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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1845.
Published online 2008 August 30. doi:  10.1107/S1600536808027219
PMCID: PMC2960482

(E)-N′-Benzyl­idene-p-toluene­sulfono­hydrazide

Abstract

In the title compound, C14H14N2O2S, a novel sulfonamide derivative, an intra­molecular C—H(...)O hydrogen bond generates an S(5) ring motif. The mol­ecule adopts a twisted E configuration around the C=N bond. An inter­molecular N—H(...)O hydrogen bond generates an R 2 2(8) ring motif. The dihedral angle between the rings is 85.37 (9)°. The H atoms of the methyl group have rotational disorder with refined site occupancies of ca 0.63/0.37. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds link neighbouring mol­ecules into dimers which stack along the a axis with a centroid–centroid distance of 3.8856 (10) Å.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For related structures and applications, see, for example: Tabatabaee et al. (2007 [triangle]); Ali et al. (2007 [triangle]); Tierney et al. (2006 [triangle]); Krygowski et al. (1998 [triangle]); Kayser et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1845-scheme1.jpg

Experimental

Crystal data

  • C14H14N2O2S
  • M r = 274.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1845-efi1.jpg
  • a = 5.9593 (7) Å
  • b = 9.6592 (7) Å
  • c = 23.712 (3) Å
  • β = 91.533 (9)°
  • V = 1364.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 293 (2) K
  • 0.50 × 0.40 × 0.03 mm

Data collection

  • STOE IPDSII diffractometer
  • Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2004 [triangle]) T min = 0.879, T max = 0.993
  • 8939 measured reflections
  • 3573 independent reflections
  • 3008 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.110
  • S = 1.10
  • 3573 reflections
  • 195 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek,2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027219/at2617sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027219/at2617Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

HM thanks Vali-e-Asr University of Rafsanjan for the financial support of this work. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HM thanks Professor H.-K. Fun for helpful comments.

supplementary crystallographic information

Comment

Sulfonamides were the first class of antimicrobial agents to be discovered. They inhibit dihydropteroate synthetase in the bacterial folic acid pathway. Although their clinical role has diminished, they are still useful in certain situations, because of its efficacy and low cost (Krygowski et al., 1998). Sulfonamides (sulfanilamide, sulfamethoxazole, sulfafurazole) are structural analogs of p-aminobenzoic acid (PABA) and compete with PABA to block its conversion to dihydrofolic acid. These agents are generally used in combination with other drugs (usually sulfonamides) to prevent or treat a number of bacterial and parasitic infections (Tierney et al., 2006). Some of the applications of sulfonamides are the anti-infective agents of choice, as follows: Bacteria as Human Pathogens, such as Antibiotic Treatment of Infections Caused by Gram-Positive Bacilli and Gram-negative Haemophilus ducreyi and Haemophilus aegyptius, Alternative Drug for treatment of Chlamydia related diseases (including C. trachomatis, Chlamydia psittaci, Chlamydia pneumonia), Anti-malarial Agents as Dihydropteroate synthetase inhibitors, alternative drugs in tuberculosis treatment, long term treatment of leprosy, treatment of ocular infections. In the latter treatment causative organisms must be identified, and it is preferable to use a drug that is not given systemically. Sulfonamides are also assumed as permitted antibiotics in Pregnancy (Kayser et al., 2004).

The title compound (I) (Fig. 1), is a novel sulfonamide derivative. Bond lengths and angles are within the normal ranges (Allen et al., 1987) and are comparable with the similar staructures (Ali et al. 2007). An intramolecular C—H···O hydrogen bond generate S(5) ring motif (Bernstein et al., 1995). The molecule adopts a twisted E configuration around the C═N. An intermolecular N—H···O hydrogen bond genarate R22(8) ring motif (Bernstein et al., 1995). The dihedral angle between the phenyl rings is 85.37 (9)°. None of the H atoms of the methyl group was clearly resolved in the difference Fourier map and they were disordered over six positions and refined with site-occupancy factors of 0.62 (3) and 0.38 (3) for the major and minor componenets, respectively. In the crystal structure, intermolecular N—H···O interactions link neighbouring molecules into dimers which stacked along the a-axis. The short distance between the centroids of the six-membered rings prove an exsistence of the π-π interactions with centroid to centroid dsiatnce of 3.8856 (10) Å. The crystal structure is stabilized by intramolecular C—H···O, intermolecular N—H···O hydrogen bonds and π-π satcking.

