N-(4-Nitro­pheneth­yl)formamide

He, L.-P.; Yang, X.-M.; Pang, D.-L.; Li, H.-Z.; Li, F.

doi:10.1107/S1600536810022737

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1721

doi:10.1107/S1600536810022737

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N-(4-Nitrophenethyl)formamide

Li-Ping He,^a Xiao-Ming Yang,^b Dao-Lin Pang,^a Hui-Zhang Li ^a and Fang Li ^a ^*

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bCollege of Pharmaceutical Sciences, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: andrea1985@yahoo.cn

(Received 2 June 2010; accepted 13 June 2010; online 23 June 2010)

The title compound, C₉H₁₀N₂O₃, was synthesized by direct N-formylation of 4-nitrophenethylamine hydrochloride with formic acid and sodium formate in the absence of catalyst and solvent. In the crystal structure, molecules are linked by intermolecular N—H⋯O hydrogen-bond interactions into chains parallel to the a axis.

Related literature

For the applications and synthesis of the title compound, see: Yu et al. (1995 ); Rahman et al. (2010 ).

Experimental

Crystal data

C₉H₁₀N₂O₃
M_r = 194.19
Monoclinic, P 2₁ /c
a = 4.4754 (1) Å
b = 17.6664 (5) Å
c = 12.1548 (4) Å
β = 93.021 (2)°
V = 959.67 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.42 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.681, T_max = 1.000
13857 measured reflections
2218 independent reflections
1407 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.157
S = 1.01
2218 reflections
167 parameters
All H-atom parameters refined
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O3ⁱ	0.762 (18)	2.194 (18)	2.8692 (15)	148.1 (16)
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022737/rz2462sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022737/rz2462Isup2.hkl

checkCIF report

Comment top

N-(4-Nitrophenethyl)formamide is used as an intermediate material in the synthesis of artificial chlordimeform antigen, which is applied in the immunity analysis of chlordimeform (Yu et al., 1995). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the ethylformamide group is approximately planar (maximum deviation 0.089 (2) Å for atom C8) and perpendicular to the benzene ring (dihedral angle 89.99 (7) °). The nitro group is substantially coplanar with the benzene ring, forming a dihedral angle of 5.64 (9)°. In the crystal packing, intermolecular O—H···O hydrogen bonds (Table 1) link the molecules into chains parallel to the a axis.

Related literature top

For the applications and synthesis of the title compound, see: Yu et al. (1995); Rahman et al. (2010).

Experimental top

A mixture of 4-nitrophenethylamine hydrochloride (4.08 g, 0.02mo1), sodium formate (2.08 g, 0.02mo1) and 88% formic acid (20 ml) was heated to reflux and the reaction was monitored by TLC (Rahman et al., 2010.). 50 ml toluene was added and the solution was evaporated under reduced pressure. Dichloromethane was added to dissolve the dry residue and the extract was filtered to remove sodium chloride. The resulting solution was washed with hydrochloric acid followed by water and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to get the crude product. The crude product was recrystallized with dichloromethane, and a light yellow crystalline powder was obtained. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

N-(4-Nitrophenethyl)formamide top

Crystal data top

C₉H₁₀N₂O₃	F(000) = 408
M_r = 194.19	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3623 reflections
a = 4.4754 (1) Å	θ = 2.9–26.8°
b = 17.6664 (5) Å	µ = 0.10 mm⁻¹
c = 12.1548 (4) Å	T = 296 K
β = 93.021 (2)°	Block, colourless
V = 959.67 (5) Å³	0.42 × 0.30 × 0.28 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2218 independent reflections
Radiation source: fine-focus sealed tube	1407 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
phi and ω scans	θ_max = 27.7°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→5
T_min = 0.681, T_max = 1.000	k = −23→23
13857 measured reflections	l = −14→15

