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The mol­ecules of the title compound, C14H15NO2S, are linked into centrosymmetric dimers via N—H...O hydrogen bonds. The packing is influenced by π–π stacking inter­actions [centroid-to-centroid separation = 3.780 (5) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703677X/hb2495sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680703677X/hb2495Isup2.hkl
Contains datablock I

CCDC reference: 660182

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For the structure of 4-methyl-N-(3-nitrophenyl)benzenesulfonamide, see: Xing et al. (2006).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. (a). The molecular structure of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids for the non-hydrogen atoms.
N-(2,4-Dimethylphenyl)benzenesulfonamide top
Crystal data top
C14H15NO2SF(000) = 552
Mr = 261.33Dx = 1.306 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2927 reflections
a = 7.999 (3) Åθ = 2.8–26.4°
b = 11.073 (4) ŵ = 0.24 mm1
c = 15.116 (5) ÅT = 294 K
β = 96.822 (6)°Block, colorless
V = 1329.4 (8) Å30.22 × 0.20 × 0.16 mm
Z = 4
Data collection top
Bruker SMART 1K CCD
diffractometer
2721 independent reflections
Radiation source: fine-focus sealed tube2098 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 26.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 910
Tmin = 0.950, Tmax = 0.963k = 1313
7489 measured reflectionsl = 1718
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: difmap and geom
wR(F2) = 0.122H 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 parametersΔρmax = 0.25 e Å3
1 restraintΔρmin = 0.34 e Å3
Crystal data top
C14H15NO2SV = 1329.4 (8) Å3
Mr = 261.33Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.999 (3) ŵ = 0.24 mm1
b = 11.073 (4) ÅT = 294 K
c = 15.116 (5) Å0.22 × 0.20 × 0.16 mm
β = 96.822 (6)°
Data collection top
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 = 0.963Rint = 0.025
7489 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0401 restraint
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.25 e Å3
2721 reflectionsΔρmin = 0.34 e Å3
168 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
S10.15860 (6)0.57386 (4)0.39513 (3)0.04420 (18)
O10.30915 (19)0.58332 (14)0.35412 (10)0.0574 (4)
C120.2428 (2)0.81756 (17)0.56051 (12)0.0415 (4)
N10.2010 (2)0.61330 (15)0.49881 (11)0.0439 (4)
C10.0102 (3)0.67673 (17)0.34296 (12)0.0454 (5)
O20.07517 (19)0.45924 (13)0.39753 (10)0.0561 (4)
C70.3079 (2)0.71364 (17)0.52683 (12)0.0383 (4)
C100.5276 (3)0.8957 (2)0.59282 (13)0.0512 (5)
C80.4797 (3)0.7013 (2)0.52497 (14)0.0508 (5)
H80.52260.63140.50200.061*
C60.1581 (3)0.6618 (2)0.35252 (15)0.0567 (6)
H60.19310.59770.38560.068*
C110.3553 (3)0.90632 (18)0.59333 (13)0.0488 (5)
H110.31330.97620.61680.059*
C140.6440 (3)0.9943 (2)0.63106 (16)0.0699 (7)
H14A0.64960.99370.69480.105*
H14B0.60231.07110.60860.105*
H14C0.75450.98100.61410.105*
C130.0571 (3)0.8347 (2)0.56425 (17)0.0614 (6)
H13A0.03730.91380.58690.092*
H13B0.01750.77490.60280.092*
H13C0.00210.82640.50550.092*
C20.0635 (3)0.7724 (2)0.29396 (14)0.0569 (6)
H20.17690.78190.28760.068*
C90.5866 (3)0.7923 (2)0.55703 (15)0.0579 (6)
H90.70160.78370.55450.070*
C40.2212 (4)0.8378 (2)0.26392 (16)0.0714 (7)
H40.29990.89210.23680.086*
C30.0537 (4)0.8530 (2)0.25501 (15)0.0703 (7)
H30.01950.91800.22260.084*
C50.2736 (3)0.7434 (3)0.31242 (17)0.0700 (7)
H50.38730.73420.31830.084*
H1A0.114 (2)0.601 (2)0.5296 (13)0.055 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0455 (3)0.0408 (3)0.0471 (3)0.0071 (2)0.0086 (2)0.0059 (2)
O10.0510 (9)0.0677 (10)0.0562 (9)0.0066 (7)0.0170 (7)0.0124 (7)
C120.0383 (10)0.0443 (11)0.0423 (10)0.0015 (8)0.0057 (8)0.0033 (8)
N10.0439 (9)0.0438 (9)0.0446 (9)0.0084 (7)0.0075 (7)0.0005 (7)
C10.0552 (12)0.0427 (11)0.0380 (10)0.0072 (9)0.0042 (9)0.0062 (8)
O20.0623 (9)0.0397 (8)0.0666 (10)0.0096 (7)0.0087 (7)0.0071 (7)
C70.0377 (10)0.0417 (10)0.0349 (9)0.0049 (8)0.0018 (7)0.0032 (8)
