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

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

doi:10.1107/S1600536809011532

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1005

doi:10.1107/S1600536809011532

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

Lei Gao,^a Li-hua Guo,^a Rui Liu,^a Dan-hua Que ^a and Hong-fei Ma ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: nj_mhf@yahoo.cn

(Received 26 March 2009; accepted 28 March 2009; online 8 April 2009)

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 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₅NO₅
M_r = 301.29
Orthorhombic, P b c a
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 ) 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[F² > 2σ(F²)] = 0.071
wR(F²) = 0.223
S = 1.06
2634 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O3ⁱ	0.93	2.58	3.466 (5)	158
C16—H16C⋯O4	0.96	2.35	2.899 (5)	115
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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).

Supporting information

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

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

checkCIF report

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.

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

	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.

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

Crystal data top

C₁₆H₁₅NO₅	F(000) = 1264
M_r = 301.29	D_x = 1.375 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 13.390 (3) Å	θ = 1.0–1.0°
b = 10.465 (2) Å	µ = 0.10 mm⁻¹
c = 20.768 (4) Å	T = 294 K
V = 2910.1 (10) Å³	Needle, colorless
Z = 8	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1446 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.2°, θ_min = 2.0°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.980, T_max = 0.990	l = 0→24
2634 measured reflections	3 standard reflections every 120 min
2634 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.223	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.118P)²] where P = (F_o² + 2F_c²)/3
2634 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₆H₁₅NO₅	V = 2910.1 (10) Å³
M_r = 301.29	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.390 (3) Å	µ = 0.10 mm⁻¹
b = 10.465 (2) Å	T = 294 K
c = 20.768 (4) Å	0.20 × 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)	R_int = 0.000
T_min = 0.980, T_max = 0.990	3 standard reflections every 120 min
2634 measured reflections	intensity decay: none
2634 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.223	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
2634 reflections	Δρ_min = −0.26 e Å⁻³
199 parameters

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

	x	y	z	U_iso*/U_eq
N	0.4084 (2)	0.3120 (3)	0.33235 (15)	0.0456 (8)
O1	0.07225 (17)	0.1644 (3)	0.38239 (11)	0.0460 (7)
O2	0.13768 (18)	0.0124 (3)	0.46870 (13)	0.0538 (8)
O3	0.5275 (2)	0.0290 (3)	0.42219 (18)	0.0748 (10)
O4	0.4987 (2)	0.2830 (3)	0.33126 (15)	0.0684 (10)
O5	0.3740 (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	−0.0196	0.2626	0.082*
C2	−0.2731 (4)	0.1305 (6)	0.3092 (3)	0.0793 (16)
H2A	−0.3394	0.1054	0.3051	0.095*
C3	−0.2488 (3)	0.2420 (5)	0.3400 (3)	0.0682 (13)
H3A	−0.2994	0.2942	0.3558	0.082*
C4	−0.1506 (3)	0.2778 (4)	0.3478 (2)	0.0546 (11)
H4A	−0.1357	0.3519	0.3706	0.065*
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	−0.0495	0.0399	0.2737	0.071*
C7	0.0318 (3)	0.2420 (4)	0.3310 (2)	0.0510 (10)
H7A	0.0690	0.2277	0.2915	0.061*
H7B	0.0364	0.3318	0.3420	0.061*
C8	0.1732 (3)	0.1672 (3)	0.39057 (17)	0.0380 (9)
C9	0.2392 (3)	0.2446 (4)	0.35806 (18)	0.0428 (9)
H9A	0.2159	0.3038	0.3282	0.051*
C10	0.3402 (2)	0.2336 (4)	0.37010 (17)	0.0409 (9)
C11	0.3807 (3)	0.1481 (4)	0.41517 (18)	0.0430 (9)
C12	0.3098 (3)	0.0707 (4)	0.44838 (19)	0.0478 (10)
H12A	0.3323	0.0118	0.4786	0.057*
C13	0.2105 (3)	0.0807 (4)	0.43705 (18)	0.0422 (9)
C14	0.1676 (3)	−0.0629 (5)	0.5236 (2)	0.0661 (13)
H14A	0.1103	−0.1054	0.5413	0.099*
H14B	0.1964	−0.0080	0.5557	0.099*
H14C	0.2160	−0.1253	0.5104	0.099*
C15	0.4875 (3)	0.1311 (4)	0.43162 (19)	0.0478 (10)
C16	0.5384 (3)	0.2346 (5)	0.4663 (2)	0.0652 (13)
H16A	0.6068	0.2115	0.4735	0.098*
H16B	0.5059	0.2486	0.5069	0.098*
H16C	0.5356	0.3115	0.4411	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0501 (17)	0.049 (2)	0.0377 (18)	−0.0016 (16)	0.0013 (14)	−0.0030 (16)
O1	0.0448 (14)	0.0553 (18)	0.0378 (15)	−0.0030 (12)	−0.0076 (11)	0.0163 (13)
O2	0.0561 (15)	0.0561 (19)	0.0492 (16)	−0.0062 (13)	−0.0013 (13)	0.0211 (14)
O3	0.0644 (19)	0.056 (2)	0.104 (3)	0.0188 (17)	−0.0083 (17)	−0.0031 (19)
O4	0.0493 (16)	0.083 (2)	0.073 (2)	−0.0008 (15)	0.0050 (14)	0.0105 (18)
O5	0.0683 (18)	0.057 (2)	0.065 (2)	−0.0072 (15)	−0.0065 (15)	0.0197 (17)
C1	0.076 (3)	0.059 (3)	0.070 (3)	−0.014 (3)	−0.017 (3)	−0.009 (2)
C2	0.059 (3)	0.081 (4)	0.098 (4)	−0.018 (3)	−0.016 (3)	0.019 (3)
C3	0.049 (2)	0.067 (3)	0.089 (3)	0.004 (2)	0.003 (2)	0.009 (3)
C4	0.055 (2)	0.048 (3)	0.060 (3)	0.003 (2)	0.005 (2)	0.000 (2)
C5	0.055 (2)	0.041 (2)	0.043 (2)	0.0047 (18)	−0.0095 (17)	0.0119 (19)
C6	0.064 (3)	0.050 (3)	0.063 (3)	0.001 (2)	−0.009 (2)	−0.001 (2)
C7	0.053 (2)	0.054 (3)	0.046 (2)	0.001 (2)	−0.0072 (18)	0.009 (2)
C8	0.0472 (19)	0.037 (2)	0.0300 (18)	−0.0084 (16)	−0.0018 (15)	0.0034 (16)
C9	0.0491 (19)	0.037 (2)	0.042 (2)	0.0030 (17)	−0.0059 (17)	0.0082 (17)
C10	0.0400 (18)	0.043 (2)	0.039 (2)	−0.0042 (16)	−0.0018 (16)	−0.0059 (17)
C11	0.050 (2)	0.038 (2)	0.040 (2)	0.0024 (18)	−0.0055 (17)	0.0017 (18)
C12	0.053 (2)	0.040 (2)	0.050 (3)	0.0087 (18)	−0.0106 (19)	0.0086 (18)
C13	0.050 (2)	0.036 (2)	0.041 (2)	−0.0040 (17)	−0.0026 (17)	0.0077 (17)
C14	0.075 (3)	0.066 (3)	0.057 (3)	−0.010 (2)	−0.008 (2)	0.019 (2)
C15	0.050 (2)	0.052 (3)	0.041 (2)	0.0042 (19)	−0.0028 (17)	−0.002 (2)
C16	0.059 (2)	0.073 (3)	0.063 (3)	0.001 (2)	−0.016 (2)	−0.016 (3)

Geometric parameters (Å, º) top

N—O5	1.209 (4)	C6—H6A	0.9300
N—O4	1.247 (4)	C7—H7A	0.9700
N—C10	1.456 (5)	C7—H7B	0.9700
O1—C8	1.363 (4)	C8—C9	1.376 (5)
O1—C7	1.446 (4)	C8—C13	1.414 (5)
O2—C13	1.376 (4)	C9—C10	1.380 (5)
O2—C14	1.443 (5)	C9—H9A	0.9300
O3—C15	1.212 (5)	C10—C11	1.404 (5)
C1—C6	1.367 (5)	C11—C12	1.426 (5)
C1—C2	1.384 (7)	C11—C15	1.480 (5)
C1—H1A	0.9300	C12—C13	1.355 (5)
C2—C3	1.370 (7)	C12—H12A	0.9300
C2—H2A	0.9300	C14—H14A	0.9600
C3—C4	1.377 (5)	C14—H14B	0.9600
C3—H3A	0.9300	C14—H14C	0.9600
C4—C5	1.389 (5)	C15—C16	1.468 (6)
C4—H4A	0.9300	C16—H16A	0.9600
C5—C6	1.398 (6)	C16—H16B	0.9600
C5—C7	1.475 (5)	C16—H16C	0.9600

