N-(2,3-Dimethyl­phen­yl)methane­sulfonamide

In the structure of the title compound (23DMPMSA), C₉H₁₃NO₂S, the conformation of the N—H bond lies between syn and anti to the methyl substituents at the ortho and meta positions, in contrast to the syn and anti conformations observed, respectively, for N-(2-methyl­phenyl)­methane­sulfonamide (2MPMSA) and N-(3-methyl­phenyl)­methane­sulfonamide (3MPMSA). The bond parameters in N-phenyl­methane­sulfonamide (PMSA), 2MPMSA, 3MPMSA and 23DMPMSA are similar except for some differences in the torsion angles. The H atom on N is on one side of the plane of the benzene ring, while the methane­sulfonyl group is on the opposite side of the plane, as in PMSA, 2MPMSA and 3MPMSA. The amide H atom is thus available to a receptor mol­ecule during its biological activity. The mol­ecules in the title compound are packed into chains through N—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 301 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.054
• wR factor = 0.130
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

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Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.36
           From the CIF: _reflns_number_total               2023
           Count of symmetry unique reflns         1242
           Completeness (_total/calc)            162.88%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       781
           Fraction of Friedel pairs measured     0.629
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The biological activity of alkyl sulfonanilides is thought to be due to the hydrogen of the phenyl N—H portion of the sulfonanilide molecules 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-(2,3-dimethylphenyl)-methanesulfonamide (23DMPMSA) has been determined to explore the substituent effects on the solid state structures of sulfonanilides (Gowda et al., 2007a-g). The structure of 23DMPMSA (Fig. 1) resembles those of N-(phenyl)-methanesulfonamide (PMSA) (Klug, 1968), N-(2-methylphenyl)-methanesulfonamide (2MPMSA) (Gowda et al., 2007d), N-(3-methylphenyl)- methanesulfonamide (3MPMSA)(Gowda et al., 2007b) and other alkyl sulfonanilides (Gowda et al., 2007a,c,e-g). The conformation of the N—H bond lies between syn and anti conformations to the methyl substituents at ortho and meta positions, in contrast to the syn and anti conformations observed, respectively, for the 2MPMSA and 3MPMSA. Dimethyl substitutions at both ortho and meta positions in PMSA changes its space group from monoclinic P2₁/c to orthorhombic P2₁2₁2₁, compared to the change over from monoclinic P2₁/c to triclinic P-1 on ortho methyl substitution in PMSA and from monoclinic P2₁/c to orthorhombic Pccn on meta substitution in PMSA. The geometric parameters in PMSA, 2MPMSA, 3MPMSA and 23DMPMSA are similar except for some difference in the torsional angles, C1S2N5C6, S2N5C6C7, S2N5C6C11, O3S2N5C6, O4S2N5C6: 62.2 (2)°, 75.5 (2)°, -106.6 (2)°, -54.4 (2)°, 177.7 (2)° (PMSA); -64.5 (2)°, 117.1 (2)°, -65.3 (3)°, 51.3 (2)°, 179.1 (2)° (2MPMSA); 57.9 (3)°, 68.1 (4)°, -114.3 (3)°, -57.7 (3)°, 174.7 (3)° (3MPMSA); 71.4 (3)°, 70.1 (4)°, -110.8 (3)°, -44.9 (3)°, -172.6 (3)° (23DMPMSA), respectively. The data included for PMSA are the values determined under the present conditions as the literature values were determined in Klug, 1968. The N—H hydrogen sits 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 that in PMSA, 2MPMSA and 3MPMSA. The amide hydrogen is thus available to a receptor molecule during its biological activity. The molecules in 23DMPMSA are packed into chains in the direction of b axis (Fig. 2) through N—H···O hydrogen bonds (Fig. 3 and Table 1).

Related literature

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

S2. Experimental

The title compound was prepared according to the literature method (Jayalakshmi & Gowda, 2004). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Jayalakshmi & Gowda, 2004). Single crystals of the title compound were obtained from a slow evaporation of its ethanolic solution and used for X-ray diffraction studied at room temperature.

S3. Refinement

The H atom of the NH group was located in a diffrerence map and its position refined. The carbon-bound H atoms were positioned with idealized geometry and refined using a riding model with C—H = 0.93 Å (CH aromatic) or 0.96 Å (CH₃). Isotropic displacement parameters for all H atoms were set equal to 1.2 U_eq (parent atom).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2004); 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. Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis.
	Fig. 3. Hydrogen bonding in the title compound. Hydrogen bonds are shown as dashed lines.

N-(2,3-dimethylphenyl)methanesulfonamide

Crystal data

C9H13NO2S	F(000) = 424
Mr = 199.26	Dx = 1.338 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2323 reflections
a = 5.2259 (6) Å	θ = 3.6–23.2°
b = 5.5567 (8) Å	µ = 0.30 mm^−1
c = 34.056 (1) Å	T = 301 K
V = 988.94 (18) Å^3	Prism, gray
Z = 4	0.50 × 0.44 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1831 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.068
Graphite monochromator	θmax = 26.4°, θmin = 4.1°
Rotation method data acquisition using ω scans	h = −6→5
6529 measured reflections	k = −6→6
2023 independent reflections	l = −40→42

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.054	w = 1/[σ^2(Fo^2) + (0.0485P)^2 + 0.7116P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.130	(Δ/σ)max = 0.035
S = 1.07	Δρmax = 0.27 e Å^−3
2023 reflections	Δρmin = −0.24 e Å^−3
122 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.016 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 781 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.22 (16)

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
S2	0.70935 (16)	0.32902 (18)	0.19688 (2)	0.0436 (3)
O3	0.4634 (4)	0.4002 (5)	0.18247 (8)	0.0547 (7)
O4	0.8125 (6)	0.4515 (5)	0.22983 (8)	0.0623 (8)
N5	0.9112 (5)	0.3672 (6)	0.16118 (8)	0.0415 (7)
H5N	1.067 (3)	0.383 (8)	0.1683 (10)	0.050*
C1	0.7014 (10)	0.0208 (8)	0.20732 (12)	0.0621 (11)
H1A	0.8676	−0.0311	0.2158	0.075*
H1B	0.6534	−0.0665	0.1841	0.075*
H1C	0.5787	−0.0093	0.2277	0.075*
C6	0.8579 (6)	0.2927 (6)	0.12190 (9)	0.0404 (8)
C7	0.9912 (6)	0.0995 (6)	0.10470 (10)	0.0422 (8)
C8	0.9385 (8)	0.0450 (7)	0.06527 (11)	0.0518 (9)
C9	0.7513 (7)	0.1698 (10)	0.04547 (11)	0.0622 (11)
H9	0.7136	0.1287	0.0196	0.075*
C10	0.6192 (8)	0.3537 (10)	0.06313 (11)	0.0643 (12)
H10	0.4922	0.4348	0.0493	0.077*
C11	0.6736 (7)	0.4186 (7)	0.10106 (11)	0.0526 (9)
H11	0.5873	0.5463	0.1127	0.063*
C12	1.0809 (9)	−0.1528 (10)	0.04468 (13)	0.0711 (12)
H12A	1.0426	−0.3040	0.0570	0.085*
H12B	1.2615	−0.1226	0.0462	0.085*
H12C	1.0295	−0.1583	0.0176	0.085*
C13	1.1869 (8)	−0.0438 (7)	0.12723 (11)	0.0530 (9)
H13A	1.1731	−0.0073	0.1547	0.064*
H13B	1.3553	−0.0031	0.1181	0.064*
H13C	1.1571	−0.2125	0.1232	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0330 (4)	0.0514 (5)	0.0465 (4)	0.0027 (4)	−0.0021 (3)	−0.0061 (4)
O3	0.0293 (12)	0.0688 (18)	0.0659 (16)	0.0086 (12)	−0.0012 (11)	−0.0061 (13)
O4	0.0571 (16)	0.0693 (18)	0.0606 (15)	0.0058 (16)	−0.0078 (14)	−0.0272 (14)
N5	0.0264 (12)	0.0488 (17)	0.0492 (16)	−0.0008 (14)	−0.0008 (11)	−0.0026 (13)
C1	0.068 (3)	0.063 (2)	0.056 (2)	−0.003 (2)	0.001 (2)	0.0135 (18)
C6	0.0276 (15)	0.0455 (19)	0.0480 (17)	−0.0013 (14)	0.0009 (13)	0.0069 (15)
C7	0.0344 (17)	0.0362 (17)	0.056 (2)	−0.0033 (14)	0.0031 (15)	0.0020 (14)
C8	0.048 (2)	0.051 (2)	0.056 (2)	−0.0109 (18)	0.0101 (18)	−0.0011 (18)
C9	0.055 (2)	0.085 (3)	0.0461 (18)	−0.008 (3)	−0.0027 (17)	0.003 (2)
C10	0.054 (2)	0.087 (3)	0.052 (2)	0.014 (2)	−0.0065 (17)	0.021 (2)
C11	0.047 (2)	0.052 (2)	0.059 (2)	0.0118 (18)	0.0027 (18)	0.0139 (17)
C12	0.068 (3)	0.075 (3)	0.070 (3)	−0.008 (3)	0.016 (2)	−0.021 (2)
C13	0.045 (2)	0.047 (2)	0.067 (2)	0.0093 (19)	−0.0044 (19)	−0.0040 (17)

Geometric parameters (Å, º)

S2—O4	1.419 (3)	C8—C9	1.376 (6)
S2—O3	1.432 (2)	C8—C12	1.501 (6)
S2—N5	1.623 (3)	C9—C10	1.373 (6)
S2—C1	1.750 (4)	C9—H9	0.9300
N5—C6	1.428 (4)	C10—C11	1.371 (6)
N5—H5N	0.854 (10)	C10—H10	0.9300
C1—H1A	0.9600	C11—H11	0.9300
C1—H1B	0.9600	C12—H12A	0.9600
C1—H1C	0.9600	C12—H12B	0.9600
C6—C11	1.386 (5)	C12—H12C	0.9600
C6—C7	1.408 (5)	C13—H13A	0.9600
C7—C8	1.404 (5)	C13—H13B	0.9600
C7—C13	1.506 (5)	C13—H13C	0.9600
O4—S2—O3	118.66 (18)	C7—C8—C12	120.5 (4)
O4—S2—N5	106.41 (17)	C10—C9—C8	121.2 (4)
O3—S2—N5	106.90 (15)	C10—C9—H9	119.4
O4—S2—C1	108.5 (2)	C8—C9—H9	119.4
O3—S2—C1	108.6 (2)	C11—C10—C9	120.3 (4)
N5—S2—C1	107.20 (19)	C11—C10—H10	119.9
C6—N5—S2	122.5 (2)	C9—C10—H10	119.9
C6—N5—H5N	119 (3)	C10—C11—C6	119.6 (4)
S2—N5—H5N	115 (2)	C10—C11—H11	120.2
S2—C1—H1A	109.5	C6—C11—H11	120.2
S2—C1—H1B	109.5	C8—C12—H12A	109.5
H1A—C1—H1B	109.5	C8—C12—H12B	109.5
S2—C1—H1C	109.5	H12A—C12—H12B	109.5
H1A—C1—H1C	109.5	C8—C12—H12C	109.5
H1B—C1—H1C	109.5	H12A—C12—H12C	109.5
C11—C6—C7	121.1 (3)	H12B—C12—H12C	109.5
C11—C6—N5	118.0 (3)	C7—C13—H13A	109.5
C7—C6—N5	121.0 (3)	C7—C13—H13B	109.5
C8—C7—C6	117.7 (3)	H13A—C13—H13B	109.5
C8—C7—C13	120.4 (3)	C7—C13—H13C	109.5
C6—C7—C13	121.8 (3)	H13A—C13—H13C	109.5
C9—C8—C7	120.0 (4)	H13B—C13—H13C	109.5
C9—C8—C12	119.5 (4)
O4—S2—N5—C6	−172.6 (3)	C13—C7—C8—C9	177.1 (4)
O3—S2—N5—C6	−44.9 (3)	C6—C7—C8—C12	177.7 (3)
C1—S2—N5—C6	71.4 (3)	C13—C7—C8—C12	−1.5 (5)
S2—N5—C6—C11	70.1 (4)	C7—C8—C9—C10	2.2 (6)
S2—N5—C6—C7	−110.8 (3)	C12—C8—C9—C10	−179.2 (4)
C11—C6—C7—C8	2.5 (5)	C8—C9—C10—C11	0.6 (7)
N5—C6—C7—C8	−176.5 (3)	C9—C10—C11—C6	−1.9 (6)
C11—C6—C7—C13	−178.3 (3)	C7—C6—C11—C10	0.2 (5)
N5—C6—C7—C13	2.7 (5)	N5—C6—C11—C10	179.3 (3)
C6—C7—C8—C9	−3.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3^i	0.85 (1)	2.13 (1)	2.981 (4)	175 (4)

Symmetry code: (i) x+1, y, z.