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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1005.
Published online 2009 April 8. doi:  10.1107/S1600536809011532
PMCID: PMC2977694

1-(4-Benz­yloxy-5-meth­oxy-2-nitro­phen­yl)ethanone

Abstract

In the mol­ecule of the title compound, C16H15NO5, the aromatic rings are oriented at a dihedral angle of 74.89 (3)°. Intra­molecular C—H(...)O inter­actions result in the formation of a seven-membered ring. In the crystal structure, weak inter­molecular C—H(...)O inter­actions link the mol­ecules into chains along the b axis.

Related literature

The title compound is an important pharmaceutical intermediate. For general background, see: Mizuta et al. (2002 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o1005-scheme1.jpg

Experimental

Crystal data

  • C16H15NO5
  • M r = 301.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1005-efi1.jpg
  • a = 13.390 (3) Å
  • b = 10.465 (2) Å
  • c = 20.768 (4) Å
  • V = 2910.1 (10) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 294 K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.980, T max = 0.990
  • 2634 measured reflections
  • 2634 independent reflections
  • 1446 reflections with I > 2σ(I)
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.071
  • wR(F 2) = 0.223
  • S = 1.06
  • 2634 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011532/hk2654sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011532/hk2654Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound contains nitro, acetyl and methoxy groups, which can react with different groups to prepare various functional organic compounds as a fine organic intermediate. We report herein its crystal structure.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C8-C13) are, of course, planar and they are oriented at a dihedral angle of 74.89 (3)°. Intramolecular C-H···O interaction (Table 1) results in the formation of a seven-membered ring C (O4/N/C10/C11/C15/C16/H16C) having twisted conformation.

In the crystal structure, weak intermolecular C-H···O interactions (Table 1) link the molecules into chains along the b axis (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, 1-(4-benzyloxy-5-methoxy-2-nitro- phenyl)ethanone (20.0 g, 66.4 mmol) were dissolved in DMF (50 ml). Then, the solution was poured into ice water (100 ml). The crystalline product was isolated by filtration, washed with water (600 ml). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted.

Crystal data

C16H15NO5F(000) = 1264
Mr = 301.29Dx = 1.375 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 13.390 (3) Åθ = 1.0–1.0°
b = 10.465 (2) ŵ = 0.10 mm1
c = 20.768 (4) ÅT = 294 K
V = 2910.1 (10) Å3Needle, colorless
Z = 80.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer1446 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 25.2°, θmin = 2.0°
ω/2θ scansh = 0→16
Absorption correction: ψ scan (North et al., 1968)k = 0→12
Tmin = 0.980, Tmax = 0.990l = 0→24
2634 measured reflections3 standard reflections every 120 min
2634 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.071Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.223H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.118P)2] where P = (Fo2 + 2Fc2)/3
2634 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.26 e Å3

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
N0.4084 (2)0.3120 (3)0.33235 (15)0.0456 (8)
O10.07225 (17)0.1644 (3)0.38239 (11)0.0460 (7)
O20.13768 (18)0.0124 (3)0.46870 (13)0.0538 (8)
O30.5275 (2)0.0290 (3)0.42219 (18)0.0748 (10)
O40.4987 (2)0.2830 (3)0.33126 (15)0.0684 (10)
O50.3740 (2)0.4020 (3)0.30338 (14)0.0633 (9)
C1−0.1972 (3)0.0558 (5)0.2841 (2)0.0683 (13)
H1A−0.2128−0.01960.26260.082*
C2−0.2731 (4)0.1305 (6)0.3092 (3)0.0793 (16)
H2A−0.33940.10540.30510.095*
C3−0.2488 (3)0.2420 (5)0.3400 (3)0.0682 (13)
H3A−0.29940.29420.35580.082*
C4−0.1506 (3)0.2778 (4)0.3478 (2)0.0546 (11)
H4A−0.13570.35190.37060.065*
C5−0.0736 (3)0.2049 (4)0.32217 (18)0.0461 (10)
C6−0.0996 (3)0.0917 (4)0.2906 (2)0.0592 (12)
H6A−0.04950.03990.27370.071*
C70.0318 (3)0.2420 (4)0.3310 (2)0.0510 (10)
H7A0.06900.22770.29150.061*
H7B0.03640.33180.34200.061*
C80.1732 (3)0.1672 (3)0.39057 (17)0.0380 (9)
C90.2392 (3)0.2446 (4)0.35806 (18)0.0428 (9)
H9A0.21590.30380.32820.051*
C100.3402 (2)0.2336 (4)0.37010 (17)0.0409 (9)
C110.3807 (3)0.1481 (4)0.41517 (18)0.0430 (9)
C120.3098 (3)0.0707 (4)0.44838 (19)0.0478 (10)
H12A0.33230.01180.47860.057*
C130.2105 (3)0.0807 (4)0.43705 (18)0.0422 (9)
C140.1676 (3)−0.0629 (5)0.5236 (2)0.0661 (13)
H14A0.1103−0.10540.54130.099*
H14B0.1964−0.00800.55570.099*
H14C0.2160−0.12530.51040.099*
C150.4875 (3)0.1311 (4)0.43162 (19)0.0478 (10)
C160.5384 (3)0.2346 (5)0.4663 (2)0.0652 (13)
H16A0.60680.21150.47350.098*
H16B0.50590.24860.50690.098*
H16C0.53560.31150.44110.098*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N0.0501 (17)0.049 (2)0.0377 (18)−0.0016 (16)0.0013 (14)−0.0030 (16)
O10.0448 (14)0.0553 (18)0.0378 (15)−0.0030 (12)−0.0076 (11)0.0163 (13)
O20.0561 (15)0.0561 (19)0.0492 (16)−0.0062 (13)−0.0013 (13)0.0211 (14)
O30.0644 (19)0.056 (2)0.104 (3)0.0188 (17)−0.0083 (17)−0.0031 (19)
O40.0493 (16)0.083 (2)0.073 (2)−0.0008 (15)0.0050 (14)0.0105 (18)
O50.0683 (18)0.057 (2)0.065 (2)−0.0072 (15)−0.0065 (15)0.0197 (17)
C10.076 (3)0.059 (3)0.070 (3)−0.014 (3)−0.017 (3)−0.009 (2)
C20.059 (3)0.081 (4)0.098 (4)−0.018 (3)−0.016 (3)0.019 (3)
C30.049 (2)0.067 (3)0.089 (3)0.004 (2)0.003 (2)0.009 (3)
C40.055 (2)0.048 (3)0.060 (3)0.003 (2)0.005 (2)0.000 (2)
C50.055 (2)0.041 (2)0.043 (2)0.0047 (18)−0.0095 (17)0.0119 (19)
C60.064 (3)0.050 (3)0.063 (3)0.001 (2)−0.009 (2)−0.001 (2)
C70.053 (2)0.054 (3)0.046 (2)0.001 (2)−0.0072 (18)0.009 (2)
C80.0472 (19)0.037 (2)0.0300 (18)−0.0084 (16)−0.0018 (15)0.0034 (16)
C90.0491 (19)0.037 (2)0.042 (2)0.0030 (17)−0.0059 (17)0.0082 (17)
C100.0400 (18)0.043 (2)0.039 (2)−0.0042 (16)−0.0018 (16)−0.0059 (17)
C110.050 (2)0.038 (2)0.040 (2)0.0024 (18)−0.0055 (17)0.0017 (18)
C120.053 (2)0.040 (2)0.050 (3)0.0087 (18)−0.0106 (19)0.0086 (18)
C130.050 (2)0.036 (2)0.041 (2)−0.0040 (17)−0.0026 (17)0.0077 (17)
C140.075 (3)0.066 (3)0.057 (3)−0.010 (2)−0.008 (2)0.019 (2)
C150.050 (2)0.052 (3)0.041 (2)0.0042 (19)−0.0028 (17)−0.002 (2)
C160.059 (2)0.073 (3)0.063 (3)0.001 (2)−0.016 (2)−0.016 (3)

Geometric parameters (Å, °)

