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Acta Cryst. (2009). E65, o1005    [ doi:10.1107/S1600536809011532 ]

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

L. Gao, L. Guo, R. Liu, D. Que and H. Ma

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
[Figure 2] 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.
1-(4-Benzyloxy-5-methoxy-2-nitrophenyl)ethanone top
Crystal data top
C16H15NO5F(000) = 1264
Mr = 301.29Dx = 1.375 Mg m−3
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 mm−1
c = 20.768 (4) ÅT = 294 K
V = 2910.1 (10) Å3Needle, colorless
Z = 80.20 × 0.10 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1446 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 top
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 = 1.06 w = 1/[σ2(Fo2) + (0.118P)2]
where P = (Fo2 + 2Fc2)/3
2634 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.24 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C16H15NO5V = 2910.1 (10) Å3
Mr = 301.29Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 13.390 (3) ŵ = 0.10 mm−1
b = 10.465 (2) ÅT = 294 K
c = 20.768 (4) Å0.20 × 0.10 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1446 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.980, Tmax = 0.990θmax = 25.2°
2634 measured reflections3 standard reflections every 120 min
2634 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.071H-atom parameters constrained
wR(F2) = 0.223Δρmax = 0.24 e Å−3
S = 1.06Δρmin = −0.26 e Å−3
2634 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
References top

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.

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Mizuta, H., Watanabe, S., Sakurai, Y., Nishiyama, K., Furuta, T., Kobayashi, Y. & Iwamura, M. (2002). Bioorg. Med. Chem. 10, 675–683.

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.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.