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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1899.
Published online 2009 July 18. doi:  10.1107/S1600536809027500
PMCID: PMC2977390

N-(4-Hydr­oxy-3-methoxy­benz­yl)benzamide

Abstract

In the mol­ecular structure of the title compound, C15H15NO3, the two benzene rings are twisted with respect to each other, making a dihedral angle of 75.11 (10)°. In the amide fragment, the C=O and C—N bond distances are 1.248 (3) and 1.321 (3) Å, respectively, indicating electron delocalization. A partially ovelapped arrangement between parallel hydroxy­methoxy­benzene rings is observed in the crystal structure, and the face-to-face distance of 3.531 (16) Å suggests the existence of weak π–π stacking. N—H(...)O and O—H(...)O hydrogen bonding is also present in the crystal structure.

Related literature

The title compound was obtained during an investigation of capsaicin and its derivatives. For the biological activity of capsaicin, see: Kaga et al. (1989 [triangle]). For related structures, see: Luo & Huang (2004 [triangle]); Tong et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1899-scheme1.jpg

Experimental

Crystal data

  • C15H15NO3
  • M r = 257.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1899-efi1.jpg
  • a = 7.2292 (18) Å
  • b = 21.057 (5) Å
  • c = 9.031 (2) Å
  • β = 106.849 (12)°
  • V = 1315.7 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 294 K
  • 0.40 × 0.28 × 0.26 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: none
  • 8839 measured reflections
  • 2353 independent reflections
  • 1304 reflections with I > 2σ(I)
  • R int = 0.060

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.186
  • S = 1.00
  • 2353 reflections
  • 182 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027500/xu2556sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027500/xu2556Isup2.hkl

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

Acknowledgments

The work was supported by the Natural Science Foundation of Zhejiang Province of China (No. M203027).

supplementary crystallographic information

Comment

Capsaicin, a pungent principle of capsicums, has been known to exhibit a variety of biological activities, including recent findings concerning its mutagenicity (Kaga et al. 1989). During the investigation on syntheses of capsaicin and its derivatives, the title compound has recently been obtained and its crystal structure is reported here.

In the molecular structure of the title compound (Fig. 1), two benzene rings are twisted to each other with a dihedral angle of 75.11 (10)°, which is similar to 72.1 (2)° found in N-2-chlorobenzylbenzamide (Luo & Huang, 2004) but is somewhat larger than 56.32 (17)° found in N-(4-Cyanobenzyl)benzamide (Tong et al. 2008). The amide flagment is nearly coplanar with the C1-benzene ring [dihedral angle 5.0 (4)°]. The C7═O1 and C7—N1 bond distances are 1.248 (3) and 1.321 (3) Å, respectively, showing the electron delocalization in the amide fragment.

A partially ovelapped arrangement between parallel C9-benzene and C9i-benzene rings is observed in the crystal structure (Fig. 2), the face-to-face distance of 3.531 (16) Å suggests the existence of weak π-π stacking between them [symmetry code: (i) 1 - x,1 - y,-z]. The N—H···O and O—H···O hydrogen bonding is present in the crystal structure (Table 1 and Fig. 2), which helps to stabilize the crystal structure.

Experimental

4-Hydroxy-3-methoxy benzylamine HCl salt (4.7 g, 25 mmol) and dimethylformamide (25 ml) were added to a 100 ml 3-necked flask equipped with an additional funnel, a thermometer and a magnetic stirrer. Water solution (10 ml) of NaOH (2.0 g) was added at room temperature. The mixture was stirred at 308 K for 30 min and then cooled to 273 K. An ether solution (10 ml) of benzoyl chloride (3.5 g, 25 mmol) was added dropwise at about 273 K over 20 min. After stirred for 2 h at room temperature the mixture was poured into water, and then extracted with ethyl acetate. The ethyl acetate extract was washed with 1 M HCl followed by saturated NaHCO3 and brine. The extract was then dried over anhydrous Na2SO4 and filtered. Solvents were removed under vacuum at about 308 K to give a solid crude. Recrystallization was performed twice with an absolute ethyl acetate to obtain single crystals of the title compound.

Refinement

Hydroxy and imino H atoms were located in a difference Fourier map and were refined isotropically. Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angle was refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93 (aromatic) and 0.97 Å (methylene), and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms).
Fig. 2.
The unit cell packing diagram showing π-π stacking between C9-benzene rings [symmetry code: (i) 1 - x, 1 - y, -z]. Dashed lines indicate the hydrogen bonding.

