Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702483X/im2016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702483X/im2016Isup2.hkl |
CCDC reference: 614955
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.107
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.96 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 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 1 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
The title compound was prepared according to the literature method (Gowda et al., 2002). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Gowda et al., 2002). Single crystals of the title compound were obtained from a slow evaporation of its ethanolic solution and used for X-ray diffraction studies at room temperature.
Many arylsulfonamides and their N-halo compounds show distinct physical, chemical and biological properties due to their oxidizing action in aqueous, partial aqueous and non-aqueous media. This class of compounds therefore is of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2002, 2003, 2005, 2007; Gowda & Shetty, 2004). In the present work, the structure of 3,4-dimethylbenzenesulfonamde (34DMBSA) has been determined to explore the substituent effects on the solid state structures of sulfonamides and N-halo arylsulfonamides (Gowda et al., 2003, 2007). The structure of 34DMBSA (Fig. 1) resembles those of other aryl sulfonamides (Gowda et al., 2003; Jones & Weinkauf, 1993; Kumar et al., 1992; O'Connor & Maslen, 1965). 34DMBSA crystallizes in monoclinic P 21/c space group in contrast to the monoclinic Pc space group of the parent benzenesulfonamide, orthorhombic Pbca space group observed with 4-fluorobenzenesulfonamide (Jones & Weinkauf, 1993) and 4-aminobenzenesulfonamide (O'Connor & Maslen, 1965), monoclinic P21/n space group with 4-chlorobenzenesulfonamide and 4-bromobenzenesulfonamide (Gowda et al., 2003), and 4-methylbenzenesulfonamide (Kumar et al., 1992). Introduction of two methyl groups at the meta and para positions of the benzenesulfonamide slightly decreases the S—N bond length while increasing the S—O bond lengths. Nevertheless, the other bond parameters are not significantly altered. The molecules in the title compound are packed into a layered supramolecular structure as viewed down the ac plane through hydrogen bonding (Fig. 2).
For related literature, see: Gowda & Shetty (2004); Gowda et al. (2002, 2003, 2005, 2007); Jones & Weinkauf (1993); Kumar et al. (1992); O'Connor & Maslen (1965).
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: REDU4 (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).
C8H11NO2S | F(000) = 392 |
Mr = 185.24 | Dx = 1.354 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 9.7939 (4) Å | θ = 9.3–30.1° |
b = 9.5488 (5) Å | µ = 2.85 mm−1 |
c = 10.3342 (8) Å | T = 299 K |
β = 109.936 (5)° | Prism, colourless |
V = 908.54 (9) Å3 | 0.58 × 0.35 × 0.2 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 1524 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 66.9°, θmin = 4.8° |
ω/2θ scans | h = −10→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→11 |
Tmin = 0.366, Tmax = 0.586 | l = −12→0 |
3312 measured reflections | 3 standard reflections every 120 min |
1618 independent reflections | intensity decay: 3.5% |
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.283P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
1618 reflections | Δρmax = 0.46 e Å−3 |
118 parameters | Δρmin = −0.44 e Å−3 |
2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0240 (16) |
C8H11NO2S | V = 908.54 (9) Å3 |
Mr = 185.24 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 9.7939 (4) Å | µ = 2.85 mm−1 |
