N-(2-Methyl­phenyl­sulfon­yl)acetamide

Abstract

In the mol­ecular structure of the title compound, C₉H₁₁NO₃S, the N—H and C=O bonds are anti to each other, while the amide H atom is syn with respect to the ortho-methyl group in the benzene ring. The C—S—N—C torsion angle is −58.2 (2)°, indicating a twist in the mol­ecule. In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into chains along the c axis.

Related literature

For the sulfanilamide moiety in sulfonamide drugs, see: Maren (1976 ▶). For hydrogen bonding modes of sulfonamides, see: Adsmond & Grant (2001 ▶). For our study of the effect of substituents on the structures of N-(ar­yl)-amides, see: Gowda et al. (2004 ▶). For background to the structures of N-(substituted phenyl­sulfon­yl)-substituted-amides, see: Gowda et al. (2010 ▶); Shakuntala et al. (2011 ▶) and for the oxidative strengths of N-chloro, N-aryl­sulfonamides, see: Gowda & Kumar (2003 ▶).

Experimental

Crystal data

• C₉H₁₁NO₃S

• M _r = 213.25

• Tetragonal,

• a = 7.9804 (5) Å

• c = 16.749 (1) Å

• V = 1066.69 (11) ų

• Z = 4

• Mo Kα radiation

• μ = 0.29 mm⁻¹

• T = 293 K

• 0.40 × 0.18 × 0.12 mm

Data collection

• Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector

• Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.895, T _max = 0.967

• 4245 measured reflections

• 1944 independent reflections

• 1690 reflections with I > 2σ(I)

• R _int = 0.016

Refinement

• R[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 0.086

• S = 1.08

• 1944 reflections

• 132 parameters

• 2 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

• Absolute structure: Flack (1983 ▶), 824 Friedel pairs

• Flack parameter: 0.03 (9)

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

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3i	0.86 (2)	1.95 (2)	2.770 (3)	162 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The structures of sulfonamide drugs contain the sulfanilamide moiety (Maren, 1976). The hydrogen bonding preferences of sulfonamides has been investigated (Adsmond & Grant, 2001). The nature and position of the substituents play a significant role on their crystal structures and other aspects of N-(aryl)-amides and N-(aryl)-sulfonamides (Gowda et al., 2003, 2004; Shakuntala et al., 2011). As a part of a study of the effects of substituents on the structures of this class of compounds, the structure of N-(2-methylphenylsulfonyl)-acetamide (I) has been determined (Fig. 1). The conformation of the N—C bond in the C—SO₂—NH—C(O) segment has gauche torsions with respect to the S═O bonds, the torsion angles being C7—N1—S1—O2 = 57.5 (3) ° and C7—N1—S1—O1 = -174.5 (2) °.

The N—H and C═O bonds are anti to each other, similar to that observed in N-(phenylsulfonyl)-acetamide (II) (Gowda et al., 2010) and N-(2-chlorophenylsulfonyl)-acetamide (III) (Shakuntala et al., 2011). Further, the conformation of the amide-H atom is syn to the ortho-methyl group in the benzene ring, similar to that observed between the amide-H atom and the ortho-chloro group in (III). The molecule of (I) is bent at the S-atom with a C—S—N—C torsion angle of -58.2 (2) °, compared to the values of -58.8 (4) ° in (II), and -71.7 (3) and 61.2 (3) ° in the two independent molecules of (III).

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains along the c axis; part of the crystal structure is shown in Fig. 2.

Experimental

The title compound was prepared by refluxing 2-methylbenzenesulfonamide (0.10 mole) with an excess of acetyl chloride (0.20 mole) for one hour on a water bath. The reaction mixture was cooled and poured into ice cold water. The resulting solid was separated, washed thoroughly with water and dissolved in warm dilute sodium hydrogen carbonate solution. The title compound was re-precipitated by acidifying the filtered solution with glacial acetic acid. It was filtered, dried and recrystallized from ethanol. Colourless rods of the title compound were obtained from a slow evaporation of its ethanol solution.

Refinement

The H atom of the NH group was located in a difference map and later restrained to the distance N—H = 0.86±0.02 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 U_eq of the parent atom.

Figures

Fig. 1.

Molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

View of the crystal packing in (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C9H11NO3S	Dx = 1.328 Mg m−3
Mr = 213.25	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43	Cell parameters from 1894 reflections
Hall symbol: P 4cw	θ = 2.5–27.8°
a = 7.9804 (5) Å	µ = 0.29 mm−1
c = 16.749 (1) Å	T = 293 K
V = 1066.69 (11) Å3	Prism, colourless
Z = 4	0.40 × 0.18 × 0.12 mm
F(000) = 448

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1944 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
graphite	Rint = 0.016
Rotation method data acquisition using ω and φ scans	θmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −9→5
Tmin = 0.895, Tmax = 0.967	k = −6→9
4245 measured reflections	l = −17→20

Refinement

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.0453P)2 + 0.1227P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.016
1944 reflections	Δρmax = 0.14 e Å−3
132 parameters	Δρmin = −0.17 e Å−3
2 restraints	Absolute structure: Flack (1983), 824 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.03 (9)

Special details

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C1	0.0401 (3)	0.5352 (3)	0.16636 (17)	0.0418 (6)
C2	0.0148 (3)	0.3636 (3)	0.15630 (19)	0.0534 (7)
C3	−0.0178 (4)	0.2719 (4)	0.2248 (3)	0.0758 (11)
H3	−0.0359	0.1571	0.2205	0.091*
C4	−0.0243 (5)	0.3456 (5)	0.2992 (2)	0.0844 (12)
H4	−0.0458	0.2805	0.3440	0.101*
C5	0.0008 (4)	0.5134 (5)	0.3071 (2)	0.0730 (10)
H5	−0.0034	0.5631	0.3573	0.088*
C6	0.0326 (4)	0.6095 (4)	0.24026 (19)	0.0571 (7)
H6	0.0490	0.7244	0.2452	0.069*
C7	0.4165 (3)	0.6071 (3)	0.10946 (17)	0.0462 (6)
C8	0.5725 (3)	0.5282 (5)	0.0766 (2)	0.0738 (10)
H8A	0.6102	0.5908	0.0310	0.089*
H8B	0.5489	0.4149	0.0608	0.089*
H8C	0.6582	0.5283	0.1168	0.089*
C9	0.0213 (5)	0.2751 (4)	0.0766 (3)	0.0830 (11)
H9A	0.1276	0.2961	0.0517	0.100*
H9B	−0.0669	0.3162	0.0429	0.100*
H9C	0.0075	0.1568	0.0845	0.100*
N1	0.2818 (3)	0.6051 (3)	0.05903 (12)	0.0413 (5)
H1N	0.278 (3)	0.556 (3)	0.0138 (12)	0.050*
O1	−0.0096 (3)	0.6269 (3)	0.01708 (12)	0.0644 (6)
O2	0.0971 (3)	0.8346 (2)	0.11214 (13)	0.0632 (6)
O3	0.4067 (2)	0.6678 (3)	0.17544 (11)	0.0588 (5)
S1	0.09057 (8)	0.66608 (8)	0.08490 (5)	0.04393 (18)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0313 (12)	0.0414 (14)	0.0526 (15)	0.0022 (11)	0.0085 (11)	−0.0017 (12)
C2	0.0416 (15)	0.0414 (15)	0.077 (2)	0.0004 (12)	0.0128 (14)	−0.0002 (14)
C3	0.068 (2)	0.0495 (18)	0.110 (3)	0.0058 (16)	0.027 (2)	0.017 (2)
C4	0.078 (2)	0.090 (3)	0.085 (3)	0.011 (2)	0.030 (2)	0.033 (2)
C5	0.069 (2)	0.098 (3)	0.0526 (19)	0.0076 (18)	0.0181 (17)	0.0058 (18)
C6	0.0480 (16)	0.0596 (17)	0.0637 (18)	0.0013 (13)	0.0148 (14)	−0.0082 (16)
C7	0.0392 (14)	0.0478 (14)	0.0515 (17)	−0.0071 (11)	−0.0043 (11)	−0.0001 (13)
C8	0.0401 (15)	0.102 (3)	0.080 (2)	0.0051 (15)	0.0006 (17)	−0.012 (2)
C9	0.084 (2)	0.0521 (18)	0.112 (3)	−0.0123 (16)	0.020 (2)	−0.030 (2)
N1	0.0379 (11)	0.0493 (12)	0.0366 (12)	−0.0012 (9)	0.0021 (9)	−0.0061 (9)
O1	0.0510 (12)	0.0821 (16)	0.0601 (14)	0.0057 (10)	−0.0138 (10)	0.0055 (12)
O2	0.0717 (13)	0.0375 (10)	0.0806 (15)	0.0068 (9)	0.0170 (11)	0.0028 (10)
O3	0.0577 (12)	0.0760 (14)	0.0426 (11)	−0.0075 (10)	−0.0091 (9)	−0.0100 (10)
S1	0.0385 (3)	0.0424 (3)	0.0509 (4)	0.0049 (3)	0.0006 (3)	0.0015 (3)