Crystal data

C15H15NO3F(000) = 544
Mr = 257.28Dx = 1.299 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4326 reflections
a = 7.2292 (18) Åθ = 2.2–25.1°
b = 21.057 (5) ŵ = 0.09 mm1
c = 9.031 (2) ÅT = 294 K
β = 106.849 (12)°Prism, colorless
V = 1315.7 (5) Å30.40 × 0.28 × 0.26 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer1304 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.060
graphiteθmax = 25.2°, θmin = 1.9°
Detector resolution: 10.0 pixels mm-1h = −8→8
ω scansk = −25→25
8839 measured reflectionsl = −10→10
2353 independent 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)] = 0.064H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.186w = 1/[σ2(Fo2) + (0.0865P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2353 reflectionsΔρmax = 0.22 e Å3
182 parametersΔρmin = −0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (4)

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*/Ueq
N10.4418 (4)0.57597 (12)0.3750 (3)0.0609 (8)
O10.2826 (3)0.61857 (10)0.5293 (2)0.0704 (7)
O20.2344 (3)0.40542 (9)−0.1741 (2)0.0699 (7)
O30.2085 (3)0.50638 (11)−0.3439 (2)0.0681 (7)
C10.5991 (4)0.65751 (12)0.5602 (3)0.0501 (7)
C20.7756 (4)0.65520 (14)0.5270 (3)0.0624 (8)
H20.79410.62570.45600.075*
C30.9237 (5)0.69650 (15)0.5988 (4)0.0730 (10)
H31.04100.69470.57600.088*
C40.8970 (5)0.74018 (16)0.7039 (4)0.0774 (10)
H40.99620.76800.75170.093*
C50.7239 (5)0.74283 (16)0.7384 (4)0.0789 (10)
H50.70630.77220.81010.095*
C60.5766 (5)0.70172 (13)0.6662 (4)0.0656 (9)
H60.45970.70390.68950.079*
C70.4317 (4)0.61524 (13)0.4864 (3)0.0526 (8)
C80.2814 (5)0.53450 (15)0.2939 (3)0.0640 (9)
H8A0.16140.55160.30500.077*
H8B0.30040.49270.34130.077*
C90.2655 (4)0.52835 (13)0.1243 (3)0.0512 (8)
C100.2606 (4)0.46920 (13)0.0575 (3)0.0530 (8)
H100.27090.43310.11860.064*
C110.2408 (4)0.46267 (13)−0.0981 (3)0.0508 (8)
C120.2250 (4)0.51616 (14)−0.1907 (3)0.0511 (7)
C130.2304 (4)0.57554 (13)−0.1242 (3)0.0569 (8)
H130.22040.6117−0.18510.068*
C140.2505 (4)0.58145 (14)0.0317 (3)0.0576 (8)
H140.25400.62170.07500.069*
C150.2403 (6)0.34901 (15)−0.0863 (4)0.0872 (11)
H15A0.36330.3459−0.00920.131*
H15B0.22210.3128−0.15370.131*
H15C0.13930.3502−0.03690.131*
H1N0.546 (4)0.5707 (13)0.350 (3)0.063 (10)*
H3A0.204 (7)0.548 (2)−0.393 (5)0.148 (18)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0560 (17)0.0776 (18)0.0497 (16)−0.0013 (14)0.0162 (14)−0.0173 (13)
O10.0796 (16)0.0755 (15)0.0682 (15)−0.0099 (12)0.0404 (12)−0.0126 (11)
O20.0938 (16)0.0555 (13)0.0618 (14)−0.0044 (11)0.0247 (12)−0.0115 (11)
O30.0854 (16)0.0777 (16)0.0449 (13)−0.0053 (12)0.0247 (11)−0.0056 (11)
C10.0671 (19)0.0473 (16)0.0358 (15)0.0076 (14)0.0149 (14)0.0045 (13)
C20.068 (2)0.0613 (19)0.0585 (19)0.0032 (16)0.0192 (16)−0.0100 (15)
C30.069 (2)0.079 (2)0.074 (2)−0.0035 (18)0.0259 (18)−0.0077 (18)
C40.082 (3)0.076 (2)0.072 (2)−0.0169 (19)0.0189 (19)−0.0176 (19)
C50.099 (3)0.068 (2)0.075 (2)−0.010 (2)0.034 (2)−0.0211 (18)
C60.073 (2)0.0619 (19)0.065 (2)−0.0006 (16)0.0253 (17)−0.0104 (16)
C70.068 (2)0.0524 (17)0.0390 (16)0.0050 (15)0.0181 (15)0.0010 (13)
C80.069 (2)0.076 (2)0.0461 (18)−0.0121 (16)0.0144 (15)−0.0081 (16)
C90.0497 (17)0.0587 (18)0.0450 (17)−0.0037 (13)0.0134 (14)−0.0059 (14)
C100.0529 (18)0.0561 (18)0.0498 (18)−0.0038 (13)0.0144 (14)0.0005 (14)
C110.0516 (18)0.0556 (17)0.0453 (17)−0.0030 (13)0.0141 (13)−0.0088 (14)
C120.0521 (18)0.0618 (18)0.0391 (17)−0.0039 (14)0.0129 (13)−0.0042 (14)
C130.065 (2)0.0556 (18)0.0521 (19)0.0024 (14)0.0206 (15)0.0029 (15)
C140.0630 (19)0.0570 (18)0.0545 (19)−0.0045 (14)0.0198 (15)−0.0098 (15)
C150.118 (3)0.056 (2)0.099 (3)−0.004 (2)0.050 (2)−0.0084 (19)

Geometric parameters (Å, °)