N—O51.209 (4)C6—H6A0.9300
N—O41.247 (4)C7—H7A0.9700
N—C101.456 (5)C7—H7B0.9700
O1—C81.363 (4)C8—C91.376 (5)
O1—C71.446 (4)C8—C131.414 (5)
O2—C131.376 (4)C9—C101.380 (5)
O2—C141.443 (5)C9—H9A0.9300
O3—C151.212 (5)C10—C111.404 (5)
C1—C61.367 (5)C11—C121.426 (5)
C1—C21.384 (7)C11—C151.480 (5)
C1—H1A0.9300C12—C131.355 (5)
C2—C31.370 (7)C12—H12A0.9300
C2—H2A0.9300C14—H14A0.9600
C3—C41.377 (5)C14—H14B0.9600
C3—H3A0.9300C14—H14C0.9600
C4—C51.389 (5)C15—C161.468 (6)
C4—H4A0.9300C16—H16A0.9600
C5—C61.398 (6)C16—H16B0.9600
C5—C71.475 (5)C16—H16C0.9600
O5—N—O4123.3 (3)C9—C8—C13119.0 (3)
O5—N—C10117.9 (3)C8—C9—C10119.4 (3)
O4—N—C10118.7 (3)C8—C9—H9A120.3
C8—O1—C7116.8 (3)C10—C9—H9A120.3
C13—O2—C14117.7 (3)C9—C10—C11123.5 (3)
C6—C1—C2120.6 (5)C9—C10—N118.0 (3)
C6—C1—H1A119.7C11—C10—N118.4 (3)
C2—C1—H1A119.7C10—C11—C12115.3 (3)
C3—C2—C1118.9 (4)C10—C11—C15127.1 (3)
C3—C2—H2A120.6C12—C11—C15117.6 (3)
C1—C2—H2A120.6C13—C12—C11121.7 (4)
C2—C3—C4120.9 (5)C13—C12—H12A119.1
C2—C3—H3A119.5C11—C12—H12A119.1
C4—C3—H3A119.5C12—C13—O2124.9 (4)
C3—C4—C5120.9 (4)C12—C13—C8121.0 (3)
C3—C4—H4A119.5O2—C13—C8114.1 (3)
C5—C4—H4A119.5O2—C14—H14A109.5
C4—C5—C6117.4 (4)O2—C14—H14B109.5
C4—C5—C7121.2 (4)H14A—C14—H14B109.5
C6—C5—C7121.3 (4)O2—C14—H14C109.5
C1—C6—C5121.1 (4)H14A—C14—H14C109.5
C1—C6—H6A119.4H14B—C14—H14C109.5
C5—C6—H6A119.4O3—C15—C16121.6 (4)
O1—C7—C5107.6 (3)O3—C15—C11119.7 (4)
O1—C7—H7A110.2C16—C15—C11118.2 (4)
C5—C7—H7A110.2C15—C16—H16A109.5
O1—C7—H7B110.2C15—C16—H16B109.5
C5—C7—H7B110.2H16A—C16—H16B109.5
H7A—C7—H7B108.5C15—C16—H16C109.5
O1—C8—C9126.0 (3)H16A—C16—H16C109.5
O1—C8—C13115.0 (3)H16B—C16—H16C109.5
C6—C1—C2—C30.8 (8)O4—N—C10—C1114.6 (5)
C1—C2—C3—C4−2.0 (8)C9—C10—C11—C120.4 (5)
C2—C3—C4—C52.9 (7)N—C10—C11—C12−177.4 (3)
C3—C4—C5—C6−2.5 (6)C9—C10—C11—C15−179.2 (4)
C3—C4—C5—C7−179.4 (4)N—C10—C11—C153.0 (6)
C2—C1—C6—C5−0.5 (7)C10—C11—C12—C13−0.4 (6)
C4—C5—C6—C11.3 (6)C15—C11—C12—C13179.2 (4)
C7—C5—C6—C1178.1 (4)C11—C12—C13—O2−177.7 (3)
C8—O1—C7—C5168.6 (3)C11—C12—C13—C81.3 (6)
C4—C5—C7—O1100.4 (4)C14—O2—C13—C128.6 (6)
C6—C5—C7—O1−76.4 (5)C14—O2—C13—C8−170.5 (4)
C7—O1—C8—C95.7 (5)O1—C8—C13—C12177.8 (4)
C7—O1—C8—C13−174.0 (3)C9—C8—C13—C12−2.0 (6)
O1—C8—C9—C10−177.9 (3)O1—C8—C13—O2−3.1 (5)
C13—C8—C9—C101.9 (5)C9—C8—C13—O2177.1 (3)
C8—C9—C10—C11−1.1 (6)C10—C11—C15—O3−118.1 (5)
C8—C9—C10—N176.7 (3)C12—C11—C15—O362.3 (5)
O5—N—C10—C916.4 (5)C10—C11—C15—C1669.2 (5)
O4—N—C10—C9−163.3 (3)C12—C11—C15—C16−110.4 (4)
O5—N—C10—C11−165.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4A···O3i0.932.583.466 (5)158
C16—H16C···O40.962.352.899 (5)115

Symmetry codes: (i) −x+1/2, y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2654).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Mizuta, H., Watanabe, S., Sakurai, Y., Nishiyama, K., Furuta, T., Kobayashi, Y. & Iwamura, M. (2002). Bioorg. Med. Chem.10, 675–683. [PubMed]
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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