Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703677X/hb2495sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703677X/hb2495Isup2.hkl |
CCDC reference: 660182
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.122
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
Alert level G 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 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A solution of benzenesulfonyl chloride in CH2Cl2 was added dropwise to a mixture of 2,4-xylidine and triethylamine in CH2Cl2 at room temperature with stirring. The reaction mixture continued stirring overnight. The resulting solid was purified by recrystallization from methanol. Colourless blocks of (I) were grown by natural evaporation of a methanolic solution.
The N-bound H atom was refined freely while the other H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
In the molecular structure of (I), Fig. 1, the N lone electron pair weakly conjugates the xylene ring due to the strong electron-withdrawing capability of benzenesulfonyl group. The sligtly long C7—N1 [1.435 (2) Å] bond length and selected torsion angles (Table 1) support this. Thus, the amide has a pyramidal arrangement of bonds around nitrogen, but the pyramid is somewhat shallower than expected for pure sp3 hybridization. The xylene ring has an angle of 59.40 (10) ° with the phenyl ring.
In the crystal of (I), a strong self-complimentary N—H···O interaction (Table 2) links the molecules into centrosymmetric dimers, which extend along the a axle to form a 1-D chain. Aromatic π-π stacking [centroid separation = 3.780 (5) Å] between the xylene and phenyl ring link the 1-D chains.
For the structure of 4-methyl-N-(3-nitrophenyl)benzenesulfonamide, see: Xing et al. (2006).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. (a). The molecular structure of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids for the non-hydrogen atoms. |
C14H15NO2S | F(000) = 552 |
Mr = 261.33 | Dx = 1.306 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2927 reflections |
a = 7.999 (3) Å | θ = 2.8–26.4° |
b = 11.073 (4) Å | µ = 0.24 mm−1 |
c = 15.116 (5) Å | T = 294 K |
β = 96.822 (6)° | Block, colorless |
V = 1329.4 (8) Å3 | 0.22 × 0.20 × 0.16 mm |
Z = 4 |
Bruker SMART 1K CCD diffractometer | 2721 independent reflections |
Radiation source: fine-focus sealed tube | 2098 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 26.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→10 |
Tmin = 0.950, Tmax = 0.963 | k = −13→13 |
7489 measured reflections | l = −17→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: difmap and geom |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0618P)2 + 0.376P] where P = (Fo2 + 2Fc2)/3 |
2721 reflections | (Δ/σ)max < 0.001 |
168 parameters | Δρmax = 0.25 e Å−3 |
1 restraint | Δρmin = −0.34 e Å−3 |
C14H15NO2S | V = 1329.4 (8) Å3 |
Mr = 261.33 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.999 (3) Å | µ = 0.24 mm−1 |
b = 11.073 (4) Å | T = 294 K |
c = 15.116 (5) Å | 0.22 × 0.20 × 0.16 mm |
β = 96.822 (6)° |
Bruker SMART 1K CCD diffractometer | 2721 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2098 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.963 | Rint = 0.025 |
7489 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 1 restraint |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.25 e Å−3 |
2721 reflections | Δρmin = −0.34 e Å−3 |
168 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 | ||
S1 | 0.15860 (6) | 0.57386 (4) | 0.39513 (3) | 0.04420 (18) | |
O1 | 0.30915 (19) | 0.58332 (14) | 0.35412 (10) | 0.0574 (4) | |
C12 | 0.2428 (2) | 0.81756 (17) | 0.56051 (12) | 0.0415 (4) | |
N1 | 0.2010 (2) | 0.61330 (15) | 0.49881 (11) | 0.0439 (4) | |
C1 | 0.0102 (3) | 0.67673 (17) | 0.34296 (12) | 0.0454 (5) | |
O2 | 0.07517 (19) | 0.45924 (13) | 0.39753 (10) | 0.0561 (4) | |
C7 | 0.3079 (2) | 0.71364 (17) | 0.52683 (12) | 0.0383 (4) | |
C10 | 0.5276 (3) | 0.8957 (2) | 0.59282 (13) | 0.0512 (5) | |
C8 | 0.4797 (3) | 0.7013 (2) | 0.52497 (14) | 0.0508 (5) | |
H8 | 0.5226 | 0.6314 | 0.5020 | 0.061* | |
C6 | −0.1581 (3) | 0.6618 (2) | 0.35252 (15) | 0.0567 (6) | |
H6 | −0.1931 | 0.5977 | 0.3856 | 0.068* | |
C11 | 0.3553 (3) | 0.90632 (18) | 0.59333 (13) | 0.0488 (5) | |
H11 | 0.3133 | 0.9762 | 0.6168 | 0.059* | |
C14 | 0.6440 (3) | 0.9943 (2) | 0.63106 (16) | 0.0699 (7) | |
H14A | 0.6496 | 0.9937 | 0.6948 | 0.105* | |
H14B | 0.6023 | 1.0711 | 0.6086 | 0.105* | |
H14C | 0.7545 | 0.9810 | 0.6141 | 0.105* | |
C13 | 0.0571 (3) | 0.8347 (2) | 0.56425 (17) | 0.0614 (6) | |
H13A | 0.0373 | 0.9138 | 0.5869 | 0.092* | |
H13B | 0.0175 | 0.7749 | 0.6028 | 0.092* | |
H13C | −0.0021 | 0.8264 | 0.5055 | 0.092* | |
C2 | 0.0635 (3) | 0.7724 (2) | 0.29396 (14) | 0.0569 (6) | |
H2 | 0.1769 | 0.7819 | 0.2876 | 0.068* | |
C9 | 0.5866 (3) | 0.7923 (2) | 0.55703 (15) | 0.0579 (6) | |
H9 | 0.7016 | 0.7837 | 0.5545 | 0.070* | |
C4 | −0.2212 (4) | 0.8378 (2) | 0.26392 (16) | 0.0714 (7) | |
H4 | −0.2999 | 0.8921 | 0.2368 | 0.086* | |
C3 | −0.0537 (4) | 0.8530 (2) | 0.25501 (15) | 0.0703 (7) | |
H3 | −0.0195 | 0.9180 | 0.2226 | 0.084* | |
C5 | −0.2736 (3) | 0.7434 (3) | 0.31242 (17) | 0.0700 (7) | |
H5 | −0.3873 | 0.7342 | 0.3183 | 0.084* | |
H1A | 0.114 (2) | 0.601 (2) | 0.5296 (13) | 0.055 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0455 (3) | 0.0408 (3) | 0.0471 (3) | −0.0071 (2) | 0.0086 (2) | −0.0059 (2) |
O1 | 0.0510 (9) | 0.0677 (10) | 0.0562 (9) | −0.0066 (7) | 0.0170 (7) | −0.0124 (7) |
C12 | 0.0383 (10) | 0.0443 (11) | 0.0423 (10) | −0.0015 (8) | 0.0057 (8) | 0.0033 (8) |
N1 | 0.0439 (9) | 0.0438 (9) | 0.0446 (9) | −0.0084 (7) | 0.0075 (7) | 0.0005 (7) |