Geometric parameters (Å, °)

C1—C6	1.374 (4)	C7—N1	1.367 (3)
C1—C2	1.395 (4)	C7—C8	1.500 (4)
C1—S1	1.765 (3)	C8—H8A	0.9600
C2—C3	1.386 (5)	C8—H8B	0.9600
C2—C9	1.511 (5)	C8—H8C	0.9600
C3—C4	1.378 (5)	C9—H9A	0.9600
C3—H3	0.9300	C9—H9B	0.9600
C4—C5	1.361 (6)	C9—H9C	0.9600
C4—H4	0.9300	N1—S1	1.659 (2)
C5—C6	1.380 (5)	N1—H1N	0.855 (17)
C5—H5	0.9300	O1—S1	1.424 (2)
C6—H6	0.9300	O2—S1	1.4213 (19)
C7—O3	1.209 (3)
C6—C1—C2	121.8 (3)	C7—C8—H8A	109.5
C6—C1—S1	116.8 (2)	C7—C8—H8B	109.5
C2—C1—S1	121.4 (2)	H8A—C8—H8B	109.5
C3—C2—C1	116.5 (3)	C7—C8—H8C	109.5
C3—C2—C9	119.4 (3)	H8A—C8—H8C	109.5
C1—C2—C9	124.1 (3)	H8B—C8—H8C	109.5
C4—C3—C2	122.0 (3)	C2—C9—H9A	109.5
C4—C3—H3	119.0	C2—C9—H9B	109.5
C2—C3—H3	119.0	H9A—C9—H9B	109.5
C5—C4—C3	120.2 (3)	C2—C9—H9C	109.5
C5—C4—H4	119.9	H9A—C9—H9C	109.5
C3—C4—H4	119.9	H9B—C9—H9C	109.5
C4—C5—C6	119.6 (3)	C7—N1—S1	123.94 (18)
C4—C5—H5	120.2	C7—N1—H1N	125.3 (19)
C6—C5—H5	120.2	S1—N1—H1N	109.7 (19)
C1—C6—C5	119.9 (3)	O2—S1—O1	119.00 (13)
C1—C6—H6	120.0	O2—S1—N1	109.12 (11)
C5—C6—H6	120.0	O1—S1—N1	104.10 (12)
O3—C7—N1	121.2 (2)	O2—S1—C1	108.68 (13)
O3—C7—C8	123.9 (3)	O1—S1—C1	110.99 (13)
N1—C7—C8	114.9 (3)	N1—S1—C1	103.79 (11)
C6—C1—C2—C3	−0.2 (4)	O3—C7—N1—S1	−6.3 (4)
S1—C1—C2—C3	177.5 (2)	C8—C7—N1—S1	173.3 (2)
C6—C1—C2—C9	180.0 (3)	C7—N1—S1—O2	57.5 (3)
S1—C1—C2—C9	−2.3 (4)	C7—N1—S1—O1	−174.5 (2)
C1—C2—C3—C4	−0.3 (5)	C7—N1—S1—C1	−58.2 (2)
C9—C2—C3—C4	179.6 (3)	C6—C1—S1—O2	−6.2 (3)
C2—C3—C4—C5	0.3 (6)	C2—C1—S1—O2	176.0 (2)
C3—C4—C5—C6	0.1 (5)	C6—C1—S1—O1	−138.9 (2)
C2—C1—C6—C5	0.6 (4)	C2—C1—S1—O1	43.3 (2)
S1—C1—C6—C5	−177.3 (2)	C6—C1—S1—N1	109.8 (2)
C4—C5—C6—C1	−0.5 (5)	C2—C1—S1—N1	−68.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3i	0.86 (2)	1.95 (2)	2.770 (3)	162 (3)

Symmetry codes: (i) −y+1, x, z−1/4.