b = 9.5488 (5) Å | T = 299 K |
c = 10.3342 (8) Å | 0.58 × 0.35 × 0.2 mm |
β = 109.936 (5)° |
Enraf–Nonius CAD-4 diffractometer | 1524 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.040 |
Tmin = 0.366, Tmax = 0.586 | 3 standard reflections every 120 min |
3312 measured reflections | intensity decay: 3.5% |
1618 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 2 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.46 e Å−3 |
1618 reflections | Δρmin = −0.44 e Å−3 |
118 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 | 0.74966 (18) | 0.27510 (19) | 0.30043 (17) | 0.0353 (4) | |
C2 | 0.86716 (19) | 0.2192 (2) | 0.40414 (19) | 0.0395 (4) | |
H2 | 0.8540 | 0.1410 | 0.4522 | 0.047* | |
C3 | 1.00472 (19) | 0.2784 (2) | 0.43747 (19) | 0.0408 (4) | |
C4 | 1.02302 (19) | 0.3965 (2) | 0.36621 (19) | 0.0430 (5) | |
C5 | 0.9025 (2) | 0.4516 (2) | 0.2627 (2) | 0.0499 (5) | |
H5 | 0.9145 | 0.5309 | 0.2154 | 0.060* | |
C6 | 0.7666 (2) | 0.3922 (2) | 0.22840 (19) | 0.0458 (5) | |
H6 | 0.6880 | 0.4299 | 0.1585 | 0.055* | |
C7 | 1.1309 (2) | 0.2136 (3) | 0.5497 (3) | 0.0624 (6) | |
H7A | 1.1701 | 0.2804 | 0.6224 | 0.075* | |
H7B | 1.2046 | 0.1869 | 0.5127 | 0.075* | |
H7C | 1.0981 | 0.1323 | 0.5854 | 0.075* | |
C8 | 1.1693 (2) | 0.4650 (3) | 0.3989 (2) | 0.0601 (6) | |
H8A | 1.1579 | 0.5548 | 0.3547 | 0.072* | |
H8B | 1.2308 | 0.4070 | 0.3663 | 0.072* | |
H8C | 1.2127 | 0.4770 | 0.4967 | 0.072* | |
N1 | 0.47754 (17) | 0.29125 (18) | 0.31866 (16) | 0.0436 (4) | |
H11N | 0.502 (2) | 0.294 (2) | 0.4059 (10) | 0.052* | |
H12N | 0.457 (2) | 0.3705 (15) | 0.281 (2) | 0.052* | |
O1 | 0.59702 (15) | 0.06501 (15) | 0.33109 (17) | 0.0574 (4) | |
O2 | 0.51100 (16) | 0.19748 (19) | 0.11336 (15) | 0.0629 (5) | |
S1 | 0.57753 (4) | 0.19636 (5) | 0.25981 (4) | 0.0384 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0331 (8) | 0.0384 (9) | 0.0333 (8) | 0.0005 (7) | 0.0098 (7) | −0.0049 (7) |
C2 | 0.0383 (9) | 0.0374 (10) | 0.0393 (9) | 0.0011 (7) | 0.0087 (7) | 0.0002 (7) |
C3 | 0.0348 (9) | 0.0437 (10) | 0.0401 (10) | 0.0022 (8) | 0.0078 (7) | −0.0046 (8) |
C4 | 0.0380 (9) | 0.0517 (11) | 0.0417 (9) | −0.0043 (8) | 0.0168 (7) | −0.0074 (8) |
C5 | 0.0527 (11) | 0.0530 (12) | 0.0464 (10) | −0.0059 (9) | 0.0200 (9) | 0.0098 (9) |
C6 | 0.0419 (10) | 0.0515 (12) | 0.0393 (9) | 0.0037 (9) | 0.0078 (7) | 0.0075 (8) |
C7 | 0.0427 (11) | 0.0646 (15) | 0.0625 (14) | 0.0030 (10) | −0.0046 (10) | 0.0050 (11) |
C8 | 0.0464 (11) | 0.0774 (16) | 0.0598 (13) | −0.0166 (11) | 0.0225 (10) | −0.0082 (11) |
N1 | 0.0402 (8) | 0.0527 (11) | 0.0380 (9) | 0.0082 (7) | 0.0135 (7) | 0.0017 (7) |
O1 | 0.0498 (8) | 0.0372 (8) | 0.0800 (11) | −0.0059 (6) | 0.0154 (7) | −0.0012 (7) |
O2 | 0.0478 (8) | 0.1006 (14) | 0.0346 (8) | −0.0125 (8) | 0.0066 (6) | −0.0214 (7) |
S1 | 0.0327 (3) | 0.0430 (3) | 0.0363 (3) | −0.00293 (16) | 0.0076 (2) | −0.00863 (16) |
C1—C6 | 1.384 (3) | C7—H7A | 0.9600 |
C1—C2 | 1.384 (3) | C7—H7B | 0.9600 |
C1—S1 | 1.7610 (18) | C7—H7C | 0.9600 |
C2—C3 | 1.392 (3) | C8—H8A | 0.9600 |
C2—H2 | 0.9300 | C8—H8B | 0.9600 |
C3—C4 | 1.392 (3) | C8—H8C | 0.9600 |
C3—C7 | 1.509 (3) | N1—S1 | 1.5987 (16) |
C4—C5 | 1.397 (3) | N1—H11N | 0.851 (10) |
C4—C8 | 1.505 (3) | N1—H12N | 0.845 (10) |
C5—C6 | 1.378 (3) | O1—S1 | 1.4340 (16) |
C5—H5 | 0.9300 | O2—S1 | 1.4292 (15) |
C6—H6 | 0.9300 | ||
C6—C1—C2 | 120.49 (17) | H7A—C7—H7B | 109.5 |
C6—C1—S1 | 119.81 (14) | C3—C7—H7C | 109.5 |
C2—C1—S1 | 119.71 (14) | H7A—C7—H7C | 109.5 |
C1—C2—C3 | 120.95 (18) | H7B—C7—H7C | 109.5 |
C1—C2—H2 | 119.5 | C4—C8—H8A | 109.5 |
C3—C2—H2 | 119.5 | C4—C8—H8B | 109.5 |
C2—C3—C4 | 119.12 (17) | H8A—C8—H8B | 109.5 |
C2—C3—C7 | 119.58 (19) | C4—C8—H8C | 109.5 |