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	All H-atom parameters refined
S = 1.01	w = 1/[σ²(F_o²) + (0.0811P)² + 0.120P] where P = (F_o² + 2F_c²)/3
2218 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₉H₁₀N₂O₃	V = 959.67 (5) Å³
M_r = 194.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.4754 (1) Å	µ = 0.10 mm⁻¹
b = 17.6664 (5) Å	T = 296 K
c = 12.1548 (4) Å	0.42 × 0.30 × 0.28 mm
β = 93.021 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2218 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1407 reflections with I > 2σ(I)
T_min = 0.681, T_max = 1.000	R_int = 0.042
13857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.157	All H-atom parameters refined
S = 1.01	Δρ_max = 0.14 e Å⁻³
2218 reflections	Δρ_min = −0.18 e Å⁻³
167 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 > 2σ(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
O1	0.5315 (4)	0.72237 (8)	0.42543 (13)	0.1333 (6)
O2	0.4550 (3)	0.60396 (8)	0.40908 (10)	0.1023 (5)
O3	0.9148 (2)	0.59710 (8)	1.14237 (8)	0.0752 (4)
N1	0.5726 (4)	0.65789 (9)	0.45577 (11)	0.0761 (4)
N2	1.3195 (3)	0.60193 (8)	1.04270 (10)	0.0584 (3)
H2B	1.490 (4)	0.6035 (9)	1.0442 (13)	0.070 (5)*
C1	0.7721 (3)	0.64453 (9)	0.55324 (11)	0.0543 (4)
C2	0.8835 (4)	0.70538 (9)	0.61230 (13)	0.0663 (4)
H2A	0.822 (4)	0.7538 (11)	0.5958 (13)	0.081 (5)*
C3	1.0705 (4)	0.69170 (9)	0.70433 (12)	0.0630 (4)
H3A	1.147 (4)	0.7334 (10)	0.7418 (12)	0.073 (5)*
C4	1.1450 (3)	0.61872 (8)	0.73625 (10)	0.0506 (4)
C5	1.0275 (3)	0.55894 (8)	0.67502 (11)	0.0548 (4)
H5A	1.082 (3)	0.5077 (9)	0.6967 (12)	0.071 (5)*
C6	0.8387 (3)	0.57117 (9)	0.58309 (11)	0.0564 (4)
H6A	0.757 (3)	0.5311 (9)	0.5390 (13)	0.067 (4)*
C7	1.3374 (3)	0.60491 (10)	0.84010 (12)	0.0580 (4)
H7B	1.495 (4)	0.6414 (9)	0.8473 (12)	0.072 (5)*
H7A	1.423 (4)	0.5531 (10)	0.8403 (13)	0.076 (5)*
C8	1.1484 (3)	0.61015 (11)	0.93831 (12)	0.0632 (5)
H8B	1.046 (4)	0.6620 (10)	0.9389 (14)	0.088 (5)*
H8A	0.986 (4)	0.5736 (10)	0.9354 (14)	0.080 (5)*
C9	1.1853 (3)	0.59714 (9)	1.13538 (12)	0.0564 (4)
H9A	1.322 (3)	0.5926 (8)	1.1993 (13)	0.058 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1864 (15)	0.0955 (10)	0.1094 (10)	0.0058 (11)	−0.0736 (10)	0.0306 (8)
O2	0.1260 (11)	0.1099 (10)	0.0660 (7)	−0.0225 (8)	−0.0411 (7)	0.0019 (7)
O3	0.0479 (6)	0.1188 (9)	0.0581 (6)	0.0041 (6)	−0.0059 (5)	0.0155 (6)
N1	0.0876 (10)	0.0875 (10)	0.0510 (7)	−0.0011 (9)	−0.0159 (7)	0.0113 (7)
N2	0.0391 (6)	0.0883 (9)	0.0464 (6)	0.0004 (6)	−0.0107 (5)	0.0035 (6)
C1	0.0570 (8)	0.0655 (9)	0.0397 (6)	−0.0022 (7)	−0.0033 (6)	0.0050 (6)
C2	0.0838 (11)	0.0552 (9)	0.0585 (9)	−0.0023 (8)	−0.0116 (8)	0.0093 (7)
C3	0.0735 (10)	0.0592 (9)	0.0548 (8)	−0.0111 (8)	−0.0107 (7)	−0.0028 (7)
C4	0.0462 (7)	0.0644 (9)	0.0412 (6)	0.0000 (6)	0.0013 (5)	0.0016 (6)
C5	0.0587 (8)	0.0552 (8)	0.0502 (7)	0.0058 (7)	0.0001 (6)	0.0028 (6)
C6	0.0620 (9)	0.0601 (9)	0.0463 (7)	−0.0029 (7)	−0.0025 (6)	−0.0040 (6)
C7	0.0467 (8)	0.0772 (10)	0.0490 (8)	0.0034 (8)	−0.0064 (6)	0.0016 (7)
C8	0.0449 (8)	0.0979 (12)	0.0456 (7)	0.0021 (8)	−0.0109 (6)	0.0008 (8)
C9	0.0497 (8)	0.0704 (9)	0.0474 (7)	0.0032 (7)	−0.0149 (6)	0.0069 (7)

Geometric parameters (Å, º) top

O1—N1	1.208 (2)	C3—H3A	0.922 (17)
O2—N1	1.2147 (19)	C4—C5	1.380 (2)
O3—C9	1.2182 (18)	C4—C7	1.5099 (19)
N1—C1	1.4647 (18)	C5—C6	1.382 (2)
N2—C9	1.3070 (19)	C5—H5A	0.971 (16)
N2—C8	1.4542 (18)	C6—H6A	0.950 (16)
N2—H2B	0.762 (18)	C7—C8	1.502 (2)
C1—C2	1.372 (2)	C7—H7B	0.957 (17)
C1—C6	1.374 (2)	C7—H7A	0.993 (17)
C2—C3	1.382 (2)	C8—H8B	1.025 (18)
C2—H2A	0.917 (18)	C8—H8A	0.971 (18)
C3—C4	1.382 (2)	C9—H9A	0.967 (15)

O1—N1—O2	122.79 (15)	C6—C5—H5A	120.0 (9)
O1—N1—C1	118.37 (15)	C1—C6—C5	118.40 (14)
O2—N1—C1	118.83 (14)	C1—C6—H6A	118.9 (9)
C9—N2—C8	120.92 (13)	C5—C6—H6A	122.7 (9)
C9—N2—H2B	119.1 (13)	C8—C7—C4	109.53 (12)
C8—N2—H2B	119.8 (13)	C8—C7—H7B	109.3 (10)
C2—C1—C6	122.21 (13)	C4—C7—H7B	110.7 (10)
C2—C1—N1	119.10 (14)	C8—C7—H7A	106.8 (9)
C6—C1—N1	118.69 (13)	C4—C7—H7A	110.7 (9)
C1—C2—C3	118.31 (14)	H7B—C7—H7A	109.7 (14)
C1—C2—H2A	121.4 (11)	N2—C8—C7	113.25 (12)
C3—C2—H2A	120.0 (10)	N2—C8—H8B	107.4 (10)
C4—C3—C2	121.13 (14)	C7—C8—H8B	109.4 (10)
C4—C3—H3A	121.9 (10)	N2—C8—H8A	108.9 (10)
C2—C3—H3A	116.9 (10)	C7—C8—H8A	112.4 (10)
C5—C4—C3	118.88 (13)	H8B—C8—H8A	105.1 (15)
C5—C4—C7	120.77 (13)	O3—C9—N2	124.31 (13)
C3—C4—C7	120.26 (13)	O3—C9—H9A	122.2 (9)
C4—C5—C6	121.06 (14)	N2—C9—H9A	113.5 (9)
C4—C5—H5A	118.9 (9)

O1—N1—C1—C2	5.8 (2)	C7—C4—C5—C6	176.62 (13)
O2—N1—C1—C2	−173.98 (16)	C2—C1—C6—C5	−0.8 (2)
O1—N1—C1—C6	−174.89 (17)	N1—C1—C6—C5	179.90 (13)
O2—N1—C1—C6	5.3 (2)	C4—C5—C6—C1	0.5 (2)
C6—C1—C2—C3	0.5 (3)	C5—C4—C7—C8	−96.40 (17)
N1—C1—C2—C3	179.72 (14)	C3—C4—C7—C8	80.06 (18)
C1—C2—C3—C4	0.2 (3)	C9—N2—C8—C7	−172.75 (15)
C2—C3—C4—C5	−0.5 (2)	C4—C7—C8—N2	−176.62 (13)
C2—C3—C4—C7	−177.03 (15)	C8—N2—C9—O3	2.0 (2)
C3—C4—C5—C6	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3ⁱ	0.762 (18)	2.194 (18)	2.8692 (15)	148.1 (16)

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₃
M_r	194.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	4.4754 (1), 17.6664 (5), 12.1548 (4)
β (°)	93.021 (2)
V (Å³)	959.67 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.42 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.681, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13857, 2218, 1407
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.157, 1.01
No. of reflections	2218
No. of parameters	167
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3ⁱ	0.762 (18)	2.194 (18)	2.8692 (15)	148.1 (16)

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors thank Mr Zhi-Yuan Zhou of the Hong Kong Polytechnic University for the X-ray data collection.

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rahman, M., Kundu, D., Hajra, A. & Majee, A. (2010). Tetrahedron Lett. 51, 2896–2899. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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