N-(2-Methyl­phen­yl)methane­sulfonamide

The conformation of the N—H bond in the structure of the title compound (2MPMSA), C₈H₁₁NO₂S, is syn to the ortho-methyl substituent, in contrast with the anti conformation observed for the meta-methyl-substituted compound (3MPMSA). The ortho substitution of the methyl group in N-phenyl­methane­sulfonamde (PMSA) changes its space group from monoclinic P2₁/c to triclinic P, compared with the change from monoclinic P2₁/c to ortho­rhom­bic Pccn on meta-substitution. The bond parameters in PMSA, 2MPMSA and 3MPMSA are similar, except for the torsion angles involving the S—N bond. The N—H H atom alone lies on one side of the plane of the phenyl group, while the whole methane­sulfonyl group is on the opposite side of the plane, similar to what was observed in PMSA and 3MPMSA. Thus, the amide H atom is available to a receptor mol­ecule during biological activity. The mol­ecules of the title compound form centrosymmetric dimers via an N—H...O(sulfon­yl) hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.098
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

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PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)        1000 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          5
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S1. Comment

The biological activity of alkyl sulfonanilides is thought to be due to the H atom of the phenyl N—H portion of the sulfonanilide molecule, as it can align itself in relation to a receptor site. Therefore, the structural studies of sulfonanilides are of interest. In the present work, the structure of N-(2-methylphenyl)methanesulfonamde (2MPMSA), (I), has been determined to explore the substituent effects on the solid-state structures of anilides and sulfonanilides (Gowda et al., 2007a,b,c,d; Gowda, Kozisek et al., 2007; Gowda et al., 2000).

The conformation of the N—H bond in the structure of 2MPMSA is syn to the ortho-methyl substituent (Fig. 1), in contrast with the anti conformation observed for the meta-methyl-substituted compound (3MPMSA) (Gowda et al., 2007c). The ortho-substitution of the methyl group in N-(phenyl)methanesulfonamde (PMSA) changes its space group from monoclinic P2₁/c (Klug, 1968) to triclinic P1, compared with the change from monoclinic P2₁/c to orthorhombic Pccn on meta-methyl substitution (Gowda et al., 2007c).

The bond parameters in PMSA (Klug, 1968), 2MPMSA and 3MPMSA (Gowda et al., 2007c) are similar except for the torsion angles C1—S2—N5—C6, S2—N5—C6—C7, S2—N5—C6—C11, which have the following values: 62.2 (2), 75.5 (2) and -106.6 (2)°, respectively, in PMSA; -64.5 (2), 117.1 (2) and -65.3 (3)°, respectively, in 2MPMSA; 57.9 (3), 68.1 (4) and -114.3 (3)°, respectively, in 3MPMSA. The data included for PMSA are the values determined under the present conditions as the literature values were determined in [Meaning not clear. Text missing?] (Klug, 1968).

The N—H H atom lies alone on one side of the plane of the phenyl group, while

the whole methanesulfonyl group is on the opposite side of the plane, similar to what was observed in PMSA and 3MPMSA. Thus, the amide H atom is available to

a receptor molecule during biological activity.

The molecules in the title compound form centrosymmetric dimers via an N5—H5N···O3(1 - x,-y, 1 - z) hydrogen bond (Table 1 and Fig. 2).

Related literature

For related literature, see: Gowda et al. (2007a,b,c,d); Gowda, Kozisek et al. (2007); Gowda et al. (2000); Jayalakshmi & Gowda (2004); Klug (1968).

S2. Experimental

The title compound was prepared according to the literature method of Jayalakshmi & Gowda (2004). The purity of the compound was checked by determining its melting point. It was characterized by recording its IR and NMR

spectra (Jayalakshmi & Gowda, 2004). Single crystals of the title compound were obtained by slow evaporation of an ethanolic solution and used for X-ray diffraction studied at room temperature.

S3. Refinement

All H atoms attached to C and N atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å (CH aromatic) or 0.96 Å (CH₃) and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C) for methyl H. [This does not match the data in the CIF, where coordinates have been refined - please provide correct text]

Computing details

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The hydrogen bonding in the title compound. Hydrogen bonds are shown as dashed lines.