C100.0493 (12)0.0627 (14)0.0409 (11)0.0179 (10)0.0021 (9)0.0024 (9)
C80.0400 (11)0.0572 (13)0.0552 (12)0.0036 (9)0.0060 (9)0.0056 (10)
C60.0536 (13)0.0626 (14)0.0542 (13)0.0001 (11)0.0081 (10)0.0031 (10)
C110.0560 (13)0.0441 (11)0.0462 (11)0.0051 (9)0.0053 (9)0.0026 (9)
C140.0701 (16)0.0786 (18)0.0583 (14)0.0342 (13)0.0034 (12)0.0022 (12)
C130.0439 (12)0.0566 (14)0.0841 (17)0.0048 (10)0.0094 (11)0.0084 (12)
C20.0717 (15)0.0492 (12)0.0495 (12)0.0151 (11)0.0057 (11)0.0032 (10)
C90.0352 (11)0.0788 (16)0.0597 (13)0.0094 (10)0.0050 (9)0.0050 (12)
C40.096 (2)0.0631 (16)0.0518 (14)0.0215 (14)0.0051 (13)0.0043 (12)
C30.113 (2)0.0462 (13)0.0500 (13)0.0051 (14)0.0040 (14)0.0024 (10)
C50.0628 (15)0.0838 (18)0.0623 (15)0.0133 (13)0.0034 (12)0.0026 (13)
Geometric parameters (Å, º) top
S1—O11.4223 (15)C6—C51.379 (3)
S1—O21.4364 (15)C6—H60.9300
S1—N11.6234 (18)C11—H110.9300
S1—C11.763 (2)C14—H14A0.9600
C12—C111.384 (3)C14—H14B0.9600
C12—C71.385 (3)C14—H14C0.9600
C12—C131.506 (3)C13—H13A0.9600
N1—C71.435 (2)C13—H13B0.9600
N1—H1A0.890 (9)C13—H13C0.9600
C1—C61.380 (3)C2—C31.375 (4)
C1—C21.389 (3)C2—H20.9300
C7—C81.385 (3)C9—H90.9300
C10—C91.375 (3)C4—C51.371 (4)
C10—C111.384 (3)C4—C31.372 (4)
C10—C141.505 (3)C4—H40.9300
C8—C91.372 (3)C3—H30.9300
C8—H80.9300C5—H50.9300
O1—S1—O2119.74 (9)C12—C11—H11118.5
O1—S1—N1108.09 (9)C10—C14—H14A109.5
O2—S1—N1104.94 (9)C10—C14—H14B109.5
O1—S1—C1108.52 (10)H14A—C14—H14B109.5
O2—S1—C1106.98 (10)C10—C14—H14C109.5
N1—S1—C1108.09 (9)H14A—C14—H14C109.5
C11—C12—C7117.73 (18)H14B—C14—H14C109.5
C11—C12—C13119.96 (18)C12—C13—H13A109.5
C7—C12—C13122.30 (17)C12—C13—H13B109.5
C7—N1—S1122.83 (13)H13A—C13—H13B109.5
C7—N1—H1A116.1 (14)C12—C13—H13C109.5
S1—N1—H1A112.1 (15)H13A—C13—H13C109.5
C6—C1—C2120.8 (2)H13B—C13—H13C109.5
C6—C1—S1119.29 (16)C3—C2—C1119.1 (2)
C2—C1—S1119.90 (17)C3—C2—H2120.4
C12—C7—C8120.45 (18)C1—C2—H2120.4
C12—C7—N1121.03 (17)C8—C9—C10121.5 (2)
C8—C7—N1118.39 (18)C8—C9—H9119.3
C9—C10—C11117.50 (19)C10—C9—H9119.3
C9—C10—C14122.0 (2)C5—C4—C3120.6 (2)
C11—C10—C14120.5 (2)C5—C4—H4119.7
C9—C8—C7119.9 (2)C3—C4—H4119.7
C9—C8—H8120.0C4—C3—C2120.1 (2)
C7—C8—H8120.0C4—C3—H3119.9
C5—C6—C1119.1 (2)C2—C3—H3119.9
C5—C6—H6120.5C4—C5—C6120.2 (3)
C1—C6—H6120.5C4—C5—H5119.9
C10—C11—C12122.91 (19)C6—C5—H5119.9
C10—C11—H11118.5
O1—S1—N1—C741.07 (18)N1—C7—C8—C9175.53 (19)
O2—S1—N1—C7169.91 (15)C2—C1—C6—C50.2 (3)
C1—S1—N1—C776.20 (17)S1—C1—C6—C5179.27 (18)
O1—S1—C1—C6161.79 (16)C9—C10—C11—C120.6 (3)
O2—S1—C1—C631.31 (19)C14—C10—C11—C12178.8 (2)
N1—S1—C1—C681.22 (18)C7—C12—C11—C100.7 (3)
O1—S1—C1—C219.14 (19)C13—C12—C11—C10179.29 (19)
O2—S1—C1—C2149.61 (16)C6—C1—C2—C30.2 (3)
N1—S1—C1—C297.85 (17)S1—C1—C2—C3178.86 (16)
C11—C12—C7—C81.2 (3)C7—C8—C9—C101.2 (3)
C13—C12—C7—C8179.7 (2)C11—C10—C9—C81.6 (3)
C11—C12—C7—N1174.51 (17)C14—C10—C9—C8177.9 (2)
C13—C12—C7—N14.0 (3)C5—C4—C3—C20.8 (4)
S1—N1—C7—C12110.71 (19)C1—C2—C3—C40.7 (3)
S1—N1—C7—C873.5 (2)C3—C4—C5—C60.4 (4)
C12—C7—C8—C90.3 (3)C1—C6—C5—C40.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.89 (1)2.09 (1)2.967 (2)170 (2)
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC14H15NO2S
Mr261.33
Crystal system, space groupMonoclinic, P21/n
Temperature (K)294
a, b, c (Å)7.999 (3), 11.073 (4), 15.116 (5)
β (°) 96.822 (6)
V3)1329.4 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.22 × 0.20 × 0.16
Data collection
DiffractometerBruker SMART 1K CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.950, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
7489, 2721, 2098
Rint0.025
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.122, 1.05
No. of reflections2721
No. of parameters168
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.34

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected torsion angles (º) top
S1—N1—C7—C12110.71 (19)S1—N1—C7—C873.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.890 (9)2.086 (11)2.967 (2)170 (2)
Symmetry code: (i) x, y+1, z+1.
 

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