4-Acetamido-3-nitro­phenyl acetate

Gu, Z.; Cheng, W.

doi:10.1107/S1600536809015797

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1194

doi:10.1107/S1600536809015797

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4-Acetamido-3-nitrophenyl acetate

Zhun Gu ^a and Wei Cheng ^b ^*

^aDepartment of Chemical Engineering, Chien-shiung Institute of Technology, Suzhou 215411, People's Republic of China, and ^bDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: larry_18@163.com

(Received 27 April 2009; accepted 28 April 2009; online 7 May 2009)

In the molecule of the title compound, C₁₀H₁₀N₂O₅, intramolecular C—H⋯O interactions result in the formation of a five- and a six-membered ring. The five-membered ring is planar and is oriented at a dihedral angle of 0.34 (3)° with respect to the plane of the aromatic ring, while the six-membered ring has a twist conformation. In the crystal structure, intermolecular C—H⋯O interactions link the molecules into chains.

Related literature

For a related structure, see: Gu (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₀N₂O₅
M_r = 238.20
Monoclinic, C 2/c
a = 24.859 (5) Å
b = 4.7060 (9) Å
c = 19.773 (4) Å
β = 108.67 (3)°
V = 2191.4 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.966, T_max = 0.988
2039 measured reflections
1992 independent reflections
1310 reflections with I > 2σ(I)
R_int = 0.021
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.187
S = 1.00
1992 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2	0.93	2.33	2.647 (4)	100
C7—H7A⋯O5	0.93	2.35	2.836 (4)	113
C10—H10C⋯O5ⁱ	0.96	2.59	3.300 (4)	130
Symmetry code: (i) x, y-1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); 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 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015797/hk2677sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015797/hk2677Isup2.hkl

checkCIF report

Comment top

The title compound is an important medical intermediate used to synthesize 3,4-diaminophenol, which is the main raw material of luxabendazole (Gu, 2007). We report herein the crystal structure of the title compound, which is of interest to us in the field.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C3-C8) is, of course, planar. Intramolecular C-H···O interactions (Table 1) result in the formations of five- and six-membered rings: B (O2/N2/C4/C5/H4A) and C (O4/O5/C5-C7/C9/H7A). Ring B is planar and it is oriented with respect to ring A at a dihedral angle of 0.34 (3)°, while ring C has a twisted conformation.

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

Related literature top

For a related structure, see: Gu (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of 4-aminophenol, fuming nitric acid and acetic anhydride (Gu, 2007). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.2 g) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 2 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bonds are shown as dashed lines.

4-Acetamido-3-nitrophenyl acetate top

Crystal data top

C₁₀H₁₀N₂O₅	F(000) = 992
M_r = 238.20	D_x = 1.444 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 24.859 (5) Å	θ = 9–13°
b = 4.7060 (9) Å	µ = 0.12 mm⁻¹
c = 19.773 (4) Å	T = 298 K
β = 108.67 (3)°	Needle, colorless
V = 2191.4 (8) Å³	0.30 × 0.10 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1310 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = 0→29
Absorption correction: ψ scan (North et al., 1968)	k = 0→5
T_min = 0.966, T_max = 0.988	l = −23→22
2039 measured reflections	3 standard reflections every 120 min
1992 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.064	H-atom parameters constrained
wR(F²) = 0.187	w = 1/[σ²(F_o²) + (0.1P)² + 1.4P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1992 reflections	Δρ_max = 0.51 e Å⁻³
136 parameters	Δρ_min = −0.56 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.091 (8)

Crystal data top

C₁₀H₁₀N₂O₅	V = 2191.4 (8) Å³
M_r = 238.20	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 24.859 (5) Å	µ = 0.12 mm⁻¹
b = 4.7060 (9) Å	T = 298 K
c = 19.773 (4) Å	0.30 × 0.10 × 0.10 mm
β = 108.67 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1310 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.021
T_min = 0.966, T_max = 0.988	3 standard reflections every 120 min
2039 measured reflections	intensity decay: 1%
1992 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 1.00	Δρ_max = 0.51 e Å⁻³
1992 reflections	Δρ_min = −0.56 e Å⁻³
136 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
N1	0.07647 (10)	0.5724 (5)	0.10146 (12)	0.0515 (4)
H1A	0.0516	0.7061	0.0897	0.062*
N2	0.06554 (11)	−0.0326 (5)	−0.09742 (14)	0.0514 (7)
O1	0.12640 (12)	0.2734 (6)	0.18301 (13)	0.0844 (9)
O2	0.02074 (10)	−0.1112 (6)	−0.09213 (14)	0.0857 (9)
O3	0.08434 (11)	−0.1300 (6)	−0.14164 (15)	0.0872 (9)
O4	0.17417 (10)	0.2065 (5)	−0.10210 (12)	0.0688 (7)
O5	0.21944 (11)	0.6153 (5)	−0.11162 (14)	0.0770 (8)
C1	0.06037 (13)	0.5863 (7)	0.21107 (15)	0.0515 (4)
H1B	0.0723	0.5004	0.2576	0.077*
H1C	0.0204	0.5560	0.1888	0.077*
H1D	0.0680	0.7866	0.2156	0.077*
C2	0.09173 (14)	0.4575 (7)	0.16704 (16)	0.0515 (4)
C3	0.10194 (13)	0.4694 (7)	0.05257 (16)	0.0515 (4)
C4	0.07426 (12)	0.2714 (6)	0.00398 (15)	0.0457 (7)
H4A	0.0399	0.1961	0.0048	0.055*
C5	0.09830 (12)	0.1834 (6)	−0.04697 (15)	0.0441 (7)
C6	0.14971 (11)	0.2930 (6)	−0.05065 (15)	0.0427 (7)
C7	0.17661 (12)	0.4918 (6)	0.00190 (17)	0.0512 (8)
H7A	0.2116	0.5645	0.0029	0.061*
C8	0.15321 (13)	0.5825 (6)	0.05171 (16)	0.0514 (8)
H8A	0.1716	0.7196	0.0850	0.062*
C9	0.20627 (12)	0.3744 (6)	−0.13076 (16)	0.0484 (7)
C10	0.22342 (15)	0.2336 (7)	−0.18863 (18)	0.0607 (9)
H10A	0.2458	0.3629	−0.2061	0.091*
H10B	0.1901	0.1808	−0.2270	0.091*
H10C	0.2454	0.0667	−0.1699	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0594 (9)	0.0497 (9)	0.0486 (8)	0.0021 (7)	0.0217 (7)	0.0021 (7)
N2	0.0494 (14)	0.0471 (15)	0.0587 (16)	−0.0106 (12)	0.0185 (12)	−0.0027 (13)
O1	0.0895 (18)	0.093 (2)	0.0743 (17)	0.0254 (16)	0.0320 (14)	0.0246 (15)
O2	0.0725 (16)	0.093 (2)	0.100 (2)	−0.0430 (15)	0.0402 (15)	−0.0344 (16)
O3	0.0887 (18)	0.095 (2)	0.0935 (19)	−0.0414 (16)	0.0506 (16)	−0.0460 (16)
O4	0.0795 (16)	0.0577 (14)	0.0814 (17)	−0.0073 (12)	0.0426 (14)	−0.0024 (12)
O5	0.109 (2)	0.0442 (14)	0.0964 (19)	−0.0279 (13)	0.0595 (16)	−0.0069 (13)
C1	0.0594 (9)	0.0497 (9)	0.0486 (8)	0.0021 (7)	0.0217 (7)	0.0021 (7)
C2	0.0594 (9)	0.0497 (9)	0.0486 (8)	0.0021 (7)	0.0217 (7)	0.0021 (7)
C3	0.0594 (9)	0.0497 (9)	0.0486 (8)	0.0021 (7)	0.0217 (7)	0.0021 (7)
C4	0.0444 (15)	0.0400 (16)	0.0561 (17)	−0.0079 (13)	0.0207 (13)	−0.0007 (14)
C5	0.0483 (15)	0.0337 (14)	0.0490 (16)	−0.0059 (13)	0.0139 (13)	−0.0002 (13)
C6	0.0463 (15)	0.0332 (14)	0.0508 (16)	−0.0008 (13)	0.0184 (13)	0.0066 (13)
C7	0.0479 (16)	0.0421 (16)	0.0637 (19)	−0.0107 (13)	0.0181 (15)	−0.0017 (15)
C8	0.0601 (18)	0.0422 (17)	0.0498 (17)	−0.0059 (15)	0.0146 (14)	−0.0020 (14)
C9	0.0521 (17)	0.0392 (17)	0.0585 (18)	−0.0001 (14)	0.0239 (14)	0.0058 (14)
C10	0.076 (2)	0.0516 (19)	0.068 (2)	−0.0007 (17)	0.0421 (18)	0.0031 (17)

Geometric parameters (Å, º) top

O1—C2	1.191 (4)	C3—C4	1.357 (4)
O4—C9	1.368 (3)	C3—C8	1.386 (4)
O4—C6	1.402 (3)	C4—C5	1.389 (4)
O5—C9	1.207 (3)	C4—H4A	0.9300
N1—C2	1.343 (4)	C5—C6	1.402 (4)
N1—C3	1.401 (4)	C6—C7	1.399 (4)
N1—H1A	0.8600	C7—C8	1.363 (4)
N2—O3	1.206 (3)	C7—H7A	0.9300
N2—O2	1.209 (3)	C8—H8A	0.9300
N2—C5	1.474 (4)	C9—C10	1.497 (4)
C1—C2	1.473 (4)	C10—H10A	0.9600
C1—H1B	0.9600	C10—H10B	0.9600
C1—H1C	0.9600	C10—H10C	0.9600
C1—H1D	0.9600

C9—O4—C6	125.4 (2)	C4—C5—C6	122.6 (3)
C2—N1—C3	118.5 (3)	C4—C5—N2	115.1 (2)
C2—N1—H1A	120.8	C6—C5—N2	122.3 (3)
C3—N1—H1A	120.8	C7—C6—C5	115.7 (3)
O2—N2—C5	118.5 (3)	C7—C6—O4	121.2 (2)
O3—N2—O2	121.8 (3)	C5—C6—O4	123.0 (3)
O3—N2—C5	119.6 (2)	C8—C7—C6	122.2 (3)
C2—C1—H1B	109.5	C8—C7—H7A	118.9
C2—C1—H1C	109.5	C6—C7—H7A	118.9
H1B—C1—H1C	109.5	C7—C8—C3	119.7 (3)
C2—C1—H1D	109.5	C7—C8—H8A	120.2
H1B—C1—H1D	109.5	C3—C8—H8A	120.2
H1C—C1—H1D	109.5	O5—C9—O4	123.2 (3)
O1—C2—N1	120.4 (3)	O5—C9—C10	122.7 (3)
O1—C2—C1	128.2 (3)	O4—C9—C10	114.1 (3)
N1—C2—C1	111.5 (3)	C9—C10—H10A	109.5
C4—C3—C8	121.0 (3)	C9—C10—H10B	109.5
C4—C3—N1	119.2 (3)	H10A—C10—H10B	109.5
C8—C3—N1	119.7 (3)	C9—C10—H10C	109.5
C3—C4—C5	118.7 (3)	H10A—C10—H10C	109.5
C3—C4—H4A	120.7	H10B—C10—H10C	109.5
C5—C4—H4A	120.7

C3—N1—C2—O1	0.4 (5)	N2—C5—C6—C7	−178.6 (3)
C3—N1—C2—C1	−179.1 (3)	C4—C5—C6—O4	−179.7 (3)
C2—N1—C3—C4	97.3 (4)	N2—C5—C6—O4	−0.2 (4)
C2—N1—C3—C8	−86.5 (4)	C9—O4—C6—C7	−33.5 (4)
C8—C3—C4—C5	0.0 (5)	C9—O4—C6—C5	148.2 (3)
N1—C3—C4—C5	176.2 (3)	C5—C6—C7—C8	−2.7 (4)
C3—C4—C5—C6	−0.7 (5)	O4—C6—C7—C8	178.9 (3)
C3—C4—C5—N2	179.8 (3)	C6—C7—C8—C3	2.2 (5)
O3—N2—C5—C4	−177.0 (3)	C4—C3—C8—C7	−0.7 (5)
O2—N2—C5—C4	1.6 (4)	N1—C3—C8—C7	−176.9 (3)
O3—N2—C5—C6	3.5 (4)	C6—O4—C9—O5	3.9 (5)
O2—N2—C5—C6	−178.0 (3)	C6—O4—C9—C10	−175.7 (3)
C4—C5—C6—C7	1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2	0.93	2.33	2.647 (4)	100
C7—H7A···O5	0.93	2.35	2.836 (4)	113
C10—H10C···O5ⁱ	0.96	2.59	3.300 (4)	130

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂O₅
M_r	238.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	24.859 (5), 4.7060 (9), 19.773 (4)
β (°)	108.67 (3)
V (Å³)	2191.4 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.966, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	2039, 1992, 1310
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.187, 1.00
No. of reflections	1992
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.56

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2	0.93	2.33	2.647 (4)	100
C7—H7A···O5	0.93	2.35	2.836 (4)	113
C10—H10C···O5ⁱ	0.96	2.59	3.300 (4)	130

Symmetry code: (i) x, y−1, z.

Acknowledgements

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

References

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