N-(2-Methylphenyl)methanesulfonamide

Crystal data

C8H11NO2S	Z = 2
Mr = 185.24	F(000) = 196
Triclinic, P1	Dx = 1.361 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 5.719 (1) Å	Cell parameters from 25 reflections
b = 9.041 (1) Å	θ = 7.7–23.7°
c = 9.225 (2) Å	µ = 2.87 mm^−1
α = 79.53 (1)°	T = 299 K
β = 87.36 (1)°	Block, grey
γ = 74.44 (1)°	0.13 × 0.13 × 0.10 mm
V = 451.85 (14) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	1259 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 66.9°, θmin = 4.9°
ω/2θ scans	h = −6→6
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
Tmin = 0.731, Tmax = 0.789	l = 0→10
1713 measured reflections	3 standard reflections every 120 min
1606 independent reflections	intensity decay: 1.8%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Only H-atom coordinates refined
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 0.0954P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1606 reflections	Δρmax = 0.17 e Å^−3
143 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0117 (14)

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
C1	0.2073 (7)	0.0168 (4)	0.1937 (4)	0.0679 (9)
H1A	0.265 (6)	−0.052 (4)	0.124 (4)	0.081*
H1B	0.142 (6)	−0.028 (4)	0.276 (4)	0.081*
H1C	0.094 (6)	0.114 (4)	0.145 (4)	0.081*
C6	0.1994 (4)	0.3574 (3)	0.2840 (3)	0.0404 (5)
C7	0.2887 (5)	0.4558 (3)	0.1760 (3)	0.0511 (7)
H7	0.447 (5)	0.424 (3)	0.142 (3)	0.061*
C8	0.1438 (6)	0.6009 (3)	0.1180 (3)	0.0623 (8)
H8	0.207 (5)	0.668 (4)	0.042 (3)	0.075*
C9	−0.0875 (6)	0.6489 (4)	0.1688 (3)	0.0648 (8)
H9	−0.194 (6)	0.749 (4)	0.136 (3)	0.078*
C10	−0.1738 (5)	0.5531 (4)	0.2789 (3)	0.0589 (7)
H10	−0.331 (6)	0.586 (4)	0.316 (3)	0.071*
C11	−0.0351 (4)	0.4046 (3)	0.3388 (3)	0.0445 (6)
C12	−0.1334 (6)	0.3018 (4)	0.4577 (4)	0.0625 (8)
H12A	−0.128 (6)	0.210 (4)	0.430 (4)	0.075*
H12B	−0.042 (6)	0.279 (4)	0.546 (4)	0.075*
H12C	−0.289 (6)	0.348 (4)	0.476 (3)	0.075*
N5	0.3555 (4)	0.2077 (2)	0.3434 (2)	0.0468 (5)
H5N	0.348 (5)	0.164 (3)	0.4324 (15)	0.056*
O3	0.6064 (4)	−0.0557 (2)	0.3450 (2)	0.0789 (7)
O4	0.5642 (4)	0.1338 (2)	0.1154 (2)	0.0607 (5)
S2	0.45723 (12)	0.07166 (7)	0.24662 (7)	0.0469 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.081 (2)	0.066 (2)	0.067 (2)	−0.0319 (18)	0.0114 (18)	−0.0207 (17)
C6	0.0437 (13)	0.0398 (12)	0.0373 (12)	−0.0079 (10)	−0.0027 (10)	−0.0098 (10)
C7	0.0554 (16)	0.0479 (14)	0.0484 (15)	−0.0124 (12)	0.0083 (13)	−0.0083 (12)
C8	0.083 (2)	0.0462 (15)	0.0524 (17)	−0.0124 (15)	0.0093 (15)	−0.0053 (13)
C9	0.079 (2)	0.0470 (16)	0.0564 (17)	0.0033 (15)	−0.0053 (16)	−0.0070 (14)
C10	0.0462 (16)	0.0626 (18)	0.0629 (18)	−0.0006 (13)	−0.0016 (13)	−0.0190 (15)
C11	0.0422 (14)	0.0506 (14)	0.0420 (13)	−0.0117 (11)	−0.0021 (10)	−0.0123 (11)
C12	0.0543 (18)	0.073 (2)	0.0635 (19)	−0.0230 (16)	0.0117 (15)	−0.0131 (17)
N5	0.0536 (13)	0.0458 (12)	0.0336 (11)	−0.0021 (10)	−0.0019 (9)	−0.0041 (9)
O3	0.0951 (16)	0.0603 (12)	0.0507 (12)	0.0292 (11)	−0.0059 (11)	−0.0045 (10)
O4	0.0651 (12)	0.0637 (12)	0.0509 (11)	−0.0162 (10)	0.0203 (9)	−0.0105 (9)
S2	0.0516 (4)	0.0431 (4)	0.0376 (3)	−0.0008 (3)	0.0031 (2)	−0.0037 (2)

