2-Methyl-5-nitro­benzene­sulfonamide

Zia-ur-Rehman, M.; Khan, I.U.; Naz, N.; Arshad, M.N.

doi:10.1107/S1600536809053069

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o136

doi:10.1107/S1600536809053069

Open

access

2-Methyl-5-nitrobenzenesulfonamide

Muhammad Zia-ur-Rehman,^a ^* Islam Ullah Khan,^b Nargis Naz ^c and Muhammad Nadeem Arshad ^b

^aApplied Chemistry Research Centre, PCSIR Laboratories Complex, Ferozpure Road, Lahore 54600, Pakistan, ^bDepartment of Chemistry, Government College University, Lahore 54000, Pakistan, and ^cLahore College for Women University, Jail Road, Lahore 54000, Pakistan
^*Correspondence e-mail: rehman_pcsir@hotmail.com

(Received 16 November 2009; accepted 9 December 2009; online 12 December 2009)

In the title compound, C₇H₈N₂O₄S, the nitro group is twisted by 9.61 (2)° relative to the benzene ring. In the crystal, molecules are linked by N—H⋯O and N—H⋯(O,O) hydrogen bonds between the amino and sulfonyl groups, forming layers parallel to (001).

Related literature

For the biological activity of sulfonamides, see: Ozbek et al. (2007 ); Parari et al. (2008 ); Ratish et al. (2009 ); Selnam et al. (2001 ). For related structures, see: Arshad et al. (2009 ); Gowda et al. (2007a ,b ,c ); Khan et al. (2009 ); Haider et al.(2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₈N₂O₄S
M_r = 216.21
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.9872 (4) Å
b = 6.2814 (5) Å
c = 28.557 (2) Å
V = 894.60 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 296 K
0.43 × 0.17 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.864, T_max = 0.962
5964 measured reflections
2113 independent reflections
1549 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.099
S = 0.89
2112 reflections
136 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 766 Friedel pairs
Flack parameter: −0.02 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N⋯O4ⁱ	0.83 (4)	2.27 (4)	3.055 (4)	158 (3)
N3—H2N⋯O4ⁱⁱ	0.89 (6)	2.30 (6)	3.107 (4)	150 (4)
N3—H2N⋯O3ⁱⁱⁱ	0.89 (6)	2.40 (4)	2.893 (4)	115 (3)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x+1, y, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809053069/is2494sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053069/is2494Isup2.hkl

checkCIF report

Comment top

Sulfonamides are familiar for their anti-HIV (Selnam et al., 2001), anti-inflamatory (Ratish et al., 2009) and anti-microbial (Ozbek et al., 2007; Parari et al., 2008) activities. In continuation of our work regarding the synthesis of various sulfonamides (Arshad et al., 2009; Khan et al., 2009), structure of 2-methyl-5-nitrobenzenesulfonamide (I) has been determined. Bond lengths and bond angles of the title molecule (Fig. 1) are almost similar to those in the related molecules (Gowda et al., 2007a,b,c; Haider et al., 2009) and are within the normal ranges (Allen et al., 1987). Each molecule is linked to its adjacent ones through intermolecular N—H···O hydrogen bonds forming a chain along the a axis, while each chain is linked to its neighbouring chain running in opposite direction via intermolecular N—H···O═S hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For the biological activity of sulfonamides, see: Ozbek et al. (2007); Parari et al. (2008); Ratish et al. (2009); Selnam et al. (2001). For related structures, see: Arshad et al. (2009); Gowda et al. (2007a,b,c); Khan et al. (2009); Haider et al.(2009). For bond-length data, see: Allen et al. (1987).

Experimental top

A well ground mixture of 2-methyl-5-nitrobenzenesulfonyl chloride (2.36 g, 10.0 mmol) and ammonium carbonate (10.0 g) was heated in a china dish till the complete removal of typical smell of sulfonyl chloride. Contents were cooled and washed with water followed by crystallization from methanol.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids at the 50% probability level.
	Fig. 2. Perspective view of the three-dimensional crystal packing showing intermolecular hydrogen-bonded interactions (dashed lines). [Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) x + 1, y, z and (iii) -x + 2, y + 1/2, -z + 3/2]. H atoms not involved in hydrogen bonding have been omitted for clarity.

