)	−0.1187 (2)	0.21575 (15)	0.0674 (6)
O4	0.29099 (8)	0.1039 (2)	0.27150 (12)	0.0622 (6)
O5	0.45481 (10)	0.4127 (3)	0.30077 (16)	0.0813 (7)
O6	0.43517 (11)	0.6151 (3)	0.2557 (2)	0.0969 (9)
N1	0.32225 (8)	0.1017 (2)	0.13871 (14)	0.0455 (5)
N2	0.42661 (11)	0.4927 (3)	0.25742 (18)	0.0634 (7)
C1	0.57602 (13)	−0.0289 (4)	0.1548 (2)	0.0845 (12)
H1A	0.5890	−0.0989	0.1223	0.127*
H1B	0.5838	−0.0537	0.2120	0.127*
H1C	0.5927	0.0572	0.1465	0.127*
C2	0.51728 (11)	−0.0150 (3)	0.12921 (18)	0.0570 (8)
C3	0.48381 (12)	−0.1222 (3)	0.1399 (2)	0.0617 (8)
H3	0.4978	−0.2045	0.1625	0.074*
C4	0.43021 (11)	−0.1092 (3)	0.11752 (18)	0.0536 (7)
H4	0.4081	−0.1818	0.1254	0.064*
C5	0.40961 (10)	0.0117 (3)	0.08350 (16)	0.0431 (6)
C6	0.44203 (11)	0.1200 (3)	0.07136 (19)	0.0537 (7)
H6	0.4280	0.2015	0.0478	0.064*
C7	0.49557 (12)	0.1052 (3)	0.0948 (2)	0.0620 (8)
H7	0.5176	0.1782	0.0872	0.074*
C8	0.07156 (13)	−0.0322 (4)	0.0105 (2)	0.0814 (11)
H8A	0.0479	0.0263	0.0339	0.122*
H8B	0.0592	−0.1255	0.0098	0.122*
H8C	0.0731	−0.0031	−0.0447	0.122*
C9	0.12544 (11)	−0.0235 (3)	0.06152 (19)	0.0551 (7)
C10	0.14279 (11)	0.0960 (3)	0.10178 (19)	0.0558 (7)
H10	0.1203	0.1713	0.0983	0.067*
C11	0.19262 (11)	0.1071 (3)	0.14717 (19)	0.0504 (7)
H11	0.2035	0.1884	0.1745	0.061*
C12	0.22587 (10)	−0.0044 (3)	0.15123 (17)	0.0423 (6)
C13	0.20953 (11)	−0.1263 (3)	0.1129 (2)	0.0552 (7)
H13	0.2320	−0.2017	0.1164	0.066*
C14	0.15919 (12)	−0.1345 (3)	0.0691 (2)	0.0623 (8)
H14	0.1477	−0.2172	0.0440	0.075*
C15	0.32900 (10)	0.2488 (3)	0.14926 (16)	0.0413 (6)
C16	0.37314 (10)	0.2977 (3)	0.19917 (16)	0.0439 (6)
H16	0.3979	0.2381	0.2276	0.053*
C17	0.37934 (11)	0.4383 (3)	0.20555 (17)	0.0488 (7)
C18	0.34264 (13)	0.5292 (3)	0.1651 (2)	0.0578 (8)
H18	0.3476	0.6236	0.1709	0.069*
C19	0.29890 (13)	0.4776 (3)	0.1165 (2)	0.0590 (8)
H19	0.2737	0.5374	0.0891	0.071*
C20	0.29180 (11)	0.3376 (3)	0.10773 (17)	0.0515 (7)
H20	0.2621	0.3030	0.0741	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0391 (4)	0.0508 (4)	0.0521 (4)	0.0014 (3)	0.0031 (3)	−0.0106 (3)