Experimental

p-Tosylhydrazine (3 mmol) was added to a stirred solution of benzaldehyde (3 mmol) in 2 ml of toluene at 20–25° C. The mixture was stirred for 6 h at 110° C. After cooling, the colorless crystalline solid was isolated by filtration, washed with cold toluene, and re-crystallized from ethanol.

Refinement

H atom bound to N1 was located from a difference Fourier map and refined freely. The methyl hydrogen atoms were located from the difference Fourier map and refined freely with the parent atom. The rest of the hydrogen atoms were positioned geometrically and refined as riding model.

Figures

Fig. 1.
The molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering. Open bonds indicate the minor disordered component. Intramolecular hydrogen bond is shown as a dashed line.
Fig. 2.
The crystal packing of the major component of (I), viewed down the a-axis, showing staking arrangement of molecules. Intermolecular and intermolecular hydrogen bonds are shown as dashed line.

Crystal data

C14H14N2O2SF000 = 576
Mr = 274.33Dx = 1.336 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2500 reflections
a = 5.9593 (7) Åθ = 2.3–29.2º
b = 9.6592 (7) ŵ = 0.24 mm1
c = 23.712 (3) ÅT = 293 (2) K
β = 91.533 (9)ºPlate, colourless
V = 1364.4 (3) Å30.50 × 0.40 × 0.03 mm
Z = 4

Data collection

STOE IPDSII diffractometer3573 independent reflections
Radiation source: fine-focus sealed tube3008 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
Detector resolution: 0.15 pixels mm-1θmax = 29.0º
T = 293(2) Kθmin = 2.3º
[var phi] scansh = −8→6
Absorption correction: numerical(X-SHAPE; Stoe & Cie, 2004)k = −12→13
Tmin = 0.879, Tmax = 0.993l = −32→32
8939 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110  w = 1/[σ2(Fo2) + (0.0507P)2 + 0.2385P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3573 reflectionsΔρmax = 0.23 e Å3
195 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/UeqOcc. (<1)
S10.24869 (6)0.18884 (4)0.001194 (15)0.04475 (12)
O10.39754 (19)0.13796 (12)−0.04087 (4)0.0555 (3)
O20.03368 (18)0.24148 (12)−0.01555 (5)0.0572 (3)
N10.2191 (2)0.05429 (14)0.04190 (6)0.0531 (3)
H1N10.328 (3)−0.004 (2)0.0425 (8)0.063 (5)*
N20.0856 (2)0.06535 (13)0.08855 (6)0.0500 (3)
C10.6026 (2)0.28675 (16)0.06340 (7)0.0504 (3)
H1A0.67060.20230.05580.060*
C20.7124 (3)0.38438 (18)0.09592 (7)0.0565 (4)
H2A0.85480.36480.11080.068*
