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Acta Cryst. (2011). E67, o917    [ doi:10.1107/S1600536811009470 ]

4-Methyl-N-(4-nitrobenzoyl)benzenesulfonamide

P. A. Suchetan, S. Foro and B. T. Gowda

Abstract top

In title compound, C14H12N2O5S, the dihedral angle between the sulfonyl benzene ring and the -SO2-NH-C-O segment is 81.5 (2)° and that between the sulfonyl and the benzoyl benzene rings is 89.8 (1)°. In the crystal, molecules are linked into chains along the b axis via intermolecular N-H...O hydrogen bonds. C-H...O interactions are also observed.

Comment top

The amide and sulfonamide moieties are important constituents of many biologically significant compounds. As a part of studying the effect of substituents on the structures of this class of compounds (Gowda et al., 2005, 2007; Suchetan et al., 2010a,b), the structure of 4-methyl-N-(4-nitrobenzoyl)-benzenesulfonamide (I) has been determined. The conformation of the N—H bond in the C—SO2—NH—C(O) segment is anti to the C=O bond (Fig.1), similar to those observed in N-(4-chlorobenzoyl)-4- methylbenzenesulfonamide (II) (Suchetan et al., 2010a) and 4-methyl-N-(4-methylbenzoyl)-benzenesulfonamide (III) (Suchetan et al., 2010b).

The molecules are twisted at the S atoms with the C—S(O2)—NH—C(O) torsional angle of 58.7 (3)°, compared to the values of 67.1 (2)° (molecule 1) and 67.7 (2)° (molecule 2) in (II) and 62.0 (2)° in (III).

The dihedral angle between the sulfonyl benzene ring and the —SO2—NH—C—O segment is 81.5 (2)°, compared to the values of 83.6 (1)° (molecule 1) and 81.0 (1)° (molecule 2) in (II) and 84.9 (1)° in (III).

The dihedral angle between the sulfonyl and the benzoyl benzene rings is 89.8 (1)°, compared to the values of 81.0 (1)° (molecule 1) and 76.3 (1)° (molecule 2) in (II) and 89.0 (1)° in (III).

In the crystal packing the molecules are linked by intermolecular N—H···O hydrogen bonds (Table 1, Fig. 2). Two C—H···O interactions are also observed.

Related literature top

For background to our study of the effect of substituents on the structures of methanesulfonamides, see: Gowda et al. (2007). For the effect of substituents in N-(aryl)-arylsulfonamides, see: Gowda et al. (2005). For the effect of substituents on the structures of N-(p-substituted benzoyl)-p-substituted benzenesulfonamides, see: Suchetan et al. (2010a,b).

Experimental top

The title compound was prepared by refluxing a mixture of 4-nitrobenzoic acid, 4-methylbenzenesulfonamide and phosphorous oxychloride for 3 hr on a water bath. The resultant mixture was cooled and poured into ice cold water. The solid obtained was filtered, washed thoroughly with water and then dissolved in sodium bicarbonate solution. The compound was later reprecipitated by acidifying the filtered solution with dilute HCl. It was filtered, dried and recrystallized.

The rod like colourless single crystals of the title compound used in X-ray diffraction studies were obtained by slow evaporation of a toluene solution at room temperature.

Refinement top

The H atom of the NH group was located in a difference map and later restrained to N—H = 0.86 (3) Å. The other H atoms were positioned with idealized geometry using a riding model with the aromatic C—H distance = 0.93 Å and methyl C—H = 0.96 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent atom).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom- labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing in the title compound. Hydrogen bonds are shown as dashed lines.
4-Methyl-N-(4-nitrobenzoyl)benzenesulfonamide top
Crystal data top
C14H12N2O5SF(000) = 332
Mr = 320.32Dx = 1.465 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1463 reflections
a = 11.722 (3) Åθ = 2.8–27.9°
b = 5.137 (1) ŵ = 0.25 mm−1
c = 12.488 (3) ÅT = 293 K
β = 105.09 (2)°Rod, colourless
V = 726.0 (3) Å30.40 × 0.12 × 0.08 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector		2265 independent reflections
Radiation source: fine-focus sealed tube1993 reflections with I > 2σ(I)
graphiteRint = 0.030
Rotation method data acquisition using ω and φ scansθmax = 26.4°, θmin = 2.8°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		h = −13→14
Tmin = 0.907, Tmax = 0.980k = −4→6
2664 measured reflectionsl = −15→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128 w = 1/[σ2(Fo2) + (0.0525P)2 + 0.6019P]
where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max = 0.001
2265 reflectionsΔρmax = 0.26 e Å−3
203 parametersΔρmin = −0.36 e Å−3
2 restraintsAbsolute structure: Flack (1983), 605 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.05 (14)
Crystal data top
C14H12N2O5SV = 726.0 (3) Å3
Mr = 320.32Z = 2
Monoclinic, P21Mo Kα radiation
a = 11.722 (3) ŵ = 0.25 mm−1
b = 5.137 (1) ÅT = 293 K
c = 12.488 (3) Å0.40 × 0.12 × 0.08 mm
β = 105.09 (2)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector		2265 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		1993 reflections with I > 2σ(I)
Tmin = 0.907, Tmax = 0.980Rint = 0.030
2664 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128Δρmax = 0.26 e Å−3
S = 1.17Δρmin = −0.36 e Å−3
2265 reflectionsAbsolute structure: Flack (1983), 605 Friedel pairs
203 parametersFlack parameter: −0.05 (14)
2 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.2737 (4)0.1687 (9)0.1307 (3)0.0362 (9)
C20.2176 (4)0.3782 (10)0.0686 (4)0.0460 (11)
H20.25100.46080.01780.055*
C30.1097 (4)0.4617 (11)0.0842 (4)0.0532 (13)
H30.07080.60110.04280.064*
C40.0597 (4)0.3414 (10)0.1600 (4)0.0481 (12)
C50.1184 (4)0.1350 (11)0.2208 (4)0.0522 (13)
H50.08530.05170.27160.063*
C60.2260 (4)0.0498 (12)0.2073 (3)0.0438 (9)
H60.2655−0.08710.25000.053*
C70.5340 (4)0.3078 (9)0.2885 (3)0.0371 (10)
C80.6231 (3)0.5138 (8)0.3373 (3)0.0343 (10)
C90.6277 (4)0.5947 (12)0.4452 (3)0.0509 (12)
H90.57790.51900.48340.061*
C100.7056 (5)0.7857 (11)0.4949 (4)0.0549 (14)
H100.70750.84380.56580.066*
C110.7808 (4)0.8898 (10)0.4380 (4)0.0449 (11)
C120.7788 (4)0.8124 (10)0.3324 (4)0.0499 (12)
H120.83010.88640.29530.060*
C130.6993 (4)0.6224 (10)0.2822 (3)0.0469 (13)
H130.69720.56720.21080.056*
C14−0.0577 (4)0.4337 (15)0.1747 (5)0.0717 (17)
H14A−0.11320.29240.16020.086*
H14B−0.08690.57340.12380.086*
H14C−0.04760.49410.24930.086*
N10.5123 (3)0.2647 (7)0.1742 (3)0.0329 (8)
H1N0.525 (4)0.377 (8)0.129 (3)0.039*
N20.8665 (4)1.0941 (10)0.4911 (3)0.0568 (11)
O10.4318 (3)−0.1903 (6)0.1572 (3)0.0502 (8)
O20.4040 (3)0.0951 (7)−0.0061 (2)0.0487 (8)
O30.4829 (3)0.1812 (7)0.3440 (2)0.0542 (9)
O40.9267 (4)1.1940 (9)0.4363 (4)0.0806 (13)
O50.8702 (4)1.1530 (10)0.5865 (3)0.0890 (15)
S10.40811 (9)0.0583 (2)0.10898 (7)0.0359 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.040 (2)0.035 (2)0.0326 (19)0.0028 (19)0.0070 (16)−0.0031 (18)
C20.048 (3)0.039 (3)0.050 (3)−0.002 (2)0.013 (2)0.001 (2)
C30.052 (3)0.053 (3)0.049 (3)0.015 (2)0.003 (2)0.010 (2)
C40.041 (2)0.061 (3)0.038 (2)0.003 (2)0.0028 (19)−0.006 (2)
C50.047 (2)0.065 (4)0.046 (2)−0.002 (2)0.0154 (19)0.003 (2)
C60.048 (2)0.045 (2)0.0384 (19)0.003 (3)0.0112 (17)0.005 (3)
C70.038 (2)0.044 (3)0.031 (2)0.006 (2)0.0105 (17)0.0044 (19)
C80.0359 (19)0.039 (3)0.0254 (16)0.0066 (19)0.0035 (14)−0.0010 (17)
C90.058 (3)0.063 (4)0.0313 (19)−0.005 (3)0.0122 (18)0.000 (2)
C100.073 (3)0.058 (4)0.031 (2)0.001 (3)0.009 (2)−0.007 (2)
C110.047 (2)0.038 (3)0.043 (2)0.008 (2)−0.001 (2)0.002 (2)
C120.051 (3)0.057 (3)0.044 (2)−0.011 (2)0.015 (2)−0.008 (2)
C130.047 (2)0.063 (4)0.0330 (19)−0.005 (2)0.0133 (18)−0.008 (2)
C140.049 (3)0.099 (5)0.066 (3)0.018 (3)0.013 (3)−0.001 (3)
N10.0442 (19)0.030 (2)0.0241 (16)0.0003 (16)0.0081 (14)0.0031 (13)
N20.064 (2)0.047 (3)0.048 (2)0.002 (2)−0.0050 (18)−0.005 (2)
O10.053 (2)0.037 (2)0.061 (2)0.0047 (16)0.0156 (15)−0.0032 (15)
O20.0562 (17)0.060 (2)0.0305 (13)−0.0034 (18)0.0115 (12)−0.0111 (16)
O30.062 (2)0.069 (2)0.0339 (15)−0.0161 (19)0.0162 (14)0.0028 (16)
O40.080 (3)0.077 (3)0.074 (3)−0.031 (3)0.002 (2)−0.004 (2)
O50.113 (3)0.089 (4)0.056 (2)−0.019 (3)0.006 (2)−0.029 (2)
S10.0428 (5)0.0325 (5)0.0324 (4)0.0018 (6)0.0099 (4)−0.0027 (5)
Geometric parameters (Å, °) top
C1—C61.371 (6)C9—H90.9300
C1—C21.388 (6)C10—C111.376 (7)
C1—S11.761 (4)C10—H100.9300
C2—C31.396 (6)C11—C121.372 (6)
C2—H20.9300C11—N21.485 (6)
C3—C41.383 (7)C12—C131.382 (6)
C3—H30.9300C12—H120.9300
C4—C51.379 (7)C13—H130.9300
C4—C141.511 (7)C14—H14A0.9600
C5—C61.385 (6)C14—H14B0.9600
C5—H50.9300C14—H14C0.9600
C6—H60.9300N1—S11.661 (4)
C7—O31.215 (5)N1—H1N0.85 (3)
C7—N11.401 (5)N2—O41.217 (6)
C7—C81.500 (6)N2—O51.219 (5)
C8—C131.379 (6)O1—S11.409 (3)
C8—C91.398 (5)O2—S11.438 (3)
C9—C101.374 (7)
C6—C1—C2121.0 (4)C11—C10—H10120.5
C6—C1—S1120.5 (4)C12—C11—C10122.1 (5)
C2—C1—S1118.4 (3)C12—C11—N2118.3 (4)
C1—C2—C3118.3 (4)C10—C11—N2119.6 (4)
C1—C2—H2120.8C11—C12—C13118.7 (4)
C3—C2—H2120.8C11—C12—H12120.6
C4—C3—C2121.3 (5)C13—C12—H12120.6
C4—C3—H3119.4C8—C13—C12120.5 (4)
C2—C3—H3119.4C8—C13—H13119.7
C5—C4—C3118.7 (4)C12—C13—H13119.7
C5—C4—C14121.0 (5)C4—C14—H14A109.5
C3—C4—C14120.3 (5)C4—C14—H14B109.5
C4—C5—C6121.1 (4)H14A—C14—H14B109.5
C4—C5—H5119.5C4—C14—H14C109.5
C6—C5—H5119.5H14A—C14—H14C109.5
C1—C6—C5119.5 (5)H14B—C14—H14C109.5
C1—C6—H6120.2C7—N1—S1121.0 (3)
C5—C6—H6120.2C7—N1—H1N124 (3)
O3—C7—N1120.7 (4)S1—N1—H1N110 (3)
O3—C7—C8122.7 (4)O4—N2—O5124.5 (5)
N1—C7—C8116.6 (3)O4—N2—C11118.1 (4)
C13—C8—C9119.5 (4)O5—N2—C11117.4 (5)
C13—C8—C7123.8 (3)O1—S1—O2119.9 (2)
C9—C8—C7116.7 (4)O1—S1—N1109.32 (19)
C10—C9—C8120.1 (4)O2—S1—N1103.62 (18)
C10—C9—H9119.9O1—S1—C1108.1 (2)
C8—C9—H9119.9O2—S1—C1108.24 (19)
C9—C10—C11119.0 (4)N1—S1—C1106.99 (19)
C9—C10—H10120.5
C6—C1—C2—C3−1.4 (7)N2—C11—C12—C13−180.0 (4)
S1—C1—C2—C3178.6 (4)C9—C8—C13—C12−0.9 (7)
C1—C2—C3—C40.5 (7)C7—C8—C13—C12179.7 (4)
C2—C3—C4—C50.0 (7)C11—C12—C13—C80.3 (7)
C2—C3—C4—C14−179.4 (5)O3—C7—N1—S15.4 (5)
C3—C4—C5—C60.5 (7)C8—C7—N1—S1−175.2 (3)
C14—C4—C5—C6179.9 (5)C12—C11—N2—O44.0 (7)
C2—C1—C6—C51.9 (7)C10—C11—N2—O4−175.5 (5)
S1—C1—C6—C5−178.1 (4)C12—C11—N2—O5−177.1 (5)
C4—C5—C6—C1−1.4 (7)C10—C11—N2—O53.4 (7)
O3—C7—C8—C13166.2 (4)C7—N1—S1—O1−58.2 (4)
N1—C7—C8—C13−13.2 (6)C7—N1—S1—O2172.9 (3)
O3—C7—C8—C9−13.2 (6)C7—N1—S1—C158.7 (3)
N1—C7—C8—C9167.4 (4)C6—C1—S1—O115.4 (4)
C13—C8—C9—C101.7 (7)C2—C1—S1—O1−164.7 (3)
C7—C8—C9—C10−178.9 (4)C6—C1—S1—O2146.7 (4)
C8—C9—C10—C11−1.9 (8)C2—C1—S1—O2−33.4 (4)
C9—C10—C11—C121.3 (8)C6—C1—S1—N1−102.2 (4)
C9—C10—C11—N2−179.3 (4)C2—C1—S1—N177.7 (4)
C10—C11—C12—C13−0.5 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.85 (3)2.22 (3)3.054 (4)164 (4)
N1—H1N···O1ii0.85 (3)2.54 (4)2.944 (5)110 (3)
C9—H9···O3iii0.932.583.254 (5)130
C13—H13···O2i0.932.533.347 (5)147
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) x, y+1, z; (iii) −x+1, y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.85 (3)2.22 (3)3.054 (4)164 (4)
N1—H1N···O1ii0.85 (3)2.54 (4)2.944 (5)110 (3)
C9—H9···O3iii0.932.583.254 (5)130
C13—H13···O2i0.932.533.347 (5)147
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) x, y+1, z; (iii) −x+1, y+1/2, −z+1.
Acknowledgements top

PAS thanks the Council of Scientific and Industrial Research (CSIR), Government of India, New Delhi, for the award of a research fellowship.

references
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2339.

Gowda, B. T., Shetty, M. & Jayalakshmi, K. L. (2005). Z. Naturforsch. Teil A, 60, 106–112.

Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Suchetan, P. A., Gowda, B. T., Foro, S. & Fuess, H. (2010a). Acta Cryst. E66, o327.

Suchetan, P. A., Gowda, B. T., Foro, S. & Fuess, H. (2010b). Acta Cryst. E66, o1510.