Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025226/lw2019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025226/lw2019Isup2.hkl |
CCDC reference: 614673
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (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
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.
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).
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).
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.
C9H13NO2S | F(000) = 424 |
Mr = 199.26 | Dx = 1.318 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 12.312 (1) Å | θ = 8.0–25.2° |
b = 6.1393 (6) Å | µ = 2.62 mm−1 |
c = 13.907 (1) Å | T = 299 K |
β = 107.206 (9)° | Prism, colourless |
V = 1004.15 (15) Å3 | 0.28 × 0.13 × 0.08 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 1177 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.129 |
Graphite monochromator | θmax = 67.0°, θmin = 4.2° |
ω/2θ scans | h = 0→14 |
Absorption correction: ψ scan (North et al., 1968) | k = −7→0 |
Tmin = 0.678, Tmax = 0.817 | l = −16→15 |
1880 measured reflections | 3 standard reflections every 120 min |
1792 independent reflections | intensity decay: 1.0% |
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)] = 0.055 | H 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 reflections | Δρmax = 0.26 e Å−3 |
122 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0055 (11) |
C9H13NO2S | V = 1004.15 (15) Å3 |
Mr = 199.26 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 12.312 (1) Å | µ = 2.62 mm−1 |
b = 6.1393 (6) Å | T = 299 K |
c = 13.907 (1) Å | 0.28 × 0.13 × 0.08 mm |
β = 107.206 (9)° |
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 = 0.817 | 3 standard reflections every 120 min |
1880 measured reflections | intensity decay: 1.0% |
1792 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.161 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.26 e Å−3 |
1792 reflections | Δρmin = −0.25 e Å−3 |
122 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7010 (4) | −0.2571 (8) | 0.1477 (3) | 0.0886 (15) | |
H1A | 0.7189 | −0.2307 | 0.2187 | 0.106* | |
H1B | 0.7603 | −0.3424 | 0.1345 | 0.106* | |
H1C | 0.6303 | −0.3346 | 0.1249 | 0.106* | |
C6 | 0.7369 (3) | −0.1836 (5) | −0.0733 (2) | 0.0437 (7) | |
C7 | 0.7099 (3) | −0.3920 (5) | −0.1136 (2) | 0.0459 (8) | |
C8 | 0.7906 (3) | −0.4983 (6) | −0.1480 (2) | 0.0524 (8) | |
H8 | 0.7733 | −0.6360 | −0.1762 | 0.063* | |
C9 | 0.8951 (3) | −0.4101 (6) | −0.1425 (2) | 0.0530 (9) | |
C10 | 0.9176 (3) | −0.2009 (7) | −0.1051 (3) | 0.0552 (9) | |
H10 | 0.9866 | −0.1358 | −0.1024 | 0.066* | |
C11 | 0.8392 (3) | −0.0878 (6) | −0.0720 (2) | 0.0503 (8) | |
H11 | 0.8549 | 0.0540 | −0.0486 | 0.060* | |
C12 | 0.9832 (4) | −0.5361 (8) | −0.1755 (3) | 0.0751 (12) | |
H12A | 0.9538 | −0.5702 | −0.2458 | 0.090* | |
H12B | 1.0009 | −0.6686 | −0.1374 | 0.090* | |
H12C | 1.0508 | −0.4497 | −0.1642 | 0.090* | |
C13 | 0.5977 (3) | −0.4991 (6) | −0.1203 (3) | 0.0622 (9) | |
H13A | 0.5368 | −0.4121 | −0.1615 | 0.075* | |
H13B | 0.5893 | −0.5121 | −0.0541 | 0.075* | |
H13C | 0.5955 | −0.6413 | −0.1495 | 0.075* | |
N5 | 0.6587 (2) | −0.0630 (5) | −0.0346 (2) | 0.0492 (7) | |
H5N | 0.593 (3) | −0.073 (7) | −0.059 (3) | 0.059* | |
O3 | 0.5930 (2) | 0.1062 (6) | 0.0961 (2) | 0.0796 (9) | |
O4 | 0.7962 (2) | 0.0944 (6) | 0.1157 (2) | 0.0867 (10) | |
S2 | 0.68909 (7) | −0.00790 (16) | 0.08391 (6) | 0.0534 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.102 (4) | 0.108 (4) | 0.062 (3) | 0.015 (3) | 0.034 (2) | 0.023 (2) |
C6 | 0.0467 (17) | 0.0439 (17) | 0.0402 (16) | 0.0047 (15) | 0.0121 (13) | 0.0017 (13) |
C7 | 0.0477 (18) | 0.0421 (17) | 0.0478 (17) | 0.0003 (15) | 0.0139 (14) | 0.0031 (14) |
