N-(2-Meth­oxy­phen­yl)-4-methyl­benzene­sulfonamide

Khan, I.U.; Sheikh, T.A.; Arshad, M.N.

doi:10.1107/S1600536810042984

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2976

https://doi.org/10.1107/S1600536810042984

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N-(2-Methoxyphenyl)-4-methylbenzenesulfonamide

Islam Ullah Khan,^a ^* Tahir Ali Sheikh ^a and Muhammad Nadeem Arshad ^a

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan
^*Correspondence e-mail: iukhan.gcu@gmail.com

(Received 20 October 2010; accepted 21 October 2010; online 30 October 2010)

In the title compound, C₁₄H₁₅NO₃S, the geometry around the S atom of the SO₂ group is distorted tetrahedral. The methoxy- and methyl-substituted aromatic rings are oriented at a dihedral angle of 71.39 (9)°. Intermolecular N—H⋯O hydrogen bonds form inversion dimers, which stabilize the crystal structure.

Related literature

For the antimicrobial activity of sulfonamide compounds, see: Gao & Pederson (2005 ). For a related thiazine molecule, see: Arshad et al. (2010 ). For a related structure, see: Aziz-ur-Rehman et al. (2010 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₅NO₃S
M_r = 277.33
Orthorhombic, P b c a
a = 12.7395 (9) Å
b = 11.4906 (6) Å
c = 18.6968 (10) Å
V = 2736.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.42 × 0.33 × 0.21 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.906, T_max = 0.951
13798 measured reflections
3376 independent reflections
1313 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.143
S = 0.91
3376 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.84	2.35	3.112 (3)	151
Symmetry code: (i) -x+1, -y+1, -z+1.

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: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810042984/sj5047sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042984/sj5047Isup2.hkl

checkCIF report

Comment top

Sulfonamide compounds are well known as antimicrobial agents (Gao & Pederson, 2005). The structure reported here is a precursor used in the synthesis of thiazine heterocycles (Arshad et al., 2010).

The bond lengths and angles in the title compound are similar to those observed in the recently published N-(2-methoxyphenyl)benzenesulfonamide (II) (Aziz-ur-Rehman et al., 2010). The two aromatic rings (C1/C2/C3/C4/C5/C6) and C7/C8/C9/C10/C11/C12) are oriented at dihedral angles of 71.39 (0.09)° unlike the dihedral angles observed for the two independent molecules in II. Similarly the torsion angle C—S—N(H)—C is -56.5 (3) compared with 67.25 (15)° in molecule A and -81.17 (16)° in molecule B of (II). Inversion related intermolecular N—H···O hydrogen bonds form dimers and generate an eight-membered R₂²(8) ring motif (Bernstein et al., 1995) Table. 1, Fig. 2.

Related literature top

For the antimicrobial activity of sulfonamide compounds, see: Gao & Pederson (2005). For a related thiazine molecule, see: Arshad et al. (2010). For a related structure, see: Aziz-ur-Rehman et al. (2010). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of para toluenesulfonyl chloride (0.00104 mol; 0.200 g), o-anisidine (0.00104 mol; 0.128 g), was stirred in 10–15 ml of distilled water, while maintaining pH of the reaction mixture at 8–10 using 3% sodium carbonate. The progress of the reaction was checked by TLC. On completion of reaction the precipitates obtained were filtered, washed with water and finally dried. Suitable crystals for X-Ray analysis were grown from DCM (dichloromethane) by slow evaporation.

Structure description top

Sulfonamide compounds are well known as antimicrobial agents (Gao & Pederson, 2005). The structure reported here is a precursor used in the synthesis of thiazine heterocycles (Arshad et al., 2010).

For the antimicrobial activity of sulfonamide compounds, see: Gao & Pederson (2005). For a related thiazine molecule, see: Arshad et al. (2010). For a related structure, see: Aziz-ur-Rehman et al. (2010). For graph-set notation, see: Bernstein et al. (1995).

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: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids.
	Fig. 2. Inversion dimers formed through N—H···O hydrogen bonds drawn as dashed lines.