2-Methyl-5-nitrobenzenesulfonamide top

Crystal data top

C₇H₈N₂O₄S	F(000) = 448
M_r = 216.21	D_x = 1.605 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1325 reflections
a = 4.9872 (4) Å	θ = 2.9–25.4°
b = 6.2814 (5) Å	µ = 0.35 mm⁻¹
c = 28.557 (2) Å	T = 296 K
V = 894.60 (12) Å³	Needles, colourless
Z = 4	0.43 × 0.17 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2113 independent reflections
Radiation source: fine-focus sealed tube	1549 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −3→6
T_min = 0.864, T_max = 0.962	k = −8→8
5964 measured reflections	l = −38→38

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0508P)² + 0.1986P] where P = (F_o² + 2F_c²)/3
S = 0.89	(Δ/σ)_max < 0.001
2112 reflections	Δρ_max = 0.23 e Å⁻³
136 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 766 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (11)

Crystal data top

C₇H₈N₂O₄S	V = 894.60 (12) Å³
M_r = 216.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.9872 (4) Å	µ = 0.35 mm⁻¹
b = 6.2814 (5) Å	T = 296 K
c = 28.557 (2) Å	0.43 × 0.17 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2113 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1549 reflections with I > 2σ(I)
T_min = 0.864, T_max = 0.962	R_int = 0.036
5964 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	Δρ_max = 0.23 e Å⁻³
S = 0.89	Δρ_min = −0.23 e Å⁻³
2112 reflections	Absolute structure: Flack (1983), 766 Friedel pairs
136 parameters	Absolute structure parameter: −0.02 (11)
0 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.7436 (6)	0.4718 (4)	0.85981 (8)	0.0294 (6)
C2	0.6274 (6)	0.6621 (4)	0.87573 (9)	0.0336 (6)
C3	0.7125 (7)	0.7374 (4)	0.91916 (10)	0.0433 (8)
H3	0.6392	0.8629	0.9308	0.052*
C4	0.9018 (6)	0.6316 (5)	0.94542 (9)	0.0425 (7)
H4	0.9568	0.6857	0.9742	0.051*
C5	1.0083 (7)	0.4455 (4)	0.92867 (9)	0.0342 (6)
C6	0.9298 (6)	0.3616 (4)	0.88605 (8)	0.0330 (6)
H6	1.0009	0.2338	0.8753	0.040*
C7	0.4234 (7)	0.7867 (5)	0.84858 (11)	0.0473 (9)
H7A	0.3861	0.9178	0.8646	0.071*
H7B	0.2615	0.7051	0.8459	0.071*
H7C	0.4922	0.8171	0.8179	0.071*
N1	1.2116 (5)	0.3335 (4)	0.95582 (8)	0.0431 (6)
O4	0.3903 (4)	0.3752 (4)	0.79524 (7)	0.0525 (6)
O1	1.3007 (5)	0.4194 (3)	0.99090 (7)	0.0568 (6)
O2	1.2851 (5)	0.1593 (4)	0.94205 (8)	0.0677 (7)
O3	0.7986 (4)	0.1599 (3)	0.80208 (7)	0.0465 (5)
N3	0.8152 (8)	0.5117 (5)	0.76612 (9)	0.0532 (8)
S1	0.67301 (15)	0.36352 (11)	0.80358 (2)	0.03595 (19)
H1N	0.720 (8)	0.605 (5)	0.7540 (12)	0.062 (12)*
H2N	0.994 (12)	0.509 (7)	0.7660 (14)	0.091 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0257 (18)	0.0334 (12)	0.0292 (11)	−0.0031 (12)	0.0030 (11)	0.0005 (10)
C2	0.0294 (18)	0.0338 (13)	0.0374 (12)	−0.0008 (13)	0.0030 (11)	0.0044 (11)
C3	0.046 (2)	0.0403 (14)	0.0437 (15)	0.0085 (15)	0.0036 (15)	−0.0086 (12)
C4	0.047 (2)	0.0469 (15)	0.0334 (12)	0.0080 (17)	−0.0022 (13)	−0.0102 (13)
C5	0.0295 (18)	0.0429 (14)	0.0301 (12)	0.0029 (13)	0.0029 (12)	0.0031 (11)
C6	0.0313 (17)	0.0345 (12)	0.0333 (12)	0.0013 (14)	0.0065 (11)	−0.0029 (12)
C7	0.045 (2)	0.0428 (16)	0.0541 (17)	0.0074 (15)	0.0010 (16)	0.0078 (13)
N1	0.0377 (16)	0.0553 (14)	0.0362 (11)	0.0095 (15)	−0.0022 (11)	0.0052 (11)
O4	0.0291 (12)	0.0768 (14)	0.0515 (12)	−0.0103 (12)	−0.0018 (9)	−0.0106 (11)
O1	0.0521 (16)	0.0746 (15)	0.0436 (11)	0.0029 (13)	−0.0166 (11)	−0.0034 (10)
O2	0.0711 (19)	0.0721 (14)	0.0598 (14)	0.0387 (16)	−0.0127 (13)	−0.0080 (12)
O3	0.0495 (14)	0.0433 (10)	0.0467 (10)	−0.0050 (11)	0.0040 (10)	−0.0132 (9)
N3	0.039 (2)	0.079 (2)	0.0415 (13)	−0.0008 (19)	0.0032 (15)	0.0203 (14)
S1	0.0296 (4)	0.0473 (4)	0.0310 (3)	−0.0068 (4)	0.0021 (3)	−0.0038 (3)

