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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o877.
Published online 2010 March 20. doi:  10.1107/S1600536810009529
PMCID: PMC2983855

3-Chloro-N-(4-hydr­oxy-3-methoxy­benz­yl)-2,2-dimethyl­propanamide

Abstract

In the mol­ecular structure of the title compound, C13H18ClNO3, the amide group is nearly perpendicular to the benzene ring, making a dihedral angle of 85.66 (9)°. The C=O bond distance of 1.242 (3) Å and the C—N bond distance of 1.333 (3) Å suggest electron delocalization in the amide fragment. Inter­molecular O—H(...)O and N—H(...)O hydrogen bonding helps to stabilize the crystal structure.

Related literature

The title compound is a derivative of capsaicin. For the biological activity of capsaicin, see: Kaga et al. (1989 [triangle]). For a related structure, see: Xia et al. (2009 [triangle]).

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Object name is e-66-0o877-scheme1.jpg

Experimental

Crystal data

  • C13H18ClNO3
  • M r = 271.73
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o877-efi1.jpg
  • a = 9.3074 (10) Å
  • b = 11.5585 (13) Å
  • c = 13.0652 (14) Å
  • β = 90.378 (4)°
  • V = 1405.5 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 294 K
  • 0.40 × 0.38 × 0.32 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • 15383 measured reflections
  • 2732 independent reflections
  • 2254 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.167
  • S = 1.05
  • 2732 reflections
  • 167 parameters
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.67 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/S1600536810009529/xu2733sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009529/xu2733Isup2.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 shown a variety of biological activities including mutagenicity (Kaga et al. 1989). During the investigation on syntheses of capsaicin derivatives, the title compound has recently been prepared in the labotory and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The amide fragment is nearly perpendicular to the benzene ring [dihedral angle 85.66 (9))°]. The longer C9═O3 bond distance of 1.242 (3) Å and the shorter C9—N1 bond distance of 1.333 (3) Å suggest the electron delocalization in the amide fragment, which is comparable to that found in the related compound N-(4-Hydroxy-3-methoxybenzyl)benzamide (Xia et al. 2009).

Intermolecular O—H···O and N—H···O hydrogen bonding is present in the crystal structure (Table 1), 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 2,2-dimethyl-3-chloropropionyl chloride (3.9 g, 25 mmol) was added dropwise at about 273 K over 15 min. After stirred for 2 h at room temperature the mixture was poured into 1M HCl solution (120 ml) , and then extracted with ethyl acetate. The ethyl acetate extract was washed with 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 colourless single crystals of the title compound.

Refinement

Hydroxy and imino H atoms were located in a difference Fourier map and were refined as riding in as-found relative positions with Uiso(H) = 1.5Ueq(N,O). 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 30% probability displacement (arbitrary spheres for H atoms).

Crystal data

C13H18ClNO3F(000) = 576
Mr = 271.73Dx = 1.284 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3466 reflections
a = 9.3074 (10) Åθ = 2.2–24.0°
b = 11.5585 (13) ŵ = 0.27 mm1
c = 13.0652 (14) ÅT = 294 K
β = 90.378 (4)°Prism, colorless
V = 1405.5 (3) Å30.40 × 0.38 × 0.32 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer2254 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
graphiteθmax = 26.0°, θmin = 2.2°
Detector resolution: 10.0 pixels mm-1h = −10→11
ω scansk = −13→14
15383 measured reflectionsl = −16→16
2732 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)] = 0.060H-atom parameters constrained
wR(F2) = 0.167w = 1/[σ2(Fo2) + (0.0726P)2 + 1.051P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2732 reflectionsΔρmax = 0.48 e Å3
167 parametersΔρmin = −0.67 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: 0.021 (3)