O5—N—O4	123.3 (3)	C9—C8—C13	119.0 (3)
O5—N—C10	117.9 (3)	C8—C9—C10	119.4 (3)
O4—N—C10	118.7 (3)	C8—C9—H9A	120.3
C8—O1—C7	116.8 (3)	C10—C9—H9A	120.3
C13—O2—C14	117.7 (3)	C9—C10—C11	123.5 (3)
C6—C1—C2	120.6 (5)	C9—C10—N	118.0 (3)
C6—C1—H1A	119.7	C11—C10—N	118.4 (3)
C2—C1—H1A	119.7	C10—C11—C12	115.3 (3)
C3—C2—C1	118.9 (4)	C10—C11—C15	127.1 (3)
C3—C2—H2A	120.6	C12—C11—C15	117.6 (3)
C1—C2—H2A	120.6	C13—C12—C11	121.7 (4)
C2—C3—C4	120.9 (5)	C13—C12—H12A	119.1
C2—C3—H3A	119.5	C11—C12—H12A	119.1
C4—C3—H3A	119.5	C12—C13—O2	124.9 (4)
C3—C4—C5	120.9 (4)	C12—C13—C8	121.0 (3)
C3—C4—H4A	119.5	O2—C13—C8	114.1 (3)
C5—C4—H4A	119.5	O2—C14—H14A	109.5
C4—C5—C6	117.4 (4)	O2—C14—H14B	109.5
C4—C5—C7	121.2 (4)	H14A—C14—H14B	109.5
C6—C5—C7	121.3 (4)	O2—C14—H14C	109.5
C1—C6—C5	121.1 (4)	H14A—C14—H14C	109.5
C1—C6—H6A	119.4	H14B—C14—H14C	109.5
C5—C6—H6A	119.4	O3—C15—C16	121.6 (4)
O1—C7—C5	107.6 (3)	O3—C15—C11	119.7 (4)
O1—C7—H7A	110.2	C16—C15—C11	118.2 (4)
C5—C7—H7A	110.2	C15—C16—H16A	109.5
O1—C7—H7B	110.2	C15—C16—H16B	109.5
C5—C7—H7B	110.2	H16A—C16—H16B	109.5
H7A—C7—H7B	108.5	C15—C16—H16C	109.5
O1—C8—C9	126.0 (3)	H16A—C16—H16C	109.5
O1—C8—C13	115.0 (3)	H16B—C16—H16C	109.5

C6—C1—C2—C3	0.8 (8)	O4—N—C10—C11	14.6 (5)
C1—C2—C3—C4	−2.0 (8)	C9—C10—C11—C12	0.4 (5)
C2—C3—C4—C5	2.9 (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—C15	3.0 (6)
C2—C1—C6—C5	−0.5 (7)	C10—C11—C12—C13	−0.4 (6)
C4—C5—C6—C1	1.3 (6)	C15—C11—C12—C13	179.2 (4)
C7—C5—C6—C1	178.1 (4)	C11—C12—C13—O2	−177.7 (3)
C8—O1—C7—C5	168.6 (3)	C11—C12—C13—C8	1.3 (6)
C4—C5—C7—O1	100.4 (4)	C14—O2—C13—C12	8.6 (6)
C6—C5—C7—O1	−76.4 (5)	C14—O2—C13—C8	−170.5 (4)
C7—O1—C8—C9	5.7 (5)	O1—C8—C13—C12	177.8 (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—C10	1.9 (5)	C9—C8—C13—O2	177.1 (3)
C8—C9—C10—C11	−1.1 (6)	C10—C11—C15—O3	−118.1 (5)
C8—C9—C10—N	176.7 (3)	C12—C11—C15—O3	62.3 (5)
O5—N—C10—C9	16.4 (5)	C10—C11—C15—C16	69.2 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3ⁱ	0.93	2.58	3.466 (5)	158
C16—H16C···O4	0.96	2.35	2.899 (5)	115

Symmetry code: (i) −x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅NO₅
M_r	301.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	13.390 (3), 10.465 (2), 20.768 (4)
V (Å³)	2910.1 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.980, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2634, 2634, 1446
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.223, 1.06
No. of reflections	2634
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3ⁱ	0.93	2.58	3.466 (5)	158
C16—H16C···O4	0.96	2.35	2.899 (5)	115

Symmetry code: (i) −x+1/2, y+1/2, z.

Acknowledgements

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

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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
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