N-(2-Methoxyphenyl)-4-methylbenzenesulfonamide top

Crystal data top

C₁₄H₁₅NO₃S	F(000) = 1168
M_r = 277.33	D_x = 1.346 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1013 reflections
a = 12.7395 (9) Å	θ = 3.2–19.2°
b = 11.4906 (6) Å	µ = 0.24 mm⁻¹
c = 18.6968 (10) Å	T = 296 K
V = 2736.9 (3) Å³	Needle, light brown
Z = 8	0.42 × 0.33 × 0.21 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3376 independent reflections
Radiation source: fine-focus sealed tube	1313 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
φ and ω scans	θ_max = 28.3°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −16→10
T_min = 0.906, T_max = 0.951	k = −11→15
13798 measured reflections	l = −24→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0552P)²] where P = (F_o² + 2F_c²)/3
3376 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₄H₁₅NO₃S	V = 2736.9 (3) Å³
M_r = 277.33	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.7395 (9) Å	µ = 0.24 mm⁻¹
b = 11.4906 (6) Å	T = 296 K
c = 18.6968 (10) Å	0.42 × 0.33 × 0.21 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3376 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1313 reflections with I > 2σ(I)
T_min = 0.906, T_max = 0.951	R_int = 0.086
13798 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 0.91	Δρ_max = 0.18 e Å⁻³
3376 reflections	Δρ_min = −0.28 e Å⁻³
174 parameters

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
S1	0.51740 (7)	0.61649 (6)	0.39096 (4)	0.0571 (3)
O1	0.60405 (18)	0.61039 (18)	0.34278 (11)	0.0706 (7)
N1	0.55946 (19)	0.6656 (2)	0.46723 (12)	0.0529 (7)
C1	0.4303 (2)	0.7199 (2)	0.35541 (14)	0.0465 (7)
O2	0.46120 (19)	0.51265 (17)	0.40827 (11)	0.0751 (7)
C2	0.4619 (3)	0.7899 (3)	0.30004 (16)	0.0584 (8)
H2	0.5298	0.7842	0.2822	0.070*
O3	0.49484 (18)	0.80720 (18)	0.56921 (11)	0.0662 (6)
C3	0.3924 (3)	0.8688 (3)	0.27103 (16)	0.0607 (9)
H3	0.4146	0.9162	0.2337	0.073*
C4	0.2908 (3)	0.8796 (2)	0.29578 (15)	0.0510 (8)
C5	0.2613 (3)	0.8091 (3)	0.35213 (17)	0.0598 (9)
H5	0.1935	0.8150	0.3703	0.072*
H1N	0.5306	0.6270	0.4999	0.072*
C6	0.3298 (3)	0.7303 (3)	0.38188 (16)	0.0610 (9)
H6	0.3082	0.6839	0.4199	0.073*
C7	0.6101 (2)	0.7748 (2)	0.47481 (15)	0.0481 (8)
C8	0.5756 (2)	0.8488 (2)	0.52917 (16)	0.0491 (8)
C9	0.6239 (3)	0.9550 (3)	0.53963 (18)	0.0650 (9)
H9	0.6006	1.0047	0.5755	0.078*
C10	0.7065 (3)	0.9868 (3)	0.4967 (2)	0.0742 (11)
H10	0.7391	1.0583	0.5038	0.089*
C11	0.7412 (3)	0.9152 (3)	0.4440 (2)	0.0766 (11)
H11	0.7969	0.9380	0.4151	0.092*
C12	0.6934 (3)	0.8076 (3)	0.43331 (16)	0.0629 (9)
H12	0.7182	0.7579	0.3979	0.075*
C13	0.2160 (3)	0.9656 (3)	0.26372 (17)	0.0697 (10)
H13A	0.2137	0.9552	0.2128	0.105*
H13B	0.2391	1.0432	0.2745	0.105*
H13C	0.1472	0.9536	0.2833	0.105*
C14	0.4637 (3)	0.8720 (3)	0.63051 (18)	0.0889 (12)
H14A	0.4396	0.9476	0.6159	0.133*
H14B	0.5224	0.8804	0.6623	0.133*
H14C	0.4079	0.8318	0.6547	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0728 (6)	0.0410 (5)	0.0575 (5)	0.0023 (4)	−0.0082 (5)	−0.0047 (4)
O1	0.0764 (17)	0.0696 (16)	0.0659 (14)	0.0201 (12)	0.0028 (13)	−0.0123 (12)
N1	0.0685 (19)	0.0410 (14)	0.0491 (14)	−0.0108 (13)	−0.0068 (13)	0.0069 (12)
C1	0.057 (2)	0.0393 (17)	0.0436 (16)	−0.0066 (15)	0.0000 (15)	−0.0013 (14)
O2	0.104 (2)	0.0370 (12)	0.0845 (16)	−0.0171 (12)	−0.0261 (14)	0.0047 (11)
C2	0.051 (2)	0.064 (2)	0.0603 (19)	0.0033 (17)	0.0091 (17)	0.0070 (17)
O3	0.0647 (17)	0.0638 (14)	0.0700 (14)	−0.0036 (12)	0.0084 (12)	−0.0086 (12)
C3	0.067 (2)	0.064 (2)	0.0515 (19)	0.0029 (19)	0.0090 (18)	0.0179 (17)
C4	0.056 (2)	0.0500 (19)	0.0469 (18)	0.0010 (16)	−0.0005 (16)	−0.0061 (16)
C5	0.051 (2)	0.063 (2)	0.065 (2)	−0.0016 (17)	0.0114 (17)	0.0007 (18)
C6	0.070 (3)	0.057 (2)	0.0552 (19)	−0.0038 (18)	0.0124 (19)	0.0129 (17)
C7	0.052 (2)	0.0433 (18)	0.0492 (18)	−0.0005 (16)	−0.0084 (16)	0.0078 (15)
C8	0.047 (2)	0.046 (2)	0.0543 (18)	−0.0001 (16)	−0.0065 (16)	0.0053 (15)
C9	0.078 (3)	0.050 (2)	0.066 (2)	−0.007 (2)	−0.014 (2)	−0.0039 (18)
C10	0.084 (3)	0.060 (2)	0.079 (2)	−0.024 (2)	−0.022 (2)	0.010 (2)
C11	0.072 (3)	0.086 (3)	0.072 (3)	−0.028 (2)	−0.007 (2)	0.020 (2)
C12	0.065 (2)	0.069 (2)	0.055 (2)	−0.0093 (19)	−0.0024 (18)	0.0010 (18)
C13	0.068 (3)	0.075 (2)	0.066 (2)	0.015 (2)	0.0018 (19)	0.0041 (18)
C14	0.098 (3)	0.100 (3)	0.069 (2)	0.005 (2)	0.012 (2)	−0.011 (2)

