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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o736.
Published online 2010 March 3. doi:  10.1107/S1600536810007075
PMCID: PMC2983826

4-Methyl­benzyl 4-amino­benzoate

Abstract

The dihedral angle between the two benzene rings in the title compound, C15H15NO2, is 65.28 (12)°. The crystal structure is stabilized by N—H(...)N and N—H(...)O hydrogen bonds, leading to the formation of supra­molecular chains along the a-axis direction.

Related literature

For the reduction of aryl-nitro compounds, see: Tafesh & Weiguny (1996 [triangle]); Vass et al. (2001 [triangle]); Entwistle et al. (1977 [triangle]); Bavin (1958 [triangle]); Yuste et al. (1982 [triangle]); Idrees et al. (2009 [triangle]). For the uses of amines, see: Kumarraja & Pitchumani (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o736-scheme1.jpg

Experimental

Crystal data

  • C15H15NO2
  • M r = 241.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o736-efi1.jpg
  • a = 8.2097 (12) Å
  • b = 5.5344 (5) Å
  • c = 14.293 (2) Å
  • β = 98.531 (12)°
  • V = 642.24 (14) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 173 K
  • 0.27 × 0.13 × 0.13 mm

Data collection

  • Stoe IPDSII two-circle diffractometer
  • 4021 measured reflections
  • 1322 independent reflections
  • 960 reflections with I > 2σ(I)
  • R int = 0.093

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.094
  • S = 0.91
  • 1322 reflections
  • 173 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007075/tk2629sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007075/tk2629Isup2.hkl

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

Acknowledgments

The authors are grateful to the Department of Chemistry, Quaid-I-Azam University, Islamabad, Pakistan, and the Institute for Inorganic Chemistry, University of Frankfurt, Germany, for providing laboratory and analytical facilities. They also thank the Higher Education Commission of Pakistan for financial support through Project No. 20–723/ R&D/06/191.

supplementary crystallographic information

Comment

Reduction of aryl-nitro compounds to their corresponding amines is an important chemical transformation in synthetic organic chemistry mainly due to the fact that the amino group can serve as the site for further derivatization (Tafesh et al., 1996; Vass et al., 2001). Amines are important intermediates in the production of many pharmaceuticals, photographic materials, agrochemicals, polymers, dyes, and rubber materials (Kumarraja & Pitchumani, 2004). Selective reduction nitro-aromatics to amines can be achieved by hydrogen transfer using Pt—C (Entwistle et al., 1977), Pd—C (Bavin et al., 1958) and Raney Ni (Yuste et al., 1982) catalysts. Most commonly applied or reported methods are direct catalytic hydrogenation and catalytic hydrazine reduction. The reduction of 1,4-bis(4-nitrobenzoyloxymethyl) benzene has been carried out using the catalytic hydrogenation method. It is important to note that the process requires much care in the addition of hydrazine, in order to prevent the breakdown of the ester linkage, as hydrazides may be formed from carboxylic esters in the absence of the catalyst or even if the catalyst is not properly charged (Idrees et al., 2009). The limited addition of the hydrazine in the presence of activated catalyst can also cause the breakage of ester linkage not from the aryl carbon but from the acyl carbon as proved by the crystal structure of the title compound, (I). Herein, the synthesis and the crystal structure of (I) are reported.

The dihedral angle between the two benzene rings in (I) is 65.28 (12)°. The crystal structure is stabilized by N—H···N and N—H···O hydrogen bonds, Table 1, which lead to supramolecular chains along the a direction.