Geometric parameters (Å, º)

C1—S2	1.749 (4)	C9—H9	0.95 (3)
C1—H1A	0.96 (3)	C10—C11	1.392 (4)
C1—H1B	0.91 (3)	C10—H10	0.94 (3)
C1—H1C	0.99 (3)	C11—C12	1.495 (4)
C6—C7	1.386 (3)	C12—H12A	0.90 (3)
C6—C11	1.395 (3)	C12—H12B	0.95 (3)
C6—N5	1.434 (3)	C12—H12C	0.90 (3)
C7—C8	1.377 (4)	N5—S2	1.617 (2)
C7—H7	0.93 (3)	N5—H5N	0.848 (10)
C8—C9	1.366 (4)	O3—S2	1.4286 (19)
C8—H8	0.96 (3)	O4—S2	1.4225 (19)
C9—C10	1.374 (4)
S2—C1—H1A	107 (2)	C11—C10—H10	117.6 (19)
S2—C1—H1B	108 (2)	C10—C11—C6	116.9 (2)
H1A—C1—H1B	114 (3)	C10—C11—C12	121.2 (3)
S2—C1—H1C	106 (2)	C6—C11—C12	121.9 (2)
H1A—C1—H1C	110 (3)	C11—C12—H12A	111 (2)
H1B—C1—H1C	112 (3)	C11—C12—H12B	112 (2)
C7—C6—C11	120.9 (2)	H12A—C12—H12B	107 (3)
C7—C6—N5	118.9 (2)	C11—C12—H12C	110 (2)
C11—C6—N5	120.1 (2)	H12A—C12—H12C	108 (3)
C8—C7—C6	120.2 (3)	H12B—C12—H12C	109 (3)
C8—C7—H7	119.5 (18)	C6—N5—S2	123.02 (16)
C6—C7—H7	120.3 (18)	C6—N5—H5N	122.6 (19)
C9—C8—C7	119.9 (3)	S2—N5—H5N	108 (2)
C9—C8—H8	120.6 (19)	O4—S2—O3	118.19 (13)
C7—C8—H8	119.5 (19)	O4—S2—N5	109.11 (12)
C8—C9—C10	119.9 (3)	O3—S2—N5	105.40 (12)
C8—C9—H9	123.7 (19)	O4—S2—C1	107.17 (15)
C10—C9—H9	116 (2)	O3—S2—C1	109.20 (17)
C9—C10—C11	122.1 (3)	N5—S2—C1	107.33 (15)
C9—C10—H10	120.3 (19)
C11—C6—C7—C8	−1.8 (4)	N5—C6—C11—C10	178.2 (2)
N5—C6—C7—C8	−179.3 (2)	C7—C6—C11—C12	−178.6 (3)
C6—C7—C8—C9	1.0 (5)	N5—C6—C11—C12	−1.1 (4)
C7—C8—C9—C10	0.9 (5)	C7—C6—N5—S2	−65.4 (3)
C8—C9—C10—C11	−2.0 (5)	C11—C6—N5—S2	117.1 (2)
C9—C10—C11—C6	1.2 (4)	C6—N5—S2—O4	51.3 (2)
C9—C10—C11—C12	−179.5 (3)	C6—N5—S2—O3	179.2 (2)
C7—C6—C11—C10	0.7 (4)	C6—N5—S2—C1	−64.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3^i	0.85 (1)	2.10 (1)	2.943 (3)	170 (3)

Symmetry code: (i) −x+1, −y, −z+1.