C1 | 0.0552 (12) | 0.0427 (11) | 0.0380 (10) | −0.0072 (9) | 0.0042 (9) | −0.0062 (8) |
O2 | 0.0623 (9) | 0.0397 (8) | 0.0666 (10) | −0.0096 (7) | 0.0087 (7) | −0.0071 (7) |
C7 | 0.0377 (10) | 0.0417 (10) | 0.0349 (9) | −0.0049 (8) | 0.0018 (7) | 0.0032 (8) |
C10 | 0.0493 (12) | 0.0627 (14) | 0.0409 (11) | −0.0179 (10) | 0.0021 (9) | 0.0024 (9) |
C8 | 0.0400 (11) | 0.0572 (13) | 0.0552 (12) | 0.0036 (9) | 0.0060 (9) | −0.0056 (10) |
C6 | 0.0536 (13) | 0.0626 (14) | 0.0542 (13) | −0.0001 (11) | 0.0081 (10) | 0.0031 (10) |
C11 | 0.0560 (13) | 0.0441 (11) | 0.0462 (11) | −0.0051 (9) | 0.0053 (9) | −0.0026 (9) |
C14 | 0.0701 (16) | 0.0786 (18) | 0.0583 (14) | −0.0342 (13) | −0.0034 (12) | −0.0022 (12) |
C13 | 0.0439 (12) | 0.0566 (14) | 0.0841 (17) | 0.0048 (10) | 0.0094 (11) | −0.0084 (12) |
C2 | 0.0717 (15) | 0.0492 (12) | 0.0495 (12) | −0.0151 (11) | 0.0057 (11) | −0.0032 (10) |
C9 | 0.0352 (11) | 0.0788 (16) | 0.0597 (13) | −0.0094 (10) | 0.0050 (9) | −0.0050 (12) |
C4 | 0.096 (2) | 0.0631 (16) | 0.0518 (14) | 0.0215 (14) | −0.0051 (13) | −0.0043 (12) |
C3 | 0.113 (2) | 0.0462 (13) | 0.0500 (13) | −0.0051 (14) | 0.0040 (14) | 0.0024 (10) |
C5 | 0.0628 (15) | 0.0838 (18) | 0.0623 (15) | 0.0133 (13) | 0.0034 (12) | −0.0026 (13) |
S1—O1 | 1.4223 (15) | C6—C5 | 1.379 (3) |
S1—O2 | 1.4364 (15) | C6—H6 | 0.9300 |
S1—N1 | 1.6234 (18) | C11—H11 | 0.9300 |
S1—C1 | 1.763 (2) | C14—H14A | 0.9600 |
C12—C11 | 1.384 (3) | C14—H14B | 0.9600 |
C12—C7 | 1.385 (3) | C14—H14C | 0.9600 |
C12—C13 | 1.506 (3) | C13—H13A | 0.9600 |
N1—C7 | 1.435 (2) | C13—H13B | 0.9600 |
N1—H1A | 0.890 (9) | C13—H13C | 0.9600 |
C1—C6 | 1.380 (3) | C2—C3 | 1.375 (4) |
C1—C2 | 1.389 (3) | C2—H2 | 0.9300 |
C7—C8 | 1.385 (3) | C9—H9 | 0.9300 |
C10—C9 | 1.375 (3) | C4—C5 | 1.371 (4) |
C10—C11 | 1.384 (3) | C4—C3 | 1.372 (4) |
C10—C14 | 1.505 (3) | C4—H4 | 0.9300 |
C8—C9 | 1.372 (3) | C3—H3 | 0.9300 |
C8—H8 | 0.9300 | C5—H5 | 0.9300 |
O1—S1—O2 | 119.74 (9) | C12—C11—H11 | 118.5 |
O1—S1—N1 | 108.09 (9) | C10—C14—H14A | 109.5 |
O2—S1—N1 | 104.94 (9) | C10—C14—H14B | 109.5 |
O1—S1—C1 | 108.52 (10) | H14A—C14—H14B | 109.5 |
O2—S1—C1 | 106.98 (10) | C10—C14—H14C | 109.5 |
N1—S1—C1 | 108.09 (9) | H14A—C14—H14C | 109.5 |
C11—C12—C7 | 117.73 (18) | H14B—C14—H14C | 109.5 |
C11—C12—C13 | 119.96 (18) | C12—C13—H13A | 109.5 |
C7—C12—C13 | 122.30 (17) | C12—C13—H13B | 109.5 |
C7—N1—S1 | 122.83 (13) | H13A—C13—H13B | 109.5 |
C7—N1—H1A | 116.1 (14) | C12—C13—H13C | 109.5 |
S1—N1—H1A | 112.1 (15) | H13A—C13—H13C | 109.5 |
C6—C1—C2 | 120.8 (2) | H13B—C13—H13C | 109.5 |
C6—C1—S1 | 119.29 (16) | C3—C2—C1 | 119.1 (2) |
C2—C1—S1 | 119.90 (17) | C3—C2—H2 | 120.4 |
C12—C7—C8 | 120.45 (18) | C1—C2—H2 | 120.4 |
C12—C7—N1 | 121.03 (17) | C8—C9—C10 | 121.5 (2) |
C8—C7—N1 | 118.39 (18) | C8—C9—H9 | 119.3 |
C9—C10—C11 | 117.50 (19) | C10—C9—H9 | 119.3 |
C9—C10—C14 | 122.0 (2) | C5—C4—C3 | 120.6 (2) |