S2	0.0430 (4)	0.0439 (4)	0.0527 (4)	−0.0060 (3)	0.0027 (3)	0.0035 (3)
O1	0.0535 (12)	0.0619 (13)	0.0912 (16)	−0.0088 (10)	0.0116 (11)	−0.0322 (12)
O2	0.0585 (12)	0.0803 (15)	0.0480 (11)	0.0216 (11)	−0.0003 (9)	0.0024 (10)
O3	0.0549 (12)	0.0501 (12)	0.0906 (16)	−0.0005 (10)	−0.0071 (11)	0.0180 (11)
O4	0.0652 (13)	0.0710 (14)	0.0502 (12)	−0.0182 (11)	0.0094 (10)	−0.0056 (10)
O5	0.0628 (14)	0.0954 (19)	0.0800 (17)	−0.0226 (14)	−0.0046 (13)	−0.0121 (15)
O6	0.0918 (19)	0.0619 (16)	0.139 (2)	−0.0401 (14)	0.0265 (17)	−0.0284 (15)
N1	0.0429 (12)	0.0388 (12)	0.0560 (14)	−0.0062 (9)	0.0114 (10)	−0.0061 (10)
N2	0.0565 (16)	0.0652 (18)	0.0715 (19)	−0.0204 (14)	0.0192 (14)	−0.0170 (14)
C1	0.0491 (19)	0.119 (3)	0.080 (3)	0.011 (2)	−0.0039 (17)	−0.021 (2)
C2	0.0439 (15)	0.076 (2)	0.0498 (17)	0.0085 (15)	0.0036 (13)	−0.0135 (15)
C3	0.0615 (19)	0.0579 (19)	0.0633 (19)	0.0173 (15)	0.0029 (15)	0.0076 (15)
C4	0.0518 (16)	0.0456 (16)	0.0637 (18)	0.0020 (12)	0.0102 (14)	0.0074 (13)
C5	0.0405 (14)	0.0442 (14)	0.0447 (14)	0.0026 (11)	0.0077 (11)	−0.0005 (11)
C6	0.0497 (16)	0.0452 (16)	0.0658 (19)	0.0022 (12)	0.0081 (14)	0.0076 (13)
C7	0.0480 (17)	0.0643 (19)	0.075 (2)	−0.0111 (14)	0.0142 (15)	−0.0034 (16)
C8	0.0517 (19)	0.109 (3)	0.080 (2)	−0.0089 (19)	0.0004 (17)	0.005 (2)
C9	0.0436 (15)	0.0660 (19)	0.0568 (18)	−0.0067 (14)	0.0111 (13)	0.0050 (15)
C10	0.0449 (16)	0.0517 (16)	0.073 (2)	0.0050 (13)	0.0157 (14)	0.0081 (15)
C11	0.0493 (16)	0.0389 (14)	0.0654 (18)	−0.0048 (12)	0.0160 (13)	−0.0052 (13)
C12	0.0381 (13)	0.0394 (13)	0.0504 (15)	−0.0047 (11)	0.0100 (11)	0.0003 (11)
C13	0.0447 (15)	0.0406 (15)	0.081 (2)	−0.0020 (12)	0.0129 (14)	−0.0058 (14)
C14	0.0524 (17)	0.0541 (18)	0.080 (2)	−0.0151 (14)	0.0096 (16)	−0.0190 (16)
C15	0.0406 (13)	0.0373 (13)	0.0471 (15)	−0.0035 (10)	0.0109 (11)	−0.0034 (11)
C16	0.0412 (14)	0.0440 (14)	0.0471 (15)	−0.0018 (11)	0.0096 (11)	0.0002 (12)
C17	0.0509 (15)	0.0477 (15)	0.0510 (16)	−0.0139 (13)	0.0183 (13)	−0.0092 (13)
C18	0.071 (2)	0.0370 (15)	0.071 (2)	0.0008 (14)	0.0272 (17)	0.0011 (14)