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
Cl10.85692 (18)0.09530 (8)0.35770 (8)0.1195 (6)
N10.7804 (2)0.39529 (17)0.22613 (15)0.0410 (5)
H1N0.74160.43560.28010.061*
O10.18986 (18)0.14975 (16)0.13257 (15)0.0539 (5)
H1A0.11200.19610.14820.081*
O20.43484 (18)0.03920 (15)0.14718 (15)0.0542 (5)
O30.95555 (18)0.27805 (16)0.17024 (13)0.0509 (5)
C10.3123 (2)0.2148 (2)0.12573 (18)0.0409 (5)
C20.4447 (2)0.1577 (2)0.13548 (18)0.0404 (5)
C30.5709 (2)0.2199 (2)0.13426 (18)0.0431 (6)
H30.65810.18150.14220.052*
C40.5700 (2)0.3402 (2)0.12130 (17)0.0400 (5)
C50.4394 (3)0.3947 (2)0.10673 (19)0.0445 (6)
H50.43710.47410.09530.053*
C60.3112 (2)0.3327 (2)0.10891 (19)0.0451 (6)
H60.22430.37100.09900.054*
C70.5646 (3)−0.0248 (2)0.1367 (2)0.0572 (7)
H7A0.6070−0.00790.07150.086*
H7B0.5441−0.10610.14090.086*
H7C0.6303−0.00360.19040.086*
C80.7093 (3)0.4073 (2)0.12661 (18)0.0445 (6)
H8A0.77320.37990.07350.053*
H8B0.68980.48850.11380.053*
C90.8956 (2)0.32899 (19)0.24198 (17)0.0371 (5)
C100.9530 (2)0.3193 (2)0.35204 (17)0.0410 (5)
C111.0014 (4)0.1958 (3)0.3707 (2)0.0669 (9)
H11A1.04190.18980.43910.080*
H11B1.07610.17610.32230.080*
C120.8444 (3)0.3548 (3)0.4336 (2)0.0599 (7)
H12A0.75750.31110.42450.090*
H12B0.82360.43580.42700.090*
H12C0.88380.33980.50030.090*
C131.0859 (4)0.3961 (3)0.3605 (2)0.0779 (11)
H13A1.12920.38650.42680.117*
H13B1.05860.47550.35130.117*
H13C1.15350.37460.30860.117*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.2206 (15)0.0570 (6)0.0811 (7)−0.0548 (7)0.0203 (7)−0.0059 (4)
N10.0349 (10)0.0439 (11)0.0441 (11)0.0031 (8)0.0016 (8)−0.0048 (8)
O10.0314 (9)0.0475 (10)0.0829 (13)0.0019 (7)0.0038 (8)−0.0097 (9)
O20.0373 (9)0.0415 (10)0.0838 (13)0.0063 (7)0.0059 (8)0.0056 (9)
O30.0412 (10)0.0648 (12)0.0466 (10)0.0112 (8)0.0010 (7)−0.0106 (8)
C10.0306 (12)0.0464 (13)0.0457 (12)0.0014 (9)0.0012 (9)−0.0064 (10)
C20.0361 (12)0.0403 (12)0.0447 (12)0.0060 (9)0.0018 (9)0.0004 (10)
C30.0334 (12)0.0479 (14)0.0480 (13)0.0078 (10)0.0009 (10)0.0037 (10)
C40.0360 (12)0.0466 (13)0.0374 (11)0.0020 (10)−0.0009 (9)0.0024 (9)
C50.0426 (14)0.0401 (13)0.0508 (14)0.0043 (10)−0.0033 (11)0.0014 (10)
C60.0323 (12)0.0461 (14)0.0568 (14)0.0087 (10)−0.0050 (10)−0.0034 (11)
C70.0478 (15)0.0458 (15)0.0780 (19)0.0146 (12)0.0061 (13)0.0059 (13)
C80.0395 (13)0.0484 (14)0.0455 (13)−0.0005 (10)0.0000 (10)0.0066 (10)
C90.0287 (11)0.0374 (11)0.0451 (12)−0.0047 (9)0.0023 (9)−0.0013 (9)
C100.0382 (13)0.0419 (13)0.0429 (12)−0.0041 (10)−0.0008 (9)−0.0005 (10)
C110.086 (2)0.0616 (18)0.0531 (16)0.0212 (16)−0.0002 (15)0.0045 (13)
C120.0694 (19)0.0669 (18)0.0436 (14)0.0124 (15)0.0050 (12)−0.0004 (12)
C130.072 (2)0.102 (3)0.0593 (18)−0.0448 (19)−0.0166 (15)0.0090 (17)