Geometric parameters (Å, º) top

C1—C6	1.379 (4)	C6—H6	0.9300
C1—C2	1.404 (4)	C7—H7A	0.9600
C1—S1	1.779 (3)	C7—H7B	0.9600
C2—C3	1.393 (4)	C7—H7C	0.9600
C2—C7	1.499 (4)	N1—O1	1.221 (3)
C3—C4	1.377 (4)	N1—O2	1.219 (3)
C3—H3	0.9300	O4—S1	1.432 (2)
C4—C5	1.370 (4)	O3—S1	1.425 (2)
C4—H4	0.9300	N3—S1	1.586 (3)
C5—C6	1.383 (3)	N3—H1N	0.83 (4)
C5—N1	1.457 (4)	N3—H2N	0.89 (6)

C6—C1—C2	122.0 (2)	C2—C7—H7A	109.5
C6—C1—S1	115.57 (19)	C2—C7—H7B	109.5
C2—C1—S1	122.4 (2)	H7A—C7—H7B	109.5
C3—C2—C1	116.8 (2)	C2—C7—H7C	109.5
C3—C2—C7	119.3 (3)	H7A—C7—H7C	109.5
C1—C2—C7	123.9 (2)	H7B—C7—H7C	109.5
C4—C3—C2	122.0 (3)	O1—N1—O2	123.5 (3)
C4—C3—H3	119.0	O1—N1—C5	118.5 (2)
C2—C3—H3	119.0	O2—N1—C5	118.1 (2)
C5—C4—C3	119.2 (3)	S1—N3—H1N	116 (3)
C5—C4—H4	120.4	S1—N3—H2N	116 (3)
C3—C4—H4	120.4	H1N—N3—H2N	126 (4)
C4—C5—C6	121.5 (3)	O3—S1—O4	118.28 (15)
C4—C5—N1	119.7 (2)	O3—S1—N3	108.08 (18)
C6—C5—N1	118.8 (2)	O4—S1—N3	107.33 (18)
C1—C6—C5	118.5 (2)	O3—S1—C1	106.47 (12)
C1—C6—H6	120.7	O4—S1—C1	108.99 (13)
C5—C6—H6	120.7	N3—S1—C1	107.21 (15)