C8 | 0.059 (2) | 0.0461 (17) | 0.0513 (18) | 0.0045 (18) | 0.0151 (15) | −0.0033 (16) |
C9 | 0.0503 (19) | 0.064 (2) | 0.0452 (17) | 0.0114 (18) | 0.0155 (14) | −0.0006 (16) |
C10 | 0.0459 (18) | 0.072 (2) | 0.0477 (18) | −0.0044 (18) | 0.0136 (15) | −0.0057 (17) |
C11 | 0.0532 (19) | 0.0530 (18) | 0.0430 (17) | −0.0027 (16) | 0.0113 (14) | −0.0021 (15) |
C12 | 0.066 (2) | 0.090 (3) | 0.074 (3) | 0.016 (2) | 0.029 (2) | −0.013 (2) |
C13 | 0.064 (2) | 0.0457 (19) | 0.080 (2) | −0.0071 (19) | 0.0266 (19) | −0.0040 (19) |
N5 | 0.0468 (15) | 0.0519 (16) | 0.0466 (16) | 0.0088 (14) | 0.0104 (12) | −0.0029 (12) |
O3 | 0.0657 (17) | 0.107 (2) | 0.0672 (17) | 0.0215 (17) | 0.0205 (13) | −0.0254 (16) |
O4 | 0.0688 (18) | 0.125 (3) | 0.0705 (18) | −0.0363 (18) | 0.0275 (14) | −0.0432 (18) |
S2 | 0.0464 (5) | 0.0694 (6) | 0.0459 (5) | 0.0012 (5) | 0.0158 (3) | −0.0083 (4) |
C1—S2 | 1.753 (5) | C10—C11 | 1.374 (5) |
C1—H1A | 0.9600 | C10—H10 | 0.9300 |
C1—H1B | 0.9600 | C11—H11 | 0.9300 |
C1—H1C | 0.9600 | C12—H12A | 0.9600 |
C6—C11 | 1.385 (4) | C12—H12B | 0.9600 |
C6—C7 | 1.397 (5) | C12—H12C | 0.9600 |
C6—N5 | 1.439 (4) | C13—H13A | 0.9600 |
C7—C8 | 1.387 (4) | C13—H13B | 0.9600 |
C7—C13 | 1.507 (4) | C13—H13C | 0.9600 |
C8—C9 | 1.377 (5) | N5—S2 | 1.615 (3) |
C8—H8 | 0.9300 | N5—H5N | 0.78 (4) |
C9—C10 | 1.383 (5) | O3—S2 | 1.427 (3) |
C9—C12 | 1.510 (5) | O4—S2 | 1.409 (3) |
S2—C1—H1A | 109.5 | C6—C11—H11 | 119.7 |
S2—C1—H1B | 109.5 | C9—C12—H12A | 109.5 |
H1A—C1—H1B | 109.5 | C9—C12—H12B | 109.5 |
S2—C1—H1C | 109.5 | H12A—C12—H12B | 109.5 |
H1A—C1—H1C | 109.5 | C9—C12—H12C | 109.5 |
H1B—C1—H1C | 109.5 | H12A—C12—H12C | 109.5 |
C11—C6—C7 | 120.1 (3) | H12B—C12—H12C | 109.5 |
C11—C6—N5 | 118.9 (3) | C7—C13—H13A | 109.5 |
C7—C6—N5 | 121.0 (3) | C7—C13—H13B | 109.5 |
C8—C7—C6 | 117.3 (3) | H13A—C13—H13B | 109.5 |
C8—C7—C13 | 120.7 (3) | C7—C13—H13C | 109.5 |
C6—C7—C13 | 121.9 (3) | H13A—C13—H13C | 109.5 |
C9—C8—C7 | 123.3 (3) | H13B—C13—H13C | 109.5 |
C9—C8—H8 | 118.4 | C6—N5—S2 | 120.7 (2) |
C7—C8—H8 | 118.4 | C6—N5—H5N | 121 (3) |
C8—C9—C10 | 117.8 (3) | S2—N5—H5N | 111 (3) |
C8—C9—C12 | 121.7 (4) | O4—S2—O3 | 118.4 (2) |
C10—C9—C12 | 120.5 (4) | O4—S2—N5 | 109.08 (16) |
C11—C10—C9 | 120.8 (3) | O3—S2—N5 | 105.93 (15) |
C11—C10—H10 | 119.6 | O4—S2—C1 | 107.4 (2) |
C9—C10—H10 | 119.6 | O3—S2—C1 | 108.4 (2) |
C10—C11—C6 | 120.5 (3) | N5—S2—C1 | 107.1 (2) |
C10—C11—H11 | 119.7 | ||
C11—C6—C7—C8 | 2.2 (5) | C12—C9—C10—C11 | −177.9 (3) |
N5—C6—C7—C8 | −179.1 (3) | C9—C10—C11—C6 | 1.5 (5) |
C11—C6—C7—C13 | −177.6 (3) | C7—C6—C11—C10 | −3.6 (5) |
N5—C6—C7—C13 | 1.0 (5) | N5—C6—C11—C10 | 177.8 (3) |
C6—C7—C8—C9 | 1.2 (5) | C11—C6—N5—S2 | −67.8 (4) |
C13—C7—C8—C9 | −179.0 (3) | C7—C6—N5—S2 | 113.5 (3) |
C7—C8—C9—C10 | −3.3 (5) | C6—N5—S2—O4 | 53.1 (3) |
C7—C8—C9—C12 | 176.5 (3) | C6—N5—S2—O3 | −178.4 (3) |
C8—C9—C10—C11 | 1.9 (5) | C6—N5—S2—C1 | −62.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···O3i | 0.78 (4) | 2.20 (4) | 2.973 (4) | 168 (4) |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C9H13NO2S |
Mr | 199.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 299 |
a, b, c (Å) | 12.312 (1), 6.1393 (6), 13.907 (1) |
β (°) | 107.206 (9) |
V (Å3) | 1004.15 (15) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.62 |
Crystal size (mm) | 0.28 × 0.13 × 0.08 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.678, 0.817 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1880, 1792, 1177 |
Rint | 0.129 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.161, 1.02 |
No. of reflections | 1792 |
No. of parameters | 122 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···O3i | 0.78 (4) | 2.20 (4) | 2.973 (4) | 168 (4) |
Symmetry code: (i) −x+1, −y, −z. |
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).