Geometric parameters (Å, °)

Cl1—C111.784 (4)C6—H60.9300
N1—C91.333 (3)C7—H7A0.9600
N1—C81.462 (3)C7—H7B0.9600
N1—H1N0.9206C7—H7C0.9600
O1—C11.369 (3)C8—H8A0.9700
O1—H1A0.9252C8—H8B0.9700
O2—C21.382 (3)C9—C101.535 (3)
O2—C71.424 (3)C10—C111.516 (4)
O3—C91.242 (3)C10—C131.526 (4)
C1—C61.380 (4)C10—C121.530 (3)
C1—C21.403 (3)C11—H11A0.9700
C2—C31.378 (3)C11—H11B0.9700
C3—C41.400 (3)C12—H12A0.9600
C3—H30.9300C12—H12B0.9600
C4—C51.381 (3)C12—H12C0.9600
C4—C81.512 (3)C13—H13A0.9600
C5—C61.392 (3)C13—H13B0.9600
C5—H50.9300C13—H13C0.9600
C9—N1—C8123.50 (19)C4—C8—H8A109.2
C9—N1—H1N119.4N1—C8—H8B109.2
C8—N1—H1N117.1C4—C8—H8B109.2
C1—O1—H1A110.5H8A—C8—H8B107.9
C2—O2—C7116.58 (19)O3—C9—N1121.3 (2)
O1—C1—C6123.2 (2)O3—C9—C10121.1 (2)
O1—C1—C2117.8 (2)N1—C9—C10117.55 (19)
C6—C1—C2119.0 (2)C11—C10—C13107.3 (3)
C3—C2—O2125.2 (2)C11—C10—C12109.7 (2)
C3—C2—C1120.2 (2)C13—C10—C12109.5 (2)
O2—C2—C1114.7 (2)C11—C10—C9108.7 (2)
C2—C3—C4121.0 (2)C13—C10—C9107.60 (19)
C2—C3—H3119.5C12—C10—C9113.9 (2)
C4—C3—H3119.5C10—C11—Cl1112.0 (2)
C5—C4—C3118.3 (2)C10—C11—H11A109.2
C5—C4—C8121.7 (2)Cl1—C11—H11A109.2
C3—C4—C8119.9 (2)C10—C11—H11B109.2
C4—C5—C6121.1 (2)Cl1—C11—H11B109.2
C4—C5—H5119.5H11A—C11—H11B107.9
C6—C5—H5119.5C10—C12—H12A109.5
C1—C6—C5120.4 (2)C10—C12—H12B109.5
C1—C6—H6119.8H12A—C12—H12B109.5
C5—C6—H6119.8C10—C12—H12C109.5
O2—C7—H7A109.5H12A—C12—H12C109.5
O2—C7—H7B109.5H12B—C12—H12C109.5
H7A—C7—H7B109.5C10—C13—H13A109.5
O2—C7—H7C109.5C10—C13—H13B109.5
H7A—C7—H7C109.5H13A—C13—H13B109.5
H7B—C7—H7C109.5C10—C13—H13C109.5
N1—C8—C4112.03 (19)H13A—C13—H13C109.5
N1—C8—H8A109.2H13B—C13—H13C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···O3i0.931.762.685 (2)175
N1—H1N···O2ii0.922.253.093 (3)152

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2733).

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.
  • 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]
  • Xia, L.-Y., Wang, W.-L., Wang, S.-H., Huang, Y.-L. & Shan, S. (2009). Acta Cryst. E65, o1899. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography