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Acta Cryst. (2009). E65, o2143    [ doi:10.1107/S1600536809031481 ]

2-[(E)-2-(4-Methylbenzenesulfonamido)ethyliminiomethyl]-4-nitrophenolate

M. Tüfekçi, G. Alpaslan, M. Macit and A. Erdönmez

Abstract top

The molecule of the title compound, C16H17N3O5S, crystallizes in a zwitterionic form, with a strong intramolecular N-H...O hydrogen bond. The dihedral angle between the two benzene rings is 7.06 (9)°. In the crystal, molecules are linked into chains along the c axis by intermolecular N-H...O hydrogen bonds.

Comment top

Schiff bases have been extensively used as ligands in the field of coordination chemistry (Calligaris et al., 1972). Schiff base compounds can be classified by their photochromic and thermochromic characteristics (Cohen et al., 1964). These properties result from a proton transfer from the hydroxyl O atom to the imine N atom (Hadjoudis et al., 1987). Schiff bases exhibit two well known tautomeric forms viz. OH and NH tautomers, and they also exist in zwitterionic form (Karabıyık et al., 2008). Our investigations show that the title compund has a zwitterionic form with a strong intramolecular N—H···O hydrogen bond (Fig. 1).

The C7N2 [1.292 (2) Å] and C6—03 [1.272 (2) Å] bond distances in the title compound are comparable to those [1.292 (2) and 1.264 (2) Å] observed in a related zwitterionic structure (Ali et al., 2008). The molecule adopts a folded conformation. The dihedral angle between the two benzene rings is 7.06 (9)°.

The intramolecular N2—H1A···O3 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). The molecules are linked into chains (Fig. 2) along the c axis by intermolecular N—H···O hydrogen bonds (Table 1).

Related literature top

For general background to Schiff bases, see: Calligaris et al. (1972); Cohen et al. (1964); Hadjoudis et al. (1987); Karabıyık et al. (2008). For the crystal structure of 2-[2-(1H-indol-3-yl)ethyliminiomethyl]-4-nitrophenolate, see: Ali et al. (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

2-Hydroxy-5-nitrobenzaldehyde (10 mg, 5.98× 10-2 mmol) in ethanol (20 ml) was added to a solution of N-p-tolyl-sulfonylethylenediamine (12.7 mg, 5.98× 10-2 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. Single crystals of the title compound were obtained by slow evaporation of an ethylacetate solution (yield 55%; m.p. 446–447 K).

Refinement top

Atoms H1 and H1A were located in a difference map and were refined freely. The remaining H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates a hydrogen bond.
[Figure 2] Fig. 2. A packing diagram for (I). H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.
2-[(E)-2-(4-Methylbenzenesulfonamido)ethyliminiomethyl]-4-nitrophenolate top
Crystal data top
C16H17N3O5SF(000) = 760
Mr = 363.39Dx = 1.448 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 37649 reflections
a = 17.915 (5) Åθ = 1.6–28.0°
b = 7.342 (5) ŵ = 0.23 mm−1
c = 13.055 (5) ÅT = 296 K
β = 103.928 (5)°Block, yellow
V = 1666.7 (14) Å30.68 × 0.50 × 0.26 mm
Z = 4
Data collection top
Stoe IPDS-II
diffractometer		3272 independent reflections
Radiation source: fine-focus sealed tube2845 reflections with I > 2σ(I)
graphiteRint = 0.024
Detector resolution: 6.67 pixels mm-1θmax = 26.0°, θmin = 2.3°
ω scansh = −22→22
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		k = −9→9
Tmin = 0.887, Tmax = 0.956l = −16→15
22908 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0542P)2 + 0.2378P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.004
3272 reflectionsΔρmax = 0.26 e Å−3
236 parametersΔρmin = −0.27 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0025 (8)
Crystal data top
C16H17N3O5SV = 1666.7 (14) Å3
Mr = 363.39Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.915 (5) ŵ = 0.23 mm−1
b = 7.342 (5) ÅT = 296 K
c = 13.055 (5) Å0.68 × 0.50 × 0.26 mm
β = 103.928 (5)°
Data collection top
Stoe IPDS-II
diffractometer		3272 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		2845 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.956Rint = 0.024
22908 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094Δρmax = 0.26 e Å−3
S = 1.07Δρmin = −0.27 e Å−3
3272 reflectionsAbsolute structure: ?
236 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.73857 (9)0.1439 (2)0.58535 (12)0.0464 (3)
C20.81399 (10)0.1345 (2)0.64584 (14)0.0559 (4)
H20.82380.14050.71900.067*
C30.87338 (10)0.1163 (3)0.59823 (15)0.0604 (4)
C40.86008 (11)0.1075 (3)0.48830 (16)0.0648 (5)
H40.90120.09580.45670.078*
C50.78743 (11)0.1160 (3)0.42812 (15)0.0642 (5)
H50.77960.10930.35520.077*
C60.72214 (10)0.1346 (2)0.47198 (13)0.0523 (4)
C70.67882 (9)0.1617 (2)0.63841 (13)0.0463 (3)
H70.69250.16480.71180.056*
C80.54749 (9)0.1973 (2)0.65034 (13)0.0466 (4)
H8A0.56610.15050.72140.056*
H8B0.50240.12750.61620.056*
C90.52559 (8)0.3947 (2)0.65549 (12)0.0438 (3)
H9A0.50850.44190.58430.053*
H9B0.48290.40350.68890.053*
C100.69671 (8)0.65737 (19)0.62312 (11)0.0400 (3)
C110.69016 (9)0.6244 (2)0.51721 (12)0.0495 (4)
H110.64200.61820.47050.059*
C120.75608 (10)0.6008 (3)0.48147 (13)0.0571 (4)
H120.75150.57810.41020.068*
C130.82838 (10)0.6100 (2)0.54833 (15)0.0553 (4)
C140.83365 (10)0.6421 (3)0.65479 (15)0.0601 (4)
H140.88180.64740.70150.072*
C150.76879 (9)0.6661 (2)0.69225 (13)0.0522 (4)