N1—C71.321 (3)C5—H50.9300
N1—C81.467 (4)C6—H60.9300
N1—H1N0.85 (3)C8—C91.508 (4)
O1—C71.248 (3)C8—H8A0.9700
O2—C111.382 (3)C8—H8B0.9700
O2—C151.422 (4)C9—C101.380 (4)
O3—C121.370 (3)C9—C141.382 (4)
O3—H3A0.98 (4)C10—C111.377 (4)
C1—C61.378 (4)C10—H100.9300
C1—C21.393 (4)C11—C121.388 (4)
C1—C71.494 (4)C12—C131.382 (4)
C2—C31.386 (4)C13—C141.379 (4)
C2—H20.9300C13—H130.9300
C3—C41.374 (4)C14—H140.9300
C3—H30.9300C15—H15A0.9600
C4—C51.375 (4)C15—H15B0.9600
C4—H40.9300C15—H15C0.9600
C5—C61.381 (4)
C7—N1—C8122.9 (3)C9—C8—H8A109.2
C7—N1—H1N122 (2)N1—C8—H8B109.2
C8—N1—H1N114.9 (19)C9—C8—H8B109.2
C11—O2—C15117.4 (2)H8A—C8—H8B107.9
C12—O3—H3A108 (3)C10—C9—C14118.6 (3)
C6—C1—C2118.2 (3)C10—C9—C8120.4 (3)
C6—C1—C7117.9 (3)C14—C9—C8121.0 (3)
C2—C1—C7123.9 (2)C11—C10—C9121.2 (3)
C3—C2—C1120.6 (3)C11—C10—H10119.4
C3—C2—H2119.7C9—C10—H10119.4
C1—C2—H2119.7C10—C11—O2124.9 (3)
C4—C3—C2119.9 (3)C10—C11—C12120.0 (3)
C4—C3—H3120.0O2—C11—C12115.1 (2)
C2—C3—H3120.0O3—C12—C13123.9 (3)
C3—C4—C5120.2 (3)O3—C12—C11117.0 (3)
C3—C4—H4119.9C13—C12—C11119.1 (3)
C5—C4—H4119.9C14—C13—C12120.4 (3)
C4—C5—C6119.7 (3)C14—C13—H13119.8
C4—C5—H5120.2C12—C13—H13119.8
C6—C5—H5120.2C13—C14—C9120.8 (3)
C1—C6—C5121.4 (3)C13—C14—H14119.6
C1—C6—H6119.3C9—C14—H14119.6
C5—C6—H6119.3O2—C15—H15A109.5
O1—C7—N1121.0 (3)O2—C15—H15B109.5
O1—C7—C1119.3 (2)H15A—C15—H15B109.5
N1—C7—C1119.7 (3)O2—C15—H15C109.5
N1—C8—C9112.0 (2)H15A—C15—H15C109.5
N1—C8—H8A109.2H15B—C15—H15C109.5
C6—C1—C2—C3−0.1 (4)N1—C8—C9—C14−54.6 (4)
C7—C1—C2—C3179.2 (3)C14—C9—C10—C11−0.1 (4)
C1—C2—C3—C40.0 (5)C8—C9—C10—C11178.2 (2)
C2—C3—C4—C50.3 (5)C9—C10—C11—O2−179.9 (3)
C3—C4—C5—C6−0.5 (5)C9—C10—C11—C12−0.1 (4)
C2—C1—C6—C5−0.1 (4)C15—O2—C11—C102.9 (4)
C7—C1—C6—C5−179.5 (3)C15—O2—C11—C12−176.9 (3)
C4—C5—C6—C10.4 (5)C10—C11—C12—O3179.1 (2)
C8—N1—C7—O10.5 (4)O2—C11—C12—O3−1.1 (4)
C8—N1—C7—C1−178.1 (2)C10—C11—C12—C130.3 (4)
C6—C1—C7—O1−4.3 (4)O2—C11—C12—C13−179.9 (2)
C2—C1—C7—O1176.4 (3)O3—C12—C13—C14−178.9 (3)
C6—C1—C7—N1174.4 (2)C11—C12—C13—C14−0.2 (4)
C2—C1—C7—N1−5.0 (4)C12—C13—C14—C90.0 (5)
C7—N1—C8—C9142.7 (3)C10—C9—C14—C130.2 (4)
N1—C8—C9—C10127.1 (3)C8—C9—C14—C13−178.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O3i0.85 (3)2.42 (3)3.145 (6)143 (2)
O3—H3A···O1ii0.98 (4)1.80 (4)2.745 (5)160 (5)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2556).

References

  • Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst.26, 343–350.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Kaga, H., Miura, M. & Orito, K. A. (1989). J. Org. Chem.54, 3477–3478.
  • Luo, J.-T. & Huang, W.-Q. (2004). Chem. J. Chin. Univ.25, 56–59.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tong, Y.-L., Guo, L.-Q., Ma, H.-J., Chen, W. & Zhu, H.-J. (2008). Acta Cryst. E64, o2271. [PMC free article] [PubMed]

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