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In the structure of the title compound (24DMPMSA), C9H13NO2S, the conformation of the N—H bond is syn to the ortho-methyl substituent, similar to the syn conformation observed for N-(2-methyl­phenyl)­methane­sulfonamide (2MPMSA). The geometric parameters in 24DMPMSA are similar to those in N-phenyl­methane­sulfonamide, 2MPMSA and N-(2,3-dimethyl­phenyl)­methane­sulfonamide, except for some differences in the torsion angles. The amide H atom is readily available to a receptor mol­ecule during its biological activity, as it lies on one side of the plane of the benzene ring, while the methane­sulfonyl group is on the opposite side, similar to those in N-aryl­methane­sulfonamides. The mol­ecules in 24DMPMSA are packed into chains through N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025226/lw2019sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025226/lw2019Isup2.hkl
Contains datablock I

CCDC reference: 614673

Key indicators

  • Single-crystal X-ray study
  • T = 299 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.055
  • wR factor = 0.161
  • Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.129 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.13 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S2 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C13 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C9 H13 N O2 S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The structural studies of sulphonanilides are of interest due to their biological activity. The latter is thought to be due to the hydrogen of the phenyl N—H portion of the sulphonanilide molecules as it can align itself, in relation to a receptor site. In the present work, the structure of N-(2,4-dimethylphenyl)-methanesulfonamde (24DMPMSA) has been determined to explore the substituent effects on the solid state structures of sulfonanilides (Gowda et al., 2007a-h). The structure of 24DMPMSA (Fig. 1) resembles those of N-(phenyl)-methanesulfonamde (PMSA) (Klug, 1968), N-(2-methylphenyl)-methanesulfonamde (2MPMSA) (Gowda et al., 2007d), N-(2,3-dimethylphenyl)- methanesulfonamde (23DMPMSA)(Gowda et al., 2007h) and other alkyl sulfonanilides (Gowda et al., 2007a-c,e-g). The conformation of of the N—H bond is syn to the ortho-methyl substituent, similar to the syn conformation observed for the 2MPMSA). The ortho substitution of a methyl group in PMSA changes its space group from monoclinic P21/c to triclinic P-1. Substitution of an additional methyl group at the para position in 2MPMSA to produce 24DMPMSA, changes the space group from triclinic P-1 to monoclinic P21/n, in contrast to the orthorhombic P212121 space group observed for 23DMPMSA. The geometric parameters in 24DMPMSA are similar to those in PMSA, 2MPMSA and 23DMPMSA except for some difference in the torsional angles, C1S2N5C6, S2N5C6C7, S2N5C6C11, O3S2N5C6 and 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); 71.4 (3)°,70.1 (4)°, -110.8 (3)°, -44.9 (3)°, -172.6 (3)° (23DMPMSA), -62.9 (3)°, -67.8 (4)°, 113.5 (3)°, 53.1 (3)°, -178.4 (3)° (24DMPMSA), respectively. The data included for PMSA are the values determined under the present conditions as the literature values were determined in 1968. The N—H hydrogen is readily available to a receptor molecule during its biological activity as it 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 those in N-(aryl)-methanesulfonamdes. The molecules in 24DMPMSA 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 top

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

Experimental top

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.

Refinement top

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 Ueq (parent atom).

Structure description top

The structural studies of sulphonanilides are of interest due to their biological activity. The latter is thought to be due to the hydrogen of the phenyl N—H portion of the sulphonanilide molecules as it can align itself, in relation to a receptor site. In the present work, the structure of N-(2,4-dimethylphenyl)-methanesulfonamde (24DMPMSA) has been determined to explore the substituent effects on the solid state structures of sulfonanilides (Gowda et al., 2007a-h). The structure of 24DMPMSA (Fig. 1) resembles those of N-(phenyl)-methanesulfonamde (PMSA) (Klug, 1968), N-(2-methylphenyl)-methanesulfonamde (2MPMSA) (Gowda et al., 2007d), N-(2,3-dimethylphenyl)- methanesulfonamde (23DMPMSA)(Gowda et al., 2007h) and other alkyl sulfonanilides (Gowda et al., 2007a-c,e-g). The conformation of of the N—H bond is syn to the ortho-methyl substituent, similar to the syn conformation observed for the 2MPMSA). The ortho substitution of a methyl group in PMSA changes its space group from monoclinic P21/c to triclinic P-1. Substitution of an additional methyl group at the para position in 2MPMSA to produce 24DMPMSA, changes the space group from triclinic P-1 to monoclinic P21/n, in contrast to the orthorhombic P212121 space group observed for 23DMPMSA. The geometric parameters in 24DMPMSA are similar to those in PMSA, 2MPMSA and 23DMPMSA except for some difference in the torsional angles, C1S2N5C6, S2N5C6C7, S2N5C6C11, O3S2N5C6 and 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); 71.4 (3)°,70.1 (4)°, -110.8 (3)°, -44.9 (3)°, -172.6 (3)° (23DMPMSA), -62.9 (3)°, -67.8 (4)°, 113.5 (3)°, 53.1 (3)°, -178.4 (3)° (24DMPMSA), respectively. The data included for PMSA are the values determined under the present conditions as the literature values were determined in 1968. The N—H hydrogen is readily available to a receptor molecule during its biological activity as it 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 those in N-(aryl)-methanesulfonamdes. The molecules in 24DMPMSA are packed into chains in the direction of b axis (Fig. 2) through N—H···O hydrogen bonds (Fig. 3 and Table 1).

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

Computing details top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed down the b axis.
[Figure 3] Fig. 3. Hydrogen bonding in the title compound. Hydrogen bonds are shown as dashed lines.
N-(2,4-dimethylphenyl)methanesulfonamide top
Crystal data top
C9H13NO2SF(000) = 424
Mr = 199.26Dx = 1.318 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 12.312 (1) Åθ = 8.0–25.2°
b = 6.1393 (6) ŵ = 2.62 mm1
c = 13.907 (1) ÅT = 299 K
β = 107.206 (9)°Prism, colourless
V = 1004.15 (15) Å30.28 × 0.13 × 0.08 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer
1177 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.129
Graphite monochromatorθmax = 67.0°, θmin = 4.2°
ω/2θ scansh = 014
Absorption correction: ψ scan
(North et al., 1968)
k = 70
Tmin = 0.678, Tmax = 0.817l = 1615
1880 measured reflections3 standard reflections every 120 min
1792 independent reflections intensity decay: 1.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.161 w = 1/[σ2(Fo2) + (0.0948P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.034
1792 reflectionsΔρmax = 0.26 e Å3
122 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0055 (11)
Crystal data top
C9H13NO2SV = 1004.15 (15) Å3
Mr = 199.26Z = 4
Monoclinic, P21/nCu Kα radiation
a = 12.312 (1) ŵ = 2.62 mm1
b = 6.1393 (6) ÅT = 299 K
c = 13.907 (1) Å0.28 × 0.13 × 0.08 mm
β = 107.206 (9)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1177 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.129
Tmin = 0.678, Tmax = 0.8173 standard reflections every 120 min
1880 measured reflections intensity decay: 1.0%
1792 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.161H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.26 e Å3
1792 reflectionsΔρmin = 0.25 e Å3
122 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.7010 (4)0.2571 (8)0.1477 (3)0.0886 (15)
H1A0.71890.23070.21870.106*
H1B0.76030.34240.13450.106*
H1C0.63030.33460.12490.106*
C60.7369 (3)0.1836 (5)0.0733 (2)0.0437 (7)
C70.7099 (3)0.3920 (5)0.1136 (2)0.0459 (8)
C80.7906 (3)0.4983 (6)0.1480 (2)0.0524 (8)
H80.77330.63600.17620.063*
C90.8951 (3)0.4101 (6)0.1425 (2)0.0530 (9)
C100.9176 (3)0.2009 (7)0.1051 (3)0.0552 (9)
H100.98660.13580.10240.066*
C110.8392 (3)0.0878 (6)0.0720 (2)0.0503 (8)
H110.85490.05400.04860.060*
C120.9832 (4)0.5361 (8)0.1755 (3)0.0751 (12)
H12A0.95380.57020.24580.090*
H12B1.00090.66860.13740.090*
H12C1.05080.44970.16420.090*
C130.5977 (3)0.4991 (6)0.1203 (3)0.0622 (9)
H13A0.53680.41210.16150.075*
H13B0.58930.51210.05410.075*
H13C0.59550.64130.14950.075*
N50.6587 (2)0.0630 (5)0.0346 (2)0.0492 (7)
H5N0.593 (3)0.073 (7)0.059 (3)0.059*
O30.5930 (2)0.1062 (6)0.0961 (2)0.0796 (9)
O40.7962 (2)0.0944 (6)0.1157 (2)0.0867 (10)
S20.68909 (7)0.00790 (16)0.08391 (6)0.0534 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.102 (4)0.108 (4)0.062 (3)0.015 (3)0.034 (2)0.023 (2)
C60.0467 (17)0.0439 (17)0.0402 (16)0.0047 (15)0.0121 (13)0.0017 (13)
C70.0477 (18)0.0421 (17)0.0478 (17)0.0003 (15)0.0139 (14)0.0031 (14)
C80.059 (2)0.0461 (17)0.0513 (18)0.0045 (18)0.0151 (15)0.0033 (16)
C90.0503 (19)0.064 (2)0.0452 (17)0.0114 (18)0.0155 (14)0.0006 (16)
C100.0459 (18)0.072 (2)0.0477 (18)0.0044 (18)0.0136 (15)0.0057 (17)
C110.0532 (19)0.0530 (18)0.0430 (17)0.0027 (16)0.0113 (14)0.0021 (15)
C120.066 (2)0.090 (3)0.074 (3)0.016 (2)0.029 (2)0.013 (2)
C130.064 (2)0.0457 (19)0.080 (2)0.0071 (19)0.0266 (19)0.0040 (19)
N50.0468 (15)0.0519 (16)0.0466 (16)0.0088 (14)0.0104 (12)0.0029 (12)
O30.0657 (17)0.107 (2)0.0672 (17)0.0215 (17)0.0205 (13)0.0254 (16)
O40.0688 (18)0.125 (3)0.0705 (18)0.0363 (18)0.0275 (14)0.0432 (18)
S20.0464 (5)0.0694 (6)0.0459 (5)0.0012 (5)0.0158 (3)0.0083 (4)
Geometric parameters (Å, º) top
C1—S21.753 (5)C10—C111.374 (5)
C1—H1A0.9600C10—H100.9300
C1—H1B0.9600C11—H110.9300
C1—H1C0.9600C12—H12A0.9600
C6—C111.385 (4)C12—H12B0.9600
C6—C71.397 (5)C12—H12C0.9600
C6—N51.439 (4)C13—H13A0.9600
C7—C81.387 (4)C13—H13B0.9600
C7—C131.507 (4)C13—H13C0.9600
C8—C91.377 (5)N5—S21.615 (3)
C8—H80.9300N5—H5N0.78 (4)
C9—C101.383 (5)O3—S21.427 (3)
C9—C121.510 (5)O4—S21.409 (3)
S2—C1—H1A109.5C6—C11—H11119.7
S2—C1—H1B109.5C9—C12—H12A109.5
H1A—C1—H1B109.5C9—C12—H12B109.5
S2—C1—H1C109.5H12A—C12—H12B109.5
H1A—C1—H1C109.5C9—C12—H12C109.5
H1B—C1—H1C109.5H12A—C12—H12C109.5
C11—C6—C7120.1 (3)H12B—C12—H12C109.5
C11—C6—N5118.9 (3)C7—C13—H13A109.5
C7—C6—N5121.0 (3)C7—C13—H13B109.5
C8—C7—C6117.3 (3)H13A—C13—H13B109.5
C8—C7—C13120.7 (3)C7—C13—H13C109.5
C6—C7—C13121.9 (3)H13A—C13—H13C109.5
C9—C8—C7123.3 (3)H13B—C13—H13C109.5
C9—C8—H8118.4C6—N5—S2120.7 (2)
C7—C8—H8118.4C6—N5—H5N121 (3)
C8—C9—C10117.8 (3)S2—N5—H5N111 (3)
C8—C9—C12121.7 (4)O4—S2—O3118.4 (2)
C10—C9—C12120.5 (4)O4—S2—N5109.08 (16)
C11—C10—C9120.8 (3)O3—S2—N5105.93 (15)
C11—C10—H10119.6O4—S2—C1107.4 (2)
C9—C10—H10119.6O3—S2—C1108.4 (2)
C10—C11—C6120.5 (3)N5—S2—C1107.1 (2)
C10—C11—H11119.7
C11—C6—C7—C82.2 (5)C12—C9—C10—C11177.9 (3)
N5—C6—C7—C8179.1 (3)C9—C10—C11—C61.5 (5)
C11—C6—C7—C13177.6 (3)C7—C6—C11—C103.6 (5)
N5—C6—C7—C131.0 (5)N5—C6—C11—C10177.8 (3)
C6—C7—C8—C91.2 (5)C11—C6—N5—S267.8 (4)
C13—C7—C8—C9179.0 (3)C7—C6—N5—S2113.5 (3)
C7—C8—C9—C103.3 (5)C6—N5—S2—O453.1 (3)
C7—C8—C9—C12176.5 (3)C6—N5—S2—O3178.4 (3)
C8—C9—C10—C111.9 (5)C6—N5—S2—C162.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5N···O3i0.78 (4)2.20 (4)2.973 (4)168 (4)
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC9H13NO2S
Mr199.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)299
a, b, c (Å)12.312 (1), 6.1393 (6), 13.907 (1)
β (°) 107.206 (9)
V3)1004.15 (15)
Z4
Radiation typeCu Kα
µ (mm1)2.62
Crystal size (mm)0.28 × 0.13 × 0.08
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.678, 0.817
No. of measured, independent and
observed [I > 2σ(I)] reflections
1880, 1792, 1177
Rint0.129
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.161, 1.02
No. of reflections1792
No. of parameters122
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.25

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), CAD-4-PC, REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5N···O3i0.78 (4)2.20 (4)2.973 (4)168 (4)
Symmetry code: (i) x+1, y, z.
 

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