C30.6147 (3)0.51220 (17)0.10705 (6)0.0542 (4)
C40.4028 (3)0.53993 (16)0.08404 (7)0.0551 (4)
H4A0.33670.62550.09050.066*
C50.2883 (2)0.44255 (15)0.05169 (6)0.0480 (3)
H5A0.14600.46190.03670.058*
C60.3884 (2)0.31589 (14)0.04191 (6)0.0418 (3)
C70.1133 (3)−0.03135 (15)0.12464 (7)0.0509 (3)
H7A0.2260−0.09620.11920.061*
C8−0.0264 (3)−0.04390 (16)0.17434 (6)0.0516 (3)
C90.0359 (3)−0.1379 (2)0.21640 (7)0.0655 (4)
H9A0.1678−0.18850.21340.079*
C10−0.0980 (5)−0.1566 (3)0.26284 (8)0.0807 (6)
H10A−0.0555−0.21960.29080.097*
C11−0.2921 (5)−0.0825 (3)0.26759 (9)0.0884 (7)
H11A−0.3815−0.09530.29870.106*
C12−0.3558 (4)0.0115 (3)0.22621 (10)0.0858 (6)
H12A−0.48760.06200.22960.103*
C13−0.2239 (3)0.0303 (2)0.17986 (8)0.0677 (5)
H13A−0.26790.09330.15210.081*
C140.7396 (5)0.6169 (3)0.14314 (10)0.0776 (6)
H14A0.651 (10)0.695 (7)0.147 (3)0.116*0.63 (4)
H14B0.855 (10)0.656 (7)0.124 (2)0.116*0.63 (4)
H14C0.789 (11)0.581 (6)0.177 (2)0.116*0.63 (4)
H14D0.73 (2)0.714 (12)0.128 (4)0.116*0.37 (4)
H14E0.920 (16)0.579 (9)0.151 (4)0.116*0.37 (4)
H14F0.648 (17)0.625 (10)0.185 (4)0.116*0.37 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.04108 (18)0.04409 (19)0.04919 (19)0.00320 (13)0.00301 (13)−0.00108 (14)
O10.0593 (6)0.0565 (6)0.0512 (5)0.0086 (5)0.0097 (5)−0.0032 (5)
O20.0440 (6)0.0602 (6)0.0668 (7)0.0048 (5)−0.0070 (5)−0.0030 (5)
N10.0518 (7)0.0427 (6)0.0656 (8)0.0037 (5)0.0150 (6)0.0018 (6)
N20.0461 (6)0.0451 (6)0.0592 (7)−0.0026 (5)0.0096 (5)−0.0020 (5)
C10.0421 (7)0.0527 (8)0.0564 (8)0.0078 (6)0.0017 (6)0.0020 (6)
C20.0445 (7)0.0672 (10)0.0573 (8)−0.0030 (7)−0.0046 (6)0.0058 (7)
C30.0606 (9)0.0558 (8)0.0463 (7)−0.0140 (7)0.0025 (6)0.0044 (6)
C40.0635 (9)0.0421 (7)0.0600 (8)0.0010 (6)0.0065 (7)0.0005 (6)
C50.0424 (7)0.0448 (7)0.0568 (8)0.0051 (5)0.0011 (6)0.0043 (6)
C60.0376 (6)0.0437 (7)0.0442 (6)0.0017 (5)0.0049 (5)0.0045 (5)
C70.0494 (8)0.0433 (7)0.0601 (8)−0.0005 (6)0.0041 (6)−0.0039 (6)
C80.0559 (8)0.0472 (7)0.0515 (7)−0.0083 (6)0.0007 (6)−0.0062 (6)
C90.0745 (11)0.0648 (10)0.0568 (9)−0.0035 (9)−0.0053 (8)−0.0001 (8)
C100.1072 (17)0.0847 (14)0.0501 (9)−0.0107 (12)−0.0013 (10)0.0050 (9)
C110.1082 (18)0.1013 (17)0.0570 (10)−0.0159 (14)0.0253 (11)−0.0081 (11)
C120.0802 (14)0.0963 (16)0.0823 (13)0.0054 (12)0.0281 (11)−0.0057 (12)
C130.0655 (11)0.0687 (11)0.0695 (10)0.0047 (8)0.0135 (8)0.0040 (9)
C140.0961 (17)0.0716 (13)0.0646 (11)−0.0275 (12)−0.0085 (11)−0.0039 (10)

Geometric parameters (Å, °)

S1—O21.4250 (11)C7—H7A0.9300
S1—O11.4389 (11)C8—C131.387 (3)
S1—N11.6313 (14)C8—C91.392 (2)
S1—C61.7573 (14)C9—C101.389 (3)
N1—N21.3840 (18)C9—H9A0.9300
N1—H1N10.86 (2)C10—C111.368 (4)
N2—C71.274 (2)C10—H10A0.9300
C1—C21.373 (2)C11—C121.382 (3)
C1—C61.3908 (19)C11—H11A0.9300
C1—H1A0.9300C12—C131.380 (3)
C2—C31.393 (2)C12—H12A0.9300
C2—H2A0.9300C13—H13A0.9300
C3—C41.388 (2)C14—H14A0.93 (7)
C3—C141.509 (2)C14—H14B0.92 (6)
C4—C51.382 (2)C14—H14C0.92 (6)
C4—H4A0.9300C14—H14D1.00 (11)
C5—C61.3832 (19)C14—H14E1.15 (10)
C5—H5A0.9300C14—H14F1.15 (10)
C7—C81.466 (2)
O2—S1—O1119.68 (7)C10—C9—H9A119.8
O2—S1—N1109.79 (7)C8—C9—H9A119.8
O1—S1—N1102.50 (7)C11—C10—C9120.2 (2)
O2—S1—C6108.24 (7)C11—C10—H10A119.9
O1—S1—C6109.13 (7)C9—C10—H10A119.9
N1—S1—C6106.76 (7)C10—C11—C12120.1 (2)
N2—N1—S1119.01 (10)C10—C11—H11A119.9
N2—N1—H1N1119.1 (13)C12—C11—H11A119.9
S1—N1—H1N1116.1 (13)C13—C12—C11120.0 (2)
C7—N2—N1114.41 (13)C13—C12—H12A120.0
C2—C1—C6119.05 (14)C11—C12—H12A120.0
C2—C1—H1A120.5C12—C13—C8120.64 (19)
C6—C1—H1A120.5C12—C13—H13A119.7
C1—C2—C3121.33 (14)C8—C13—H13A119.7
C1—C2—H2A119.3C3—C14—H14A109 (4)
C3—C2—H2A119.3C3—C14—H14B111 (3)
C4—C3—C2118.47 (14)H14A—C14—H14B99 (4)
C4—C3—C14121.57 (19)C3—C14—H14C113 (3)
C2—C3—C14119.96 (19)H14A—C14—H14C112 (5)
C5—C4—C3121.13 (15)H14B—C14—H14C112 (5)
C5—C4—H4A119.4C3—C14—H14D113 (5)
C3—C4—H4A119.4H14A—C14—H14D41 (6)
C4—C5—C6119.10 (14)H14B—C14—H14D59 (5)
C4—C5—H5A120.4H14C—C14—H14D133 (6)
C6—C5—H5A120.4C3—C14—H14E109 (4)
C5—C6—C1120.88 (14)H14A—C14—H14E141 (5)
C5—C6—S1120.65 (11)H14B—C14—H14E60 (4)
C1—C6—S1118.47 (11)H14C—C14—H14E58 (4)
N2—C7—C8122.31 (14)H14D—C14—H14E114 (7)
N2—C7—H7A118.8C3—C14—H14F108 (4)
C8—C7—H7A118.8H14A—C14—H14F64 (5)
C13—C8—C9118.70 (16)H14B—C14—H14F141 (5)
C13—C8—C7122.31 (15)H14C—C14—H14F54 (4)
C9—C8—C7118.94 (16)H14D—C14—H14F102 (7)
C10—C9—C8120.3 (2)H14E—C14—H14F110 (6)
O2—S1—N1—N2−52.51 (14)N1—S1—C6—C5−119.42 (12)
O1—S1—N1—N2179.27 (11)O2—S1—C6—C1179.55 (11)
C6—S1—N1—N264.61 (13)O1—S1—C6—C1−48.69 (13)
S1—N1—N2—C7−164.31 (11)N1—S1—C6—C161.41 (13)
C6—C1—C2—C3−0.9 (2)N1—N2—C7—C8−174.66 (13)
C1—C2—C3—C4−0.5 (2)N2—C7—C8—C1313.1 (2)
C1—C2—C3—C14179.77 (17)N2—C7—C8—C9−169.75 (15)
C2—C3—C4—C51.2 (2)C13—C8—C9—C100.0 (3)
C14—C3—C4—C5−179.06 (17)C7—C8—C9—C10−177.21 (16)
C3—C4—C5—C6−0.5 (2)C8—C9—C10—C11−0.1 (3)
C4—C5—C6—C1−1.0 (2)C9—C10—C11—C12−0.1 (4)
C4—C5—C6—S1179.82 (11)C10—C11—C12—C130.3 (4)
C2—C1—C6—C51.7 (2)C11—C12—C13—C8−0.3 (3)
C2—C1—C6—S1−179.11 (12)C9—C8—C13—C120.1 (3)
O2—S1—C6—C5−1.28 (14)C7—C8—C13—C12177.28 (18)
O1—S1—C6—C5130.48 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1i0.863 (19)2.082 (19)2.9446 (17)177.0 (18)
C5—H5A···O20.932.542.9133 (18)104

Symmetry codes: (i) −x+1, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2617).

References

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  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Stoe & Cie (2004). X-SHAPE. Stoe & Cie, Darmstadt, Germany.
  • Stoe & Cie (2005). X-AREA. Stoe & Cie, Darmstadt, Germany.
  • Tabatabaee, M., Anari-Abbasnejad, M., Nozari, N., Sadegheian, S. & Ghasemzadeh, M. (2007). Acta Cryst. E63, o2099–o2100.
  • Tierney, L. M., McPhee, S. J. & Papadakis, M. A. (2006). Current Medical Diagnosis & Treatment, 45th ed., pp. 1–50. New York: McGraw-Hill Medical.

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