C19	0.0645 (19)	0.0500 (17)	0.0631 (19)	0.0145 (14)	0.0123 (16)	0.0057 (14)
C20	0.0469 (15)	0.0554 (17)	0.0514 (16)	0.0041 (13)	0.0059 (13)	−0.0022 (13)

Geometric parameters (Å, º)

S1—O1	1.411 (2)	C7—H7	0.9300
S1—O2	1.421 (2)	C8—C9	1.502 (4)
S1—N1	1.679 (2)	C8—H8A	0.9600
S1—C5	1.755 (3)	C8—H8B	0.9600
S2—O3	1.415 (2)	C8—H8C	0.9600
S2—O4	1.418 (2)	C9—C10	1.375 (4)
S2—N1	1.700 (2)	C9—C14	1.379 (4)
S2—C12	1.754 (3)	C10—C11	1.380 (4)
O5—N2	1.213 (4)	C10—H10	0.9300
O6—N2	1.211 (3)	C11—C12	1.376 (4)
N1—C15	1.448 (3)	C11—H11	0.9300
N2—C17	1.467 (4)	C12—C13	1.376 (4)
C1—C2	1.509 (4)	C13—C14	1.379 (4)
C1—H1A	0.9600	C13—H13	0.9300
C1—H1B	0.9600	C14—H14	0.9300
C1—H1C	0.9600	C15—C16	1.374 (4)
C2—C7	1.377 (4)	C15—C20	1.384 (4)
C2—C3	1.383 (4)	C16—C17	1.378 (4)
C3—C4	1.376 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.383 (4)
C4—C5	1.370 (4)	C18—C19	1.366 (5)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.380 (4)	C19—C20	1.378 (4)
C6—C7	1.378 (4)	C19—H19	0.9300
C6—H6	0.9300	C20—H20	0.9300
O1—S1—O2	120.07 (14)	C9—C8—H8A	109.5
O1—S1—N1	106.96 (13)	C9—C8—H8B	109.5
O2—S1—N1	106.03 (12)	H8A—C8—H8B	109.5
O1—S1—C5	110.14 (13)	C9—C8—H8C	109.5
O2—S1—C5	108.27 (13)	H8A—C8—H8C	109.5
N1—S1—C5	104.16 (12)	H8B—C8—H8C	109.5
O3—S2—O4	120.91 (14)	C10—C9—C14	117.9 (3)
O3—S2—N1	107.36 (13)	C10—C9—C8	120.9 (3)
O4—S2—N1	103.34 (12)	C14—C9—C8	121.2 (3)
O3—S2—C12	109.90 (12)	C9—C10—C11	121.8 (3)
O4—S2—C12	109.52 (13)	C9—C10—H10	119.1
N1—S2—C12	104.36 (12)	C11—C10—H10	119.1
C15—N1—S1	117.25 (17)	C12—C11—C10	118.8 (3)
C15—N1—S2	119.33 (17)	C12—C11—H11	120.6
S1—N1—S2	123.13 (13)	C10—C11—H11	120.6
O6—N2—O5	123.4 (3)	C11—C12—C13	121.0 (3)
O6—N2—C17	118.6 (3)	C11—C12—S2	118.9 (2)
O5—N2—C17	118.1 (3)	C13—C12—S2	120.1 (2)
C2—C1—H1A	109.5	C12—C13—C14	118.7 (3)
C2—C1—H1B	109.5	C12—C13—H13	120.7
H1A—C1—H1B	109.5	C14—C13—H13	120.7
C2—C1—H1C	109.5	C13—C14—C9	121.8 (3)
H1A—C1—H1C	109.5	C13—C14—H14	119.1
H1B—C1—H1C	109.5	C9—C14—H14	119.1
C7—C2—C3	118.2 (3)	C16—C15—C20	121.2 (2)
C7—C2—C1	120.8 (3)	C16—C15—N1	119.0 (2)
C3—C2—C1	121.0 (3)	C20—C15—N1	119.8 (2)
C4—C3—C2	121.1 (3)	C15—C16—C17	117.6 (3)
C4—C3—H3	119.4	C15—C16—H16	121.2
C2—C3—H3	119.4	C17—C16—H16	121.2
C5—C4—C3	119.5 (3)	C16—C17—C18	122.4 (3)
C5—C4—H4	120.2	C16—C17—N2	118.5 (3)
C3—C4—H4	120.2	C18—C17—N2	119.1 (3)
C4—C5—C6	120.7 (3)	C19—C18—C17	118.7 (3)
C4—C5—S1	120.2 (2)	C19—C18—H18	120.7
C6—C5—S1	119.1 (2)	C17—C18—H18	120.7
C7—C6—C5	118.9 (3)	C18—C19—C20	120.4 (3)
C7—C6—H6	120.6	C18—C19—H19	119.8
C5—C6—H6	120.6	C20—C19—H19	119.8
C2—C7—C6	121.6 (3)	C19—C20—C15	119.7 (3)
C2—C7—H7	119.2	C19—C20—H20	120.1
C6—C7—H7	119.2	C15—C20—H20	120.1
O1—S1—N1—C15	−162.34 (19)	C10—C11—C12—C13	−1.9 (4)
O2—S1—N1—C15	−33.1 (2)	C10—C11—C12—S2	176.7 (2)
C5—S1—N1—C15	81.0 (2)	O3—S2—C12—C11	168.2 (2)
O1—S1—N1—S2	11.4 (2)	O4—S2—C12—C11	33.1 (3)
O2—S1—N1—S2	140.62 (16)	N1—S2—C12—C11	−77.0 (2)
C5—S1—N1—S2	−105.25 (16)	O3—S2—C12—C13	−13.3 (3)
O3—S2—N1—C15	−145.6 (2)	O4—S2—C12—C13	−148.4 (2)
O4—S2—N1—C15	−16.7 (2)	N1—S2—C12—C13	101.5 (2)
C12—S2—N1—C15	97.8 (2)	C11—C12—C13—C14	0.8 (4)
O3—S2—N1—S1	40.84 (19)	S2—C12—C13—C14	−177.7 (2)
O4—S2—N1—S1	169.69 (15)	C12—C13—C14—C9	1.3 (5)
C12—S2—N1—S1	−75.78 (17)	C10—C9—C14—C13	−2.4 (5)
C7—C2—C3—C4	−0.6 (5)	C8—C9—C14—C13	177.3 (3)
C1—C2—C3—C4	179.2 (3)	S1—N1—C15—C16	−96.1 (3)
C2—C3—C4—C5	0.5 (5)	S2—N1—C15—C16	89.9 (3)
C3—C4—C5—C6	0.1 (4)	S1—N1—C15—C20	82.4 (3)
C3—C4—C5—S1	−179.4 (2)	S2—N1—C15—C20	−91.6 (3)
O1—S1—C5—C4	−21.6 (3)	C20—C15—C16—C17	−0.8 (4)
O2—S1—C5—C4	−154.7 (2)	N1—C15—C16—C17	177.7 (2)
N1—S1—C5—C4	92.8 (2)	C15—C16—C17—C18	1.2 (4)
O1—S1—C5—C6	158.9 (2)	C15—C16—C17—N2	−179.0 (2)
O2—S1—C5—C6	25.8 (3)	O6—N2—C17—C16	171.6 (3)
N1—S1—C5—C6	−86.8 (2)	O5—N2—C17—C16	−9.4 (4)
C4—C5—C6—C7	−0.6 (4)	O6—N2—C17—C18	−8.6 (4)
S1—C5—C6—C7	178.9 (2)	O5—N2—C17—C18	170.5 (3)
C3—C2—C7—C6	0.1 (5)	C16—C17—C18—C19	−0.6 (4)
C1—C2—C7—C6	−179.7 (3)	N2—C17—C18—C19	179.6 (3)
C5—C6—C7—C2	0.5 (5)	C17—C18—C19—C20	−0.4 (5)
C14—C9—C10—C11	1.3 (5)	C18—C19—C20—C15	0.7 (5)
C8—C9—C10—C11	−178.3 (3)	C16—C15—C20—C19	−0.1 (4)
C9—C10—C11—C12	0.7 (4)	N1—C15—C20—C19	−178.6 (2)