H150.77330.68820.76360.063*
C160.89969 (12)0.5917 (3)0.50703 (19)0.0795 (6)
H16A0.88630.54030.43740.119*
H16B0.93590.51360.55290.119*
H16C0.92230.70970.50450.119*
N10.95110 (10)0.1062 (3)0.66326 (18)0.0917 (6)
N20.60663 (7)0.17413 (18)0.59235 (11)0.0456 (3)
N30.58876 (7)0.50612 (18)0.71366 (10)0.0448 (3)
O10.96069 (10)0.1084 (5)0.75840 (16)0.1571 (12)
O21.00420 (9)0.0954 (4)0.62016 (16)0.1183 (7)
O30.65360 (7)0.1427 (2)0.41569 (9)0.0669 (4)
O40.55334 (6)0.75149 (15)0.58460 (9)0.0479 (3)
O50.63776 (6)0.81294 (15)0.76080 (9)0.0522 (3)
S10.614192 (19)0.69488 (5)0.67146 (3)0.03887 (13)
H10.6088 (10)0.478 (2)0.7710 (14)0.048 (5)*
H1A0.5970 (12)0.176 (3)0.5235 (17)0.067 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0470 (8)0.0456 (8)0.0471 (8)−0.0002 (6)0.0121 (7)−0.0028 (7)
C20.0522 (9)0.0660 (10)0.0494 (9)−0.0005 (8)0.0124 (7)0.0003 (8)
C30.0452 (9)0.0709 (11)0.0658 (11)0.0025 (8)0.0148 (8)0.0017 (9)
C40.0601 (11)0.0720 (12)0.0701 (12)0.0056 (9)0.0307 (9)−0.0012 (10)
C50.0709 (12)0.0753 (12)0.0507 (9)0.0086 (10)0.0232 (9)−0.0062 (9)
C60.0568 (10)0.0516 (9)0.0487 (9)0.0038 (7)0.0130 (7)−0.0072 (7)
C70.0505 (9)0.0449 (8)0.0432 (8)−0.0021 (6)0.0107 (7)−0.0007 (6)
C80.0438 (8)0.0475 (8)0.0502 (9)−0.0058 (6)0.0147 (7)0.0030 (7)
C90.0348 (7)0.0498 (8)0.0472 (8)−0.0037 (6)0.0109 (6)0.0008 (7)
C100.0389 (7)0.0409 (7)0.0399 (7)−0.0016 (6)0.0089 (6)0.0033 (6)
C110.0425 (8)0.0643 (10)0.0407 (8)−0.0008 (7)0.0079 (6)0.0049 (7)
C120.0556 (10)0.0750 (12)0.0440 (9)0.0037 (8)0.0185 (7)0.0086 (8)
C130.0469 (9)0.0583 (10)0.0651 (11)0.0003 (7)0.0222 (8)0.0094 (8)
C140.0378 (8)0.0749 (12)0.0637 (11)−0.0013 (8)0.0044 (7)0.0005 (9)
C150.0444 (8)0.0643 (10)0.0450 (8)0.0001 (7)0.0054 (7)−0.0027 (7)
C160.0553 (11)0.0987 (16)0.0943 (15)0.0034 (11)0.0372 (11)0.0117 (13)
N10.0490 (9)0.1412 (19)0.0847 (13)0.0029 (11)0.0154 (9)0.0064 (13)
N20.0471 (7)0.0463 (7)0.0444 (7)−0.0015 (5)0.0131 (6)−0.0026 (6)
N30.0466 (7)0.0521 (8)0.0328 (7)−0.0071 (6)0.0041 (5)0.0045 (6)
O10.0575 (10)0.327 (4)0.0791 (12)0.0105 (15)0.0021 (9)0.0096 (18)
O20.0494 (8)0.195 (2)0.1165 (14)0.0089 (11)0.0310 (9)−0.0005 (14)
O30.0600 (8)0.0888 (9)0.0472 (7)0.0093 (7)0.0038 (6)−0.0159 (6)
O40.0417 (5)0.0488 (6)0.0494 (6)0.0043 (4)0.0034 (5)0.0055 (5)
O50.0512 (6)0.0543 (6)0.0504 (6)−0.0036 (5)0.0108 (5)−0.0159 (5)
S10.03696 (19)0.0403 (2)0.0382 (2)0.00009 (14)0.00693 (14)−0.00238 (14)
Geometric parameters (Å, °) top
C1—C21.393 (2)C10—C151.387 (2)
C1—C71.414 (2)C10—S11.7631 (15)
C1—C61.440 (2)C11—C121.381 (2)
C2—C31.362 (2)C11—H110.93
C2—H20.93C12—C131.378 (3)
C3—C41.399 (3)C12—H120.93
C3—N11.448 (3)C13—C141.390 (3)
C4—C51.350 (3)C13—C161.507 (2)
C4—H40.93C14—C151.376 (2)
C5—C61.427 (2)C14—H140.93
C5—H50.93C15—H150.93
C6—O31.272 (2)C16—H16A0.96
C7—N21.292 (2)C16—H16B0.96
C7—H70.93C16—H16C0.96
C8—N21.4529 (19)N1—O11.212 (3)
C8—C91.507 (2)N1—O21.219 (2)
C8—H8A0.97N2—H1A0.87 (2)
C8—H8B0.97N3—S11.5976 (16)
C9—N31.4537 (19)N3—H10.777 (18)
C9—H9A0.97O4—S11.4325 (11)
C9—H9B0.97O5—S11.4329 (12)
C10—C111.381 (2)
C2—C1—C7118.18 (15)C10—C11—C12119.13 (15)
C2—C1—C6120.72 (15)C10—C11—H11120.4
C7—C1—C6121.10 (15)C12—C11—H11120.4
C3—C2—C1120.26 (16)C13—C12—C11121.97 (16)
C3—C2—H2119.9C13—C12—H12119.0
C1—C2—H2119.9C11—C12—H12119.0
C2—C3—C4120.93 (17)C12—C13—C14117.95 (15)
C2—C3—N1118.96 (18)C12—C13—C16121.15 (18)
C4—C3—N1120.11 (17)C14—C13—C16120.87 (17)
C5—C4—C3119.81 (16)C15—C14—C13121.12 (16)
C5—C4—H4120.1C15—C14—H14119.4
C3—C4—H4120.1C13—C14—H14119.4
C4—C5—C6122.64 (17)C14—C15—C10119.75 (16)
C4—C5—H5118.7C14—C15—H15120.1
C6—C5—H5118.7C10—C15—H15120.1
O3—C6—C5122.91 (16)C13—C16—H16A109.5
O3—C6—C1121.46 (15)C13—C16—H16B109.5
C5—C6—C1115.63 (16)H16A—C16—H16B109.5
N2—C7—C1124.73 (15)C13—C16—H16C109.5
N2—C7—H7117.6H16A—C16—H16C109.5
C1—C7—H7117.6H16B—C16—H16C109.5
N2—C8—C9111.47 (12)O1—N1—O2122.7 (2)
N2—C8—H8A109.3O1—N1—C3118.65 (18)
C9—C8—H8A109.3O2—N1—C3118.7 (2)
N2—C8—H8B109.3C7—N2—C8122.67 (14)
C9—C8—H8B109.3C7—N2—H1A114.1 (14)
H8A—C8—H8B108.0C8—N2—H1A123.0 (14)
N3—C9—C8112.72 (13)C9—N3—S1123.98 (11)
N3—C9—H9A109.0C9—N3—H1118.3 (13)
C8—C9—H9A109.0S1—N3—H1117.4 (13)
N3—C9—H9B109.0O4—S1—O5119.20 (8)
C8—C9—H9B109.0O4—S1—N3107.39 (7)
H9A—C9—H9B107.8O5—S1—N3107.26 (8)
C11—C10—C15120.07 (14)O4—S1—C10107.82 (7)
C11—C10—S1120.62 (11)O5—S1—C10106.12 (7)
C15—C10—S1119.29 (12)N3—S1—C10108.74 (7)
C7—C1—C2—C3179.67 (16)C12—C13—C14—C15−0.7 (3)
C6—C1—C2—C30.0 (3)C16—C13—C14—C15177.35 (18)
C1—C2—C3—C40.2 (3)C13—C14—C15—C100.3 (3)
C1—C2—C3—N1−179.76 (18)C11—C10—C15—C140.1 (3)
C2—C3—C4—C5−0.4 (3)S1—C10—C15—C14−178.20 (13)
N1—C3—C4—C5179.6 (2)C2—C3—N1—O12.3 (4)
C3—C4—C5—C60.3 (3)C4—C3—N1—O1−177.7 (3)
C4—C5—C6—O3180.00 (19)C2—C3—N1—O2−177.8 (2)
C4—C5—C6—C10.0 (3)C4—C3—N1—O22.2 (4)
C2—C1—C6—O3179.83 (16)C1—C7—N2—C8−178.27 (14)
C7—C1—C6—O30.2 (3)C9—C8—N2—C796.71 (17)
C2—C1—C6—C5−0.1 (2)C8—C9—N3—S1131.22 (13)
C7—C1—C6—C5−179.75 (16)C9—N3—S1—O414.65 (14)
C2—C1—C7—N2179.17 (15)C9—N3—S1—O5143.88 (12)
C6—C1—C7—N2−1.2 (3)C9—N3—S1—C10−101.76 (13)
N2—C8—C9—N3−63.94 (17)C11—C10—S1—O4−21.41 (15)
C15—C10—C11—C12−0.1 (2)C15—C10—S1—O4156.87 (13)
S1—C10—C11—C12178.14 (13)C11—C10—S1—O5−150.18 (13)
C10—C11—C12—C13−0.3 (3)C15—C10—S1—O528.09 (15)
C11—C12—C13—C140.7 (3)C11—C10—S1—N394.72 (14)
C11—C12—C13—C16−177.38 (18)C15—C10—S1—N3−87.00 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H1···O3i0.78 (2)2.06 (2)2.833 (2)170 (2)
N2—H1A···O30.87 (2)1.94 (2)2.648 (2)137 (2)
Symmetry codes: (i) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H1···O3i0.78 (2)2.06 (2)2.833 (2)170 (2)
N2—H1A···O30.87 (2)1.94 (2)2.648 (2)137 (2)
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS-II diffractometer (purchased under grant No. F279 of the University Research Fund).

references
References top

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