Experimental

Compound (I) was synthesized in two steps. In the first step, a mixture of 1,4-bis(chloromethyl)benzene Aldrich; 2.00 g, 0.0114 mol), anhydrous K2CO3 (3.154 g, 0.0229 mol) and 4-nitrobenzoic acid (3.824 g, 0.0229 mol) were added to a two neck round bottom flask charged with DMF (50 ml). This was heated at 393 K for 12 h under an nitrogen atmosphere. After cooling to room temperature, the reaction mixture was poured into water (800 ml) to precipitate a yellow solid which was washed thoroughly with water and then separated by filtration. In the second step a 250 ml two neck flask was charged with the just synthesised yellow solid (1.00 g, 2.84 mmol) and was refluxed in ethanol with 5% palladium on carbon (Pd/C, 0.06 g), followed by the drop-wise addition of hydrated hydrazine (80%) diluted in ethanol. The mixture was refluxed for 8 h and then filtered to remove Pd/C. The solvent was evaporated and the resulting crude solid was recrystallized from ethanol to afford crystals (yield:68%, m.pt.: 397 K).

Refinement

Hydrogen atoms bonded to C were included in calculated positions [C—H = 0.95–0.99 Å] and refined as riding [Uiso(H) = 1.2–1.5Ueq(C)]. The H atoms bonded to N were isotropically refined. Due to the absence of anomalous scatterers, the absolute structure could not be determined and 773 Friedel pairs were merged.

Figures

Fig. 1.
Perspective view of (I) with the atom numbering scheme. The displacement ellipsoids are at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii.

Crystal data

C15H15NO2F(000) = 256
Mr = 241.28Dx = 1.248 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2492 reflections
a = 8.2097 (12) Åθ = 4.0–25.9°
b = 5.5344 (5) ŵ = 0.08 mm1
c = 14.293 (2) ÅT = 173 K
β = 98.531 (12)°Prism, colourless
V = 642.24 (14) Å30.27 × 0.13 × 0.13 mm
Z = 2

Data collection

Stoe IPDSII two-circle diffractometer960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.093
graphiteθmax = 25.7°, θmin = 3.5°
ω scansh = −9→9
4021 measured reflectionsk = −6→5
1322 independent reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094w = 1/[σ2(Fo2) + (0.0405P)2] where P = (Fo2 + 2Fc2)/3
S = 0.91(Δ/σ)max = 0.028
1322 reflectionsΔρmax = 0.14 e Å3
173 parametersΔρmin = −0.13 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.077 (11)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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*/Ueq
N10.0100 (4)0.0360 (6)0.9396 (2)0.0442 (8)
H1A−0.086 (5)0.090 (9)0.911 (3)0.057 (12)*
H1B0.007 (7)−0.130 (11)0.958 (3)0.090 (17)*
O10.5634 (3)0.6085 (5)0.77036 (17)0.0454 (6)
O20.7240 (3)0.3098 (5)0.83952 (16)0.0468 (7)
C10.7064 (5)0.7251 (7)0.7398 (3)0.0475 (9)
H1C0.80640.68330.78450.057*
H1D0.69220.90270.74120.057*
C20.5874 (4)0.4043 (6)0.8206 (2)0.0347 (8)
C110.7290 (4)0.6485 (6)0.6420 (2)0.0383 (8)
C120.8155 (4)0.4400 (6)0.6259 (2)0.0414 (9)
H120.85930.34100.67790.050*
C130.8388 (4)0.3743 (6)0.5354 (2)0.0405 (9)
H130.89940.23210.52650.049*
C140.7755 (4)0.5117 (6)0.4576 (2)0.0405 (8)
C150.6888 (5)0.7204 (7)0.4742 (3)0.0511 (11)
H150.64460.81950.42240.061*
C160.6659 (4)0.7853 (7)0.5643 (3)0.0464 (9)
H160.60530.92760.57330.056*
C170.7999 (6)0.4368 (9)0.3599 (3)0.0601 (12)
H17A0.69880.36120.32780.090*
H17B0.89090.32100.36390.090*
H17C0.82580.57920.32410.090*
C210.4371 (4)0.3093 (6)0.8495 (2)0.0337 (8)
C220.4413 (4)0.0941 (6)0.9016 (2)0.0345 (8)
H220.54250.00990.91720.041*
C230.3008 (4)0.0031 (6)0.9306 (2)0.0376 (8)
H230.3064−0.14300.96590.045*
C240.1503 (4)0.1226 (6)0.90885 (19)0.0321 (7)
C250.1451 (4)0.3382 (7)0.8578 (2)0.0373 (8)
H250.04370.42250.84290.045*
C260.2854 (4)0.4302 (6)0.82882 (19)0.0352 (8)
H260.27960.57740.79430.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0384 (18)0.047 (2)0.0480 (17)−0.0004 (15)0.0081 (14)0.0099 (15)
O10.0416 (14)0.0390 (13)0.0604 (14)0.0023 (12)0.0232 (11)0.0028 (12)
O20.0303 (13)0.0573 (16)0.0533 (14)0.0020 (13)0.0077 (11)−0.0018 (13)
C10.048 (2)0.036 (2)0.064 (2)−0.0084 (18)0.0270 (18)−0.0041 (17)
C20.0344 (19)0.0332 (18)0.0375 (16)0.0003 (16)0.0084 (14)−0.0069 (15)
C110.0316 (18)0.0346 (19)0.0508 (18)−0.0047 (15)0.0133 (14)−0.0020 (15)
C120.042 (2)0.040 (2)0.0413 (16)0.0086 (17)0.0056 (14)0.0014 (15)
C130.040 (2)0.0333 (19)0.0489 (19)0.0037 (15)0.0086 (15)−0.0030 (15)
C140.037 (2)0.038 (2)0.0455 (17)−0.0061 (17)0.0059 (15)−0.0006 (16)
C150.044 (2)0.047 (2)0.060 (2)−0.0007 (19)0.0001 (18)0.0148 (18)
C160.040 (2)0.0305 (18)0.073 (2)0.0047 (17)0.0207 (17)0.0053 (18)
C170.067 (3)0.069 (3)0.0439 (19)−0.011 (2)0.0063 (18)−0.004 (2)
C210.0356 (18)0.0357 (18)0.0300 (14)0.0023 (16)0.0059 (13)−0.0047 (14)
C220.0321 (18)0.0365 (18)0.0349 (15)0.0051 (16)0.0054 (13)−0.0051 (14)
C230.043 (2)0.0371 (18)0.0314 (16)0.0012 (17)0.0011 (14)−0.0023 (13)
C240.0346 (18)0.0328 (17)0.0295 (14)−0.0026 (16)0.0069 (13)−0.0048 (14)
C250.0319 (17)0.045 (2)0.0349 (16)0.0060 (17)0.0061 (13)0.0029 (15)
C260.039 (2)0.0351 (18)0.0328 (15)0.0049 (16)0.0090 (14)0.0021 (14)

Geometric parameters (Å, °)

N1—C241.378 (5)C14—C171.499 (5)
N1—H1A0.88 (4)C15—C161.377 (5)
N1—H1B0.96 (6)C15—H150.9500
O1—C21.338 (4)C16—H160.9500
O1—C11.462 (4)C17—H17A0.9800
O2—C21.230 (4)C17—H17B0.9800
C1—C111.499 (5)C17—H17C0.9800
C1—H1C0.9900C21—C221.402 (5)
C1—H1D0.9900C21—C261.406 (4)
C2—C211.457 (5)C22—C231.378 (5)
C11—C161.379 (5)C22—H220.9500
C11—C121.392 (5)C23—C241.395 (5)
C12—C131.384 (5)C23—H230.9500
C12—H120.9500C24—C251.396 (5)
C13—C141.383 (5)C25—C261.378 (5)
C13—H130.9500C25—H250.9500
C14—C151.395 (5)C26—H260.9500
C24—N1—H1A118 (3)C15—C16—C11121.5 (3)
C24—N1—H1B119 (3)C15—C16—H16119.3
H1A—N1—H1B113 (5)C11—C16—H16119.3
C2—O1—C1118.2 (3)C14—C17—H17A109.5
O1—C1—C11111.7 (3)C14—C17—H17B109.5
O1—C1—H1C109.3H17A—C17—H17B109.5
C11—C1—H1C109.3C14—C17—H17C109.5
O1—C1—H1D109.3H17A—C17—H17C109.5
C11—C1—H1D109.3H17B—C17—H17C109.5
H1C—C1—H1D107.9C22—C21—C26117.9 (3)
O2—C2—O1122.3 (3)C22—C21—C2120.1 (3)
O2—C2—C21124.5 (3)C26—C21—C2122.0 (3)
O1—C2—C21113.2 (3)C23—C22—C21121.0 (3)
C16—C11—C12117.5 (3)C23—C22—H22119.5
C16—C11—C1120.8 (3)C21—C22—H22119.5
C12—C11—C1121.7 (3)C22—C23—C24120.8 (3)
C13—C12—C11121.1 (3)C22—C23—H23119.6
C13—C12—H12119.5C24—C23—H23119.6
C11—C12—H12119.5N1—C24—C23121.2 (3)
C14—C13—C12121.3 (3)N1—C24—C25120.1 (3)
C14—C13—H13119.4C23—C24—C25118.6 (3)
C12—C13—H13119.4C26—C25—C24120.7 (3)
C13—C14—C15117.3 (3)C26—C25—H25119.6
C13—C14—C17120.7 (3)C24—C25—H25119.6
C15—C14—C17122.0 (3)C25—C26—C21121.0 (3)
C16—C15—C14121.3 (3)C25—C26—H26119.5
C16—C15—H15119.4C21—C26—H26119.5
C14—C15—H15119.4
C2—O1—C1—C1194.1 (4)O2—C2—C21—C22−0.9 (4)
C1—O1—C2—O2−1.9 (5)O1—C2—C21—C22179.1 (3)
C1—O1—C2—C21178.1 (3)O2—C2—C21—C26177.6 (3)
O1—C1—C11—C1695.1 (4)O1—C2—C21—C26−2.4 (4)
O1—C1—C11—C12−85.7 (4)C26—C21—C22—C230.7 (4)
C16—C11—C12—C130.8 (5)C2—C21—C22—C23179.2 (3)
C1—C11—C12—C13−178.5 (4)C21—C22—C23—C240.0 (4)
C11—C12—C13—C14−0.8 (5)C22—C23—C24—N1−178.3 (3)
C12—C13—C14—C150.7 (5)C22—C23—C24—C25−0.7 (4)
C12—C13—C14—C17−179.2 (4)N1—C24—C25—C26178.2 (3)
C13—C14—C15—C16−0.6 (5)C23—C24—C25—C260.6 (4)
C17—C14—C15—C16179.3 (4)C24—C25—C26—C210.2 (4)
C14—C15—C16—C110.7 (6)C22—C21—C26—C25−0.8 (4)
C12—C11—C16—C15−0.7 (5)C2—C21—C26—C25−179.3 (3)
C1—C11—C16—C15178.5 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.88 (4)2.12 (5)2.977 (4)164 (4)
N1—H1B···N1ii0.96 (6)2.37 (6)3.278 (3)158 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x, y−1/2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2629).

References

  • Bavin, P. M. G. (1958). Can. J. Chem.36, 238–241.
  • Entwistle, I. D., Jackson, A. E., Johnston, R. A. & Telford, R. P. (1977). J. Chem. Soc. Perkin Trans. 1, pp. 443–444.
  • Idrees, G. A., Abuo-Rahma, G., Aly, O. M. & Radwan, M. F. (2009). Eur. J. Med. Chem.44, 2679–2684. [PubMed]
  • Kumarraja, M. & Pitchumani, K. (2004). J. Appl. Catal. A, 265, 135–139.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.
  • Tafesh, M. & Weiguny, J. (1996). Chem. Rev.96, 2035–2052. [PubMed]
  • Vass, A., Dudas, J., Toth, J. & Varma, R. S. (2001). Tetrahedron Lett.42, 5347–5349
  • Yuste, F., Saldana, M. & Walls, F. (1982). Tetrahedron Lett.23, 147–148.

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