4-Methyl­benzyl 4-amino­benzoate

Haider, A.; Akhter, Z.; Khan, M.S.U.; Bolte, M.; Siddiqi, H.M.

doi:10.1107/S1600536810007075

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o736

doi:10.1107/S1600536810007075

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4-Methylbenzyl 4-aminobenzoate

Ali Haider,^a Zareen Akhter,^a ^* Mohammad Saif Ullah Khan,^a Michael Bolte ^b and Humaira M. Siddiqi ^a

^aDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan, and ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: zareenakhter@yahoo.com

(Received 10 February 2010; accepted 24 February 2010; online 3 March 2010)

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 ); Vass et al. (2001 ); Entwistle et al. (1977 ); Bavin (1958 ); Yuste et al. (1982 ); Idrees et al. (2009 ). For the uses of amines, see: Kumarraja & Pitchumani (2004 ).

Experimental

Crystal data

C₁₅H₁₅NO₂
M_r = 241.28
Monoclinic, P 2₁
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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.094
S = 0.91
1322 reflections
173 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.88 (4)	2.12 (5)	2.977 (4)	164 (4)
N1—H1B⋯N1ⁱⁱ	0.96 (6)	2.37 (6)	3.278 (3)	158 (4)
Symmetry codes: (i) x-1, y, z; (ii) $[-x, y-{\script{1\over 2}}, -z+2]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

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

Figures top

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.

4-Methylbenzyl 4-aminobenzoate top

Crystal data top

C₁₅H₁₅NO₂	F(000) = 256
M_r = 241.28	D_x = 1.248 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2492 reflections
a = 8.2097 (12) Å	θ = 4.0–25.9°
b = 5.5344 (5) Å	µ = 0.08 mm⁻¹
c = 14.293 (2) Å	T = 173 K
β = 98.531 (12)°	Prism, colourless
V = 642.24 (14) Å³	0.27 × 0.13 × 0.13 mm
Z = 2

Data collection top

Stoe IPDSII two-circle diffractometer	960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.093
Graphite monochromator	θ_max = 25.7°, θ_min = 3.5°
ω scans	h = −9→9
4021 measured reflections	k = −6→5
1322 independent reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0405P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max = 0.028
1322 reflections	Δρ_max = 0.14 e Å⁻³
173 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.077 (11)

Crystal data top

C₁₅H₁₅NO₂	V = 642.24 (14) Å³
M_r = 241.28	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.2097 (12) Å	µ = 0.08 mm⁻¹
b = 5.5344 (5) Å	T = 173 K
c = 14.293 (2) Å	0.27 × 0.13 × 0.13 mm
β = 98.531 (12)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	Δρ_max = 0.14 e Å⁻³
1322 reflections	Δρ_min = −0.13 e Å⁻³
173 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N1	0.0100 (4)	0.0360 (6)	0.9396 (2)	0.0442 (8)
H1A	−0.086 (5)	0.090 (9)	0.911 (3)	0.057 (12)*
H1B	0.007 (7)	−0.130 (11)	0.958 (3)	0.090 (17)*
O1	0.5634 (3)	0.6085 (5)	0.77036 (17)	0.0454 (6)
O2	0.7240 (3)	0.3098 (5)	0.83952 (16)	0.0468 (7)
C1	0.7064 (5)	0.7251 (7)	0.7398 (3)	0.0475 (9)
H1C	0.8064	0.6833	0.7845	0.057*
H1D	0.6922	0.9027	0.7412	0.057*
C2	0.5874 (4)	0.4043 (6)	0.8206 (2)	0.0347 (8)
C11	0.7290 (4)	0.6485 (6)	0.6420 (2)	0.0383 (8)
C12	0.8155 (4)	0.4400 (6)	0.6259 (2)	0.0414 (9)
H12	0.8593	0.3410	0.6779	0.050*
C13	0.8388 (4)	0.3743 (6)	0.5354 (2)	0.0405 (9)
H13	0.8994	0.2321	0.5265	0.049*
C14	0.7755 (4)	0.5117 (6)	0.4576 (2)	0.0405 (8)
C15	0.6888 (5)	0.7204 (7)	0.4742 (3)	0.0511 (11)
H15	0.6446	0.8195	0.4224	0.061*
C16	0.6659 (4)	0.7853 (7)	0.5643 (3)	0.0464 (9)
H16	0.6053	0.9276	0.5733	0.056*
C17	0.7999 (6)	0.4368 (9)	0.3599 (3)	0.0601 (12)
H17A	0.6988	0.3612	0.3278	0.090*
H17B	0.8909	0.3210	0.3639	0.090*
H17C	0.8258	0.5792	0.3241	0.090*
C21	0.4371 (4)	0.3093 (6)	0.8495 (2)	0.0337 (8)
C22	0.4413 (4)	0.0941 (6)	0.9016 (2)	0.0345 (8)
H22	0.5425	0.0099	0.9172	0.041*
C23	0.3008 (4)	0.0031 (6)	0.9306 (2)	0.0376 (8)
H23	0.3064	−0.1430	0.9659	0.045*
C24	0.1503 (4)	0.1226 (6)	0.90885 (19)	0.0321 (7)
C25	0.1451 (4)	0.3382 (7)	0.8578 (2)	0.0373 (8)
H25	0.0437	0.4225	0.8429	0.045*
C26	0.2854 (4)	0.4302 (6)	0.82882 (19)	0.0352 (8)
H26	0.2796	0.5774	0.7943	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0384 (18)	0.047 (2)	0.0480 (17)	−0.0004 (15)	0.0081 (14)	0.0099 (15)
O1	0.0416 (14)	0.0390 (13)	0.0604 (14)	0.0023 (12)	0.0232 (11)	0.0028 (12)
O2	0.0303 (13)	0.0573 (16)	0.0533 (14)	0.0020 (13)	0.0077 (11)	−0.0018 (13)
C1	0.048 (2)	0.036 (2)	0.064 (2)	−0.0084 (18)	0.0270 (18)	−0.0041 (17)
C2	0.0344 (19)	0.0332 (18)	0.0375 (16)	0.0003 (16)	0.0084 (14)	−0.0069 (15)
C11	0.0316 (18)	0.0346 (19)	0.0508 (18)	−0.0047 (15)	0.0133 (14)	−0.0020 (15)
C12	0.042 (2)	0.040 (2)	0.0413 (16)	0.0086 (17)	0.0056 (14)	0.0014 (15)
C13	0.040 (2)	0.0333 (19)	0.0489 (19)	0.0037 (15)	0.0086 (15)	−0.0030 (15)
C14	0.037 (2)	0.038 (2)	0.0455 (17)	−0.0061 (17)	0.0059 (15)	−0.0006 (16)
C15	0.044 (2)	0.047 (2)	0.060 (2)	−0.0007 (19)	0.0001 (18)	0.0148 (18)
C16	0.040 (2)	0.0305 (18)	0.073 (2)	0.0047 (17)	0.0207 (17)	0.0053 (18)
C17	0.067 (3)	0.069 (3)	0.0439 (19)	−0.011 (2)	0.0063 (18)	−0.004 (2)
C21	0.0356 (18)	0.0357 (18)	0.0300 (14)	0.0023 (16)	0.0059 (13)	−0.0047 (14)
C22	0.0321 (18)	0.0365 (18)	0.0349 (15)	0.0051 (16)	0.0054 (13)	−0.0051 (14)
C23	0.043 (2)	0.0371 (18)	0.0314 (16)	0.0012 (17)	0.0011 (14)	−0.0023 (13)
C24	0.0346 (18)	0.0328 (17)	0.0295 (14)	−0.0026 (16)	0.0069 (13)	−0.0048 (14)
C25	0.0319 (17)	0.045 (2)	0.0349 (16)	0.0060 (17)	0.0061 (13)	0.0029 (15)
C26	0.039 (2)	0.0351 (18)	0.0328 (15)	0.0049 (16)	0.0090 (14)	0.0021 (14)

Geometric parameters (Å, º) top

N1—C24	1.378 (5)	C14—C17	1.499 (5)
N1—H1A	0.88 (4)	C15—C16	1.377 (5)
N1—H1B	0.96 (6)	C15—H15	0.9500
O1—C2	1.338 (4)	C16—H16	0.9500
O1—C1	1.462 (4)	C17—H17A	0.9800
O2—C2	1.230 (4)	C17—H17B	0.9800
C1—C11	1.499 (5)	C17—H17C	0.9800
C1—H1C	0.9900	C21—C22	1.402 (5)
C1—H1D	0.9900	C21—C26	1.406 (4)
C2—C21	1.457 (5)	C22—C23	1.378 (5)
C11—C16	1.379 (5)	C22—H22	0.9500
C11—C12	1.392 (5)	C23—C24	1.395 (5)
C12—C13	1.384 (5)	C23—H23	0.9500
C12—H12	0.9500	C24—C25	1.396 (5)
C13—C14	1.383 (5)	C25—C26	1.378 (5)
C13—H13	0.9500	C25—H25	0.9500
C14—C15	1.395 (5)	C26—H26	0.9500

C24—N1—H1A	118 (3)	C15—C16—C11	121.5 (3)
C24—N1—H1B	119 (3)	C15—C16—H16	119.3
H1A—N1—H1B	113 (5)	C11—C16—H16	119.3
C2—O1—C1	118.2 (3)	C14—C17—H17A	109.5
O1—C1—C11	111.7 (3)	C14—C17—H17B	109.5
O1—C1—H1C	109.3	H17A—C17—H17B	109.5
C11—C1—H1C	109.3	C14—C17—H17C	109.5
O1—C1—H1D	109.3	H17A—C17—H17C	109.5
C11—C1—H1D	109.3	H17B—C17—H17C	109.5
H1C—C1—H1D	107.9	C22—C21—C26	117.9 (3)
O2—C2—O1	122.3 (3)	C22—C21—C2	120.1 (3)
O2—C2—C21	124.5 (3)	C26—C21—C2	122.0 (3)
O1—C2—C21	113.2 (3)	C23—C22—C21	121.0 (3)
C16—C11—C12	117.5 (3)	C23—C22—H22	119.5
C16—C11—C1	120.8 (3)	C21—C22—H22	119.5
C12—C11—C1	121.7 (3)	C22—C23—C24	120.8 (3)
C13—C12—C11	121.1 (3)	C22—C23—H23	119.6
C13—C12—H12	119.5	C24—C23—H23	119.6
C11—C12—H12	119.5	N1—C24—C23	121.2 (3)
C14—C13—C12	121.3 (3)	N1—C24—C25	120.1 (3)
C14—C13—H13	119.4	C23—C24—C25	118.6 (3)
C12—C13—H13	119.4	C26—C25—C24	120.7 (3)
C13—C14—C15	117.3 (3)	C26—C25—H25	119.6
C13—C14—C17	120.7 (3)	C24—C25—H25	119.6
C15—C14—C17	122.0 (3)	C25—C26—C21	121.0 (3)
C16—C15—C14	121.3 (3)	C25—C26—H26	119.5
C16—C15—H15	119.4	C21—C26—H26	119.5
C14—C15—H15	119.4

C2—O1—C1—C11	94.1 (4)	O2—C2—C21—C22	−0.9 (4)
C1—O1—C2—O2	−1.9 (5)	O1—C2—C21—C22	179.1 (3)
C1—O1—C2—C21	178.1 (3)	O2—C2—C21—C26	177.6 (3)
O1—C1—C11—C16	95.1 (4)	O1—C2—C21—C26	−2.4 (4)
O1—C1—C11—C12	−85.7 (4)	C26—C21—C22—C23	0.7 (4)
C16—C11—C12—C13	0.8 (5)	C2—C21—C22—C23	179.2 (3)
C1—C11—C12—C13	−178.5 (4)	C21—C22—C23—C24	0.0 (4)
C11—C12—C13—C14	−0.8 (5)	C22—C23—C24—N1	−178.3 (3)
C12—C13—C14—C15	0.7 (5)	C22—C23—C24—C25	−0.7 (4)
C12—C13—C14—C17	−179.2 (4)	N1—C24—C25—C26	178.2 (3)
C13—C14—C15—C16	−0.6 (5)	C23—C24—C25—C26	0.6 (4)
C17—C14—C15—C16	179.3 (4)	C24—C25—C26—C21	0.2 (4)
C14—C15—C16—C11	0.7 (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—C15	178.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.88 (4)	2.12 (5)	2.977 (4)	164 (4)
N1—H1B···N1ⁱⁱ	0.96 (6)	2.37 (6)	3.278 (3)	158 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₂
M_r	241.28
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	173
a, b, c (Å)	8.2097 (12), 5.5344 (5), 14.293 (2)
β (°)	98.531 (12)
V (Å³)	642.24 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.27 × 0.13 × 0.13

Data collection
Diffractometer	Stoe IPDSII two-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4021, 1322, 960
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.094, 0.91
No. of reflections	1322
No. of parameters	173
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.88 (4)	2.12 (5)	2.977 (4)	164 (4)
N1—H1B···N1ⁱⁱ	0.96 (6)	2.37 (6)	3.278 (3)	158 (4)

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

Acknowledgements

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.

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