C11—C10—C14 | 120.5 (2) | C5—C4—H4 | 119.7 |
C9—C8—C7 | 119.9 (2) | C3—C4—H4 | 119.7 |
C9—C8—H8 | 120.0 | C4—C3—C2 | 120.1 (2) |
C7—C8—H8 | 120.0 | C4—C3—H3 | 119.9 |
C5—C6—C1 | 119.1 (2) | C2—C3—H3 | 119.9 |
C5—C6—H6 | 120.5 | C4—C5—C6 | 120.2 (3) |
C1—C6—H6 | 120.5 | C4—C5—H5 | 119.9 |
C10—C11—C12 | 122.91 (19) | C6—C5—H5 | 119.9 |
C10—C11—H11 | 118.5 | ||
O1—S1—N1—C7 | 41.07 (18) | N1—C7—C8—C9 | −175.53 (19) |
O2—S1—N1—C7 | 169.91 (15) | C2—C1—C6—C5 | 0.2 (3) |
C1—S1—N1—C7 | −76.20 (17) | S1—C1—C6—C5 | 179.27 (18) |
O1—S1—C1—C6 | 161.79 (16) | C9—C10—C11—C12 | 0.6 (3) |
O2—S1—C1—C6 | 31.31 (19) | C14—C10—C11—C12 | −178.8 (2) |
N1—S1—C1—C6 | −81.22 (18) | C7—C12—C11—C10 | 0.7 (3) |
O1—S1—C1—C2 | −19.14 (19) | C13—C12—C11—C10 | 179.29 (19) |
O2—S1—C1—C2 | −149.61 (16) | C6—C1—C2—C3 | 0.2 (3) |
N1—S1—C1—C2 | 97.85 (17) | S1—C1—C2—C3 | −178.86 (16) |
C11—C12—C7—C8 | −1.2 (3) | C7—C8—C9—C10 | 1.2 (3) |
C13—C12—C7—C8 | −179.7 (2) | C11—C10—C9—C8 | −1.6 (3) |
C11—C12—C7—N1 | 174.51 (17) | C14—C10—C9—C8 | 177.9 (2) |
C13—C12—C7—N1 | −4.0 (3) | C5—C4—C3—C2 | 0.8 (4) |
S1—N1—C7—C12 | 110.71 (19) | C1—C2—C3—C4 | −0.7 (3) |
S1—N1—C7—C8 | −73.5 (2) | C3—C4—C5—C6 | −0.4 (4) |
C12—C7—C8—C9 | 0.3 (3) | C1—C6—C5—C4 | −0.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.89 (1) | 2.09 (1) | 2.967 (2) | 170 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H15NO2S |
Mr | 261.33 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 7.999 (3), 11.073 (4), 15.116 (5) |
β (°) | 96.822 (6) |
V (Å3) | 1329.4 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.22 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.950, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7489, 2721, 2098 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.122, 1.05 |
No. of reflections | 2721 |
No. of parameters | 168 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.34 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.890 (9) | 2.086 (11) | 2.967 (2) | 170 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
In the molecular structure of (I), Fig. 1, the N lone electron pair weakly conjugates the xylene ring due to the strong electron-withdrawing capability of benzenesulfonyl group. The sligtly long C7—N1 [1.435 (2) Å] bond length and selected torsion angles (Table 1) support this. Thus, the amide has a pyramidal arrangement of bonds around nitrogen, but the pyramid is somewhat shallower than expected for pure sp3 hybridization. The xylene ring has an angle of 59.40 (10) ° with the phenyl ring.
In the crystal of (I), a strong self-complimentary N—H···O interaction (Table 2) links the molecules into centrosymmetric dimers, which extend along the a axle to form a 1-D chain. Aromatic π-π stacking [centroid separation = 3.780 (5) Å] between the xylene and phenyl ring link the 1-D chains.