C4—C3—C7 | 121.30 (19) | H8A—C8—H8C | 109.5 |
C3—C4—C5 | 118.86 (17) | H8B—C8—H8C | 109.5 |
C3—C4—C8 | 121.20 (18) | S1—N1—H11N | 115.8 (16) |
C5—C4—C8 | 119.94 (19) | S1—N1—H12N | 114.3 (15) |
C6—C5—C4 | 122.11 (19) | H11N—N1—H12N | 114 (2) |
C6—C5—H5 | 118.9 | O2—S1—O1 | 118.90 (10) |
C4—C5—H5 | 118.9 | O2—S1—N1 | 106.34 (9) |
C5—C6—C1 | 118.47 (17) | O1—S1—N1 | 106.97 (9) |
C5—C6—H6 | 120.8 | O2—S1—C1 | 107.64 (9) |
C1—C6—H6 | 120.8 | O1—S1—C1 | 107.58 (9) |
C3—C7—H7A | 109.5 | N1—S1—C1 | 109.15 (9) |
C3—C7—H7B | 109.5 | ||
C6—C1—C2—C3 | −0.6 (3) | C4—C5—C6—C1 | 0.7 (3) |
S1—C1—C2—C3 | 179.33 (14) | C2—C1—C6—C5 | −0.2 (3) |
C1—C2—C3—C4 | 0.8 (3) | S1—C1—C6—C5 | 179.89 (15) |
C1—C2—C3—C7 | −179.12 (19) | C6—C1—S1—O2 | 40.23 (17) |
C2—C3—C4—C5 | −0.4 (3) | C2—C1—S1—O2 | −139.66 (16) |
C7—C3—C4—C5 | 179.6 (2) | C6—C1—S1—O1 | 169.48 (15) |
C2—C3—C4—C8 | 179.62 (18) | C2—C1—S1—O1 | −10.41 (17) |
C7—C3—C4—C8 | −0.4 (3) | C6—C1—S1—N1 | −74.79 (16) |
C3—C4—C5—C6 | −0.4 (3) | C2—C1—S1—N1 | 105.31 (16) |
C8—C4—C5—C6 | 179.60 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11N···O2i | 0.85 (1) | 2.12 (1) | 2.952 (2) | 167 (2) |
N1—H12N···O1ii | 0.85 (1) | 2.16 (1) | 2.999 (2) | 176 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H11NO2S |
Mr | 185.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 299 |
a, b, c (Å) | 9.7939 (4), 9.5488 (5), 10.3342 (8) |
β (°) | 109.936 (5) |
V (Å3) | 908.54 (9) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.85 |
Crystal size (mm) | 0.58 × 0.35 × 0.2 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.366, 0.586 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3312, 1618, 1524 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.107, 1.11 |
No. of reflections | 1618 |
No. of parameters | 118 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.44 |
Computer programs: STADI4 (Stoe & Cie, 1996), STADI4, REDU4 (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11N···O2i | 0.85 (1) | 2.12 (1) | 2.952 (2) | 167 (2) |
N1—H12N···O1ii | 0.85 (1) | 2.16 (1) | 2.999 (2) | 176 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
Many arylsulfonamides and their N-halo compounds show distinct physical, chemical and biological properties due to their oxidizing action in aqueous, partial aqueous and non-aqueous media. This class of compounds therefore is of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2002, 2003, 2005, 2007; Gowda & Shetty, 2004). In the present work, the structure of 3,4-dimethylbenzenesulfonamde (34DMBSA) has been determined to explore the substituent effects on the solid state structures of sulfonamides and N-halo arylsulfonamides (Gowda et al., 2003, 2007). The structure of 34DMBSA (Fig. 1) resembles those of other aryl sulfonamides (Gowda et al., 2003; Jones & Weinkauf, 1993; Kumar et al., 1992; O'Connor & Maslen, 1965). 34DMBSA crystallizes in monoclinic P 21/c space group in contrast to the monoclinic Pc space group of the parent benzenesulfonamide, orthorhombic Pbca space group observed with 4-fluorobenzenesulfonamide (Jones & Weinkauf, 1993) and 4-aminobenzenesulfonamide (O'Connor & Maslen, 1965), monoclinic P21/n space group with 4-chlorobenzenesulfonamide and 4-bromobenzenesulfonamide (Gowda et al., 2003), and 4-methylbenzenesulfonamide (Kumar et al., 1992). Introduction of two methyl groups at the meta and para positions of the benzenesulfonamide slightly decreases the S—N bond length while increasing the S—O bond lengths. Nevertheless, the other bond parameters are not significantly altered. The molecules in the title compound are packed into a layered supramolecular structure as viewed down the ac plane through hydrogen bonding (Fig. 2).