Geometric parameters (Å, º) top

S1—O1	1.426 (2)	C6—H6	0.9300
S1—O2	1.429 (2)	C7—C12	1.368 (4)
S1—N1	1.625 (2)	C7—C8	1.396 (4)
S1—C1	1.756 (3)	C8—C9	1.381 (4)
N1—C7	1.418 (3)	C9—C10	1.373 (5)
N1—H1N	0.8394	C9—H9	0.9300
C1—C2	1.371 (4)	C10—C11	1.357 (5)
C1—C6	1.378 (4)	C10—H10	0.9300
C2—C3	1.378 (4)	C11—C12	1.393 (4)
C2—H2	0.9300	C11—H11	0.9300
O3—C8	1.359 (3)	C12—H12	0.9300
O3—C14	1.424 (3)	C13—H13A	0.9600
C3—C4	1.379 (4)	C13—H13B	0.9600
C3—H3	0.9300	C13—H13C	0.9600
C4—C5	1.382 (4)	C14—H14A	0.9600
C4—C13	1.498 (4)	C14—H14B	0.9600
C5—C6	1.375 (4)	C14—H14C	0.9600
C5—H5	0.9300

O1—S1—O2	119.32 (14)	C12—C7—N1	122.7 (3)
O1—S1—N1	108.43 (13)	C8—C7—N1	117.9 (3)
O2—S1—N1	104.86 (12)	O3—C8—C9	124.8 (3)
O1—S1—C1	106.45 (14)	O3—C8—C7	115.1 (3)
O2—S1—C1	109.52 (15)	C9—C8—C7	120.1 (3)
N1—S1—C1	107.79 (13)	C10—C9—C8	119.6 (3)
C7—N1—S1	123.03 (19)	C10—C9—H9	120.2
C7—N1—H1N	126.5	C8—C9—H9	120.2
S1—N1—H1N	108.1	C11—C10—C9	120.9 (3)
C2—C1—C6	119.5 (3)	C11—C10—H10	119.6
C2—C1—S1	119.8 (3)	C9—C10—H10	119.6
C6—C1—S1	120.6 (2)	C10—C11—C12	120.0 (4)
C1—C2—C3	119.7 (3)	C10—C11—H11	120.0
C1—C2—H2	120.2	C12—C11—H11	120.0
C3—C2—H2	120.2	C7—C12—C11	120.1 (3)
C8—O3—C14	118.1 (3)	C7—C12—H12	119.9
C2—C3—C4	122.0 (3)	C11—C12—H12	119.9
C2—C3—H3	119.0	C4—C13—H13A	109.5
C4—C3—H3	119.0	C4—C13—H13B	109.5
C3—C4—C5	117.3 (3)	H13A—C13—H13B	109.5
C3—C4—C13	121.4 (3)	C4—C13—H13C	109.5
C5—C4—C13	121.2 (3)	H13A—C13—H13C	109.5
C6—C5—C4	121.4 (3)	H13B—C13—H13C	109.5
C6—C5—H5	119.3	O3—C14—H14A	109.5
C4—C5—H5	119.3	O3—C14—H14B	109.5
C5—C6—C1	120.1 (3)	H14A—C14—H14B	109.5
C5—C6—H6	120.0	O3—C14—H14C	109.5
C1—C6—H6	120.0	H14A—C14—H14C	109.5
C12—C7—C8	119.3 (3)	H14B—C14—H14C	109.5

O1—S1—N1—C7	58.3 (3)	C2—C1—C6—C5	1.0 (5)
O2—S1—N1—C7	−173.2 (2)	S1—C1—C6—C5	−178.0 (2)
C1—S1—N1—C7	−56.5 (3)	S1—N1—C7—C12	−51.4 (4)
O1—S1—C1—C2	−11.4 (3)	S1—N1—C7—C8	131.6 (2)
O2—S1—C1—C2	−141.7 (2)	C14—O3—C8—C9	−6.2 (4)
N1—S1—C1—C2	104.7 (2)	C14—O3—C8—C7	173.0 (3)
O1—S1—C1—C6	167.6 (2)	C12—C7—C8—O3	−177.7 (3)
O2—S1—C1—C6	37.3 (3)	N1—C7—C8—O3	−0.6 (4)
N1—S1—C1—C6	−76.3 (3)	C12—C7—C8—C9	1.5 (4)
C6—C1—C2—C3	−0.7 (4)	N1—C7—C8—C9	178.6 (3)
S1—C1—C2—C3	178.3 (2)	O3—C8—C9—C10	178.5 (3)
C1—C2—C3—C4	−0.3 (5)	C7—C8—C9—C10	−0.6 (5)
C2—C3—C4—C5	1.0 (5)	C8—C9—C10—C11	0.1 (5)
C2—C3—C4—C13	−179.9 (3)	C9—C10—C11—C12	−0.5 (6)
C3—C4—C5—C6	−0.7 (5)	C8—C7—C12—C11	−1.8 (5)
C13—C4—C5—C6	−179.8 (3)	N1—C7—C12—C11	−178.9 (3)
C4—C5—C6—C1	−0.3 (5)	C10—C11—C12—C7	1.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.84	2.35	3.112 (3)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO₃S
M_r	277.33
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	12.7395 (9), 11.4906 (6), 18.6968 (10)
V (Å³)	2736.9 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.42 × 0.33 × 0.21

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.906, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	13798, 3376, 1313
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.143, 0.91
No. of reflections	3376
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), 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
N1—H1N···O2ⁱ	0.84	2.35	3.112 (3)	150.6

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors acknowledge the Higher Education Commission of Pakistan for providing grant for the project to strengthen the Materials Chemistry Laboratory at GC University Lahore, Pakistan.

References

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