C6—C1—C2—C3	1.2 (4)	N1—C5—C6—C1	−177.9 (2)
S1—C1—C2—C3	−175.9 (2)	C4—C5—N1—O1	−6.9 (4)
C6—C1—C2—C7	−179.7 (3)	C6—C5—N1—O1	172.3 (3)
S1—C1—C2—C7	3.3 (4)	C4—C5—N1—O2	173.7 (3)
C1—C2—C3—C4	0.1 (4)	C6—C5—N1—O2	−7.1 (4)
C7—C2—C3—C4	−179.1 (3)	C6—C1—S1—O3	9.8 (2)
C2—C3—C4—C5	−0.6 (5)	C2—C1—S1—O3	−173.0 (2)
C3—C4—C5—C6	0.0 (4)	C6—C1—S1—O4	138.5 (2)
C3—C4—C5—N1	179.2 (3)	C2—C1—S1—O4	−44.3 (3)
C2—C1—C6—C5	−1.8 (4)	C6—C1—S1—N3	−105.7 (2)
S1—C1—C6—C5	175.4 (2)	C2—C1—S1—N3	71.6 (3)
C4—C5—C6—C1	1.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···O4ⁱ	0.83 (4)	2.27 (4)	3.055 (4)	158 (3)
N3—H2N···O4ⁱⁱ	0.89 (6)	2.30 (6)	3.107 (4)	150 (4)
N3—H2N···O3ⁱⁱⁱ	0.89 (6)	2.40 (4)	2.893 (4)	115 (3)

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O₄S
M_r	216.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	4.9872 (4), 6.2814 (5), 28.557 (2)
V (Å³)	894.60 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.43 × 0.17 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.864, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	5964, 2113, 1549
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.099, 0.89
No. of reflections	2112
No. of parameters	136
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23
Absolute structure	Flack (1983), 766 Friedel pairs
Absolute structure parameter	−0.02 (11)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···O4ⁱ	0.83 (4)	2.27 (4)	3.055 (4)	158 (3)
N3—H2N···O4ⁱⁱ	0.89 (6)	2.30 (6)	3.107 (4)	150 (4)
N3—H2N···O3ⁱⁱⁱ	0.89 (6)	2.40 (4)	2.893 (4)	115 (3)

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) −x+2, y+1/2, −z+3/2.

Acknowledgements

The authors are grateful to PCSIR Laboratories Complex, Lahore, Pakistan, for the provision of necessary chemicals and to the Higher Education Commission of Pakistan for its grant for the purchase of diffractometer.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans 2, pp. S1–19. CrossRef Web of Science Google Scholar
Arshad, M. N., Khan, I. U., Zia-ur-Rehman, M. & Shafiq, M. (2009). Acta Cryst. E65, o1204. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gowda, B. T., Foro, S. & Fuess, H. (2007a). Acta Cryst. E63, o2339. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Foro, S. & Fuess, H. (2007b). Acta Cryst. E63, o2570. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Foro, S. & Fuess, H. (2007c). Acta Cryst. E63, o2597. Web of Science CSD CrossRef IUCr Journals Google Scholar
Haider, Z., Khan, I. U., Zia-ur-Rehman, M. & Arshad, M. N. (2009). Acta Cryst. E65, o3053. Web of Science CSD CrossRef IUCr Journals Google Scholar
Khan, I. U., Haider, Z., Zia-ur-Rehman, M., Arshad, M. N. & Shafiq, M. (2009). Acta Cryst. E65, o2867. Web of Science CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ozbek, N., Katircioğ lu, H., Karacan, N. & Baykal, T. (2007). Bioorg. Med. Chem. 15, 5105–5109. Web of Science CrossRef PubMed Google Scholar
Parari, M. K., Panda, G., Srivastava, K. & Puri, S. K. (2008). Bioorg. Med. Chem. Lett. 18, 776–781. PubMed Google Scholar
Ratish, G. I., Javed, K., Ahmad, S., Bano, S., Alam, M. S., Pillai, K. K., Singh, S. & Bagchi, V. (2009). Bioorg. Med. Chem. Lett. 19, 255–258. Web of Science PubMed Google Scholar
Selnam, P., Chandramohan, M., Clercq, E. D., Witvrouw, M. & Pannecouque, C. (2001). Eur. J. Pharm. Sci. 14, 313–316. Web of Science PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar