Methyl N-(4-nitro­phen­yl)carbamate

Cai, Q.; Fei, Z.; Li, L.

doi:10.1107/S1600536811018757

organic compounds

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Volume 67| Part 6| June 2011| Page o1494

doi:10.1107/S1600536811018757

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Methyl N-(4-nitrophenyl)carbamate

Qun Cai,^a Zhuan Fei ^a and Lin Li ^a ^*

^aKey Laboratory of Pesticide and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: caiqun275885586@163.com

(Received 12 April 2011; accepted 17 May 2011; online 25 May 2011)

In the title molecule, C₈H₈N₂O₄, the nitro and methoxycarbonyl groups are twisted from the plane of aromatic ring by 5.1 (1) and 6.2 (1)°, respectively. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules related by translation along the b axis into chains. Weak intermolecular C—H⋯O interactions link further these chains into sheets parallel to the bc plane.

Related literature

For the preparation of the title compound, see: Wilshire (1990 ). For a related structure, see: Yakimanski et al. (1997 ).

Experimental

Crystal data

C₈H₈N₂O₄
M_r = 196.16
Triclinic, $[P \overline 1]$
a = 7.4269 (11) Å
b = 8.1003 (12) Å
c = 8.5376 (12) Å
α = 101.634 (2)°
β = 97.914 (2)°
γ = 116.660 (2)°
V = 434.04 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.04 mm

Data collection

Bruker SMART APEX diffractometer
4507 measured reflections
1686 independent reflections
1539 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.162
S = 1.26
1686 reflections
132 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O2ⁱ	0.93	2.57	3.471 (3)	163
C1—H1B⋯O4ⁱⁱ	0.96	2.53	3.324 (4)	140
N1—H1⋯O3ⁱⁱⁱ	0.82 (3)	2.20 (4)	3.016 (3)	170 (3)
Symmetry codes: (i) x, y, z-1; (ii) x, y-1, z+1; (iii) x, y-1, z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018757/cv5074sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018757/cv5074Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018757/cv5074Isup3.cml

checkCIF report

Comment top

4-Nitrophenylhexyl derivatives are studied in the crystal engineering and design of nonlinear optical (NLO) materials (Yakimanski et al., 1997). Herewith we report the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those observed in 4-nitrophenyl-hexyl-urethane (Yakimanski et al., 1997). The nitro and methoxycarbonyl groups are twisted from the plane of aromatic ring at 5.1 (1) and 6.2 (1)°, respectively. In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules related by translation along axis b<ι> into chains. Weak intermolecular C—H···O interactions (Table 1) link further these chains into sheets parallel to bc<ι> plane.

Related literature top

For the preparation of the title compound, see: Wilshire (1990). For a related structure, see: Yakimanski et al. (1997).

Experimental top

The title compound was synthesized according to Wilshire (1990). Crystals of (I) suitable for X-ray diffraction were grown by slow evaporation of a chloroform-methanol (2:1) solution of the title compound under 293 K.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I), showing the atom-labelling scheme, with displacement ellipsoids drawn at the 30% probability level.

Methyl N-(4-nitrophenyl)carbamate top

Crystal data top

C₈H₈N₂O₄	Z = 2
M_r = 196.16	F(000) = 204
Triclinic, P1	D_x = 1.501 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4269 (11) Å	Cell parameters from 2193 reflections
b = 8.1003 (12) Å	θ = 2.5–28.2°
c = 8.5376 (12) Å	µ = 0.12 mm⁻¹
α = 101.634 (2)°	T = 298 K
β = 97.914 (2)°	Block, yellow
γ = 116.660 (2)°	0.40 × 0.30 × 0.04 mm
V = 434.04 (11) Å³

Data collection top

Bruker SMART APEX diffractometer	1539 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 26.0°, θ_min = 2.5°
ϕ and ω scans	h = −9→9
4507 measured reflections	k = −9→9
1686 independent reflections	l = −10→10

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ²(F_o²) + (0.047P)² + 0.2842P] where P = (F_o² + 2F_c²)/3
1686 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₈H₈N₂O₄	γ = 116.660 (2)°
M_r = 196.16	V = 434.04 (11) Å³
Triclinic, P1	Z = 2
a = 7.4269 (11) Å	Mo Kα radiation
b = 8.1003 (12) Å	µ = 0.12 mm⁻¹
c = 8.5376 (12) Å	T = 298 K
α = 101.634 (2)°	0.40 × 0.30 × 0.04 mm
β = 97.914 (2)°

Data collection top

Bruker SMART APEX diffractometer	1539 reflections with I > 2σ(I)
4507 measured reflections	R_int = 0.051
1686 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	Δρ_max = 0.21 e Å⁻³
1686 reflections	Δρ_min = −0.32 e Å⁻³
132 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
C1	0.2798 (6)	0.1171 (5)	0.4095 (4)	0.0645 (10)
H1A	0.4024	0.2283	0.4846	0.097*
H1B	0.2871	0.0023	0.4122	0.097*
H1C	0.1582	0.1095	0.4419	0.097*
C2	0.2591 (4)	0.2904 (4)	0.2229 (3)	0.0400 (6)
C3	0.2433 (4)	0.4234 (4)	−0.0116 (3)	0.0351 (6)
C4	0.2670 (4)	0.5997 (4)	0.0750 (3)	0.0391 (6)
H4	0.2853	0.6318	0.1891	0.047*
C5	0.2633 (4)	0.7260 (4)	−0.0091 (3)	0.0399 (6)
H5	0.2796	0.8445	0.0481	0.048*
C6	0.2355 (4)	0.6774 (4)	−0.1782 (3)	0.0377 (6)
C7	0.2141 (5)	0.5042 (4)	−0.2666 (3)	0.0427 (7)
H7	0.1979	0.4739	−0.3804	0.051*
C8	0.2173 (4)	0.3786 (4)	−0.1826 (3)	0.0415 (7)
H8	0.2018	0.2607	−0.2405	0.050*
N2	0.2288 (4)	0.8111 (4)	−0.2670 (3)	0.0479 (6)
N1	0.2450 (4)	0.2846 (4)	0.0624 (3)	0.0436 (6)
O1	0.2673 (4)	0.1340 (3)	0.2437 (2)	0.0538 (6)
O2	0.2635 (4)	0.4136 (3)	0.3310 (2)	0.0545 (6)
O3	0.2327 (4)	0.9584 (3)	−0.1911 (3)	0.0695 (7)
O4	0.2176 (4)	0.7718 (4)	−0.4139 (3)	0.0733 (8)
H1	0.235 (5)	0.187 (5)	0.001 (4)	0.059 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.089 (3)	0.073 (2)	0.0476 (18)	0.045 (2)	0.0229 (17)	0.0351 (17)
C2	0.0426 (16)	0.0416 (16)	0.0391 (14)	0.0211 (13)	0.0138 (12)	0.0152 (13)
C3	0.0356 (14)	0.0342 (14)	0.0388 (14)	0.0188 (12)	0.0108 (11)	0.0128 (11)
C4	0.0481 (16)	0.0400 (15)	0.0286 (12)	0.0224 (13)	0.0106 (11)	0.0064 (11)
C5	0.0458 (16)	0.0310 (14)	0.0441 (15)	0.0224 (13)	0.0101 (12)	0.0061 (11)
C6	0.0362 (14)	0.0361 (15)	0.0429 (14)	0.0185 (12)	0.0089 (11)	0.0150 (12)
C7	0.0567 (18)	0.0455 (17)	0.0338 (14)	0.0307 (15)	0.0129 (12)	0.0129 (12)
C8	0.0562 (18)	0.0350 (15)	0.0365 (14)	0.0271 (14)	0.0122 (12)	0.0051 (11)
N2	0.0539 (15)	0.0430 (15)	0.0545 (15)	0.0282 (13)	0.0137 (12)	0.0194 (12)
N1	0.0675 (17)	0.0398 (14)	0.0324 (12)	0.0334 (13)	0.0155 (11)	0.0101 (10)
O1	0.0864 (16)	0.0512 (13)	0.0429 (11)	0.0426 (12)	0.0242 (11)	0.0254 (10)
O2	0.0838 (16)	0.0558 (13)	0.0366 (11)	0.0421 (12)	0.0224 (10)	0.0157 (10)
O3	0.106 (2)	0.0434 (13)	0.0709 (16)	0.0476 (14)	0.0179 (14)	0.0174 (11)
O4	0.120 (2)	0.0758 (17)	0.0552 (15)	0.0635 (17)	0.0334 (14)	0.0378 (13)

Geometric parameters (Å, º) top

C1—O1	1.444 (3)	C4—H4	0.9300
C1—H1A	0.9600	C5—C6	1.378 (4)
C1—H1B	0.9600	C5—H5	0.9300
C1—H1C	0.9600	C6—C7	1.379 (4)
C2—O2	1.200 (3)	C6—N2	1.456 (3)
C2—O1	1.340 (3)	C7—C8	1.364 (4)
C2—N1	1.350 (3)	C7—H7	0.9300
C3—C4	1.390 (4)	C8—H8	0.9300
C3—C8	1.394 (4)	N2—O4	1.211 (3)
C3—N1	1.400 (3)	N2—O3	1.223 (3)
C4—C5	1.370 (4)	N1—H1	0.82 (3)

O1—C1—H1A	109.5	C6—C5—H5	120.0
O1—C1—H1B	109.5	C5—C6—C7	121.6 (2)
H1A—C1—H1B	109.5	C5—C6—N2	119.7 (2)
O1—C1—H1C	109.5	C7—C6—N2	118.7 (2)
H1A—C1—H1C	109.5	C8—C7—C6	118.3 (2)
H1B—C1—H1C	109.5	C8—C7—H7	120.9
O2—C2—O1	124.7 (3)	C6—C7—H7	120.9
O2—C2—N1	126.5 (3)	C7—C8—C3	121.3 (2)
O1—C2—N1	108.8 (2)	C7—C8—H8	119.3
C4—C3—C8	119.3 (2)	C3—C8—H8	119.3
C4—C3—N1	124.0 (2)	O4—N2—O3	122.3 (3)
C8—C3—N1	116.7 (2)	O4—N2—C6	118.9 (2)
C5—C4—C3	119.5 (2)	O3—N2—C6	118.9 (2)
C5—C4—H4	120.3	C2—N1—C3	127.9 (2)
C3—C4—H4	120.3	C2—N1—H1	116 (2)
C4—C5—C6	120.0 (2)	C3—N1—H1	116 (2)
C4—C5—H5	120.0	C2—O1—C1	115.7 (2)

C8—C3—C4—C5	0.4 (4)	C5—C6—N2—O4	175.4 (3)
N1—C3—C4—C5	179.9 (3)	C7—C6—N2—O4	−4.5 (4)
C3—C4—C5—C6	0.2 (4)	C5—C6—N2—O3	−5.3 (4)
C4—C5—C6—C7	−1.0 (4)	C7—C6—N2—O3	174.8 (3)
C4—C5—C6—N2	179.2 (2)	O2—C2—N1—C3	3.5 (5)
C5—C6—C7—C8	1.2 (4)	O1—C2—N1—C3	−176.5 (3)
N2—C6—C7—C8	−179.0 (2)	C4—C3—N1—C2	3.4 (5)
C6—C7—C8—C3	−0.6 (4)	C8—C3—N1—C2	−177.0 (3)
C4—C3—C8—C7	−0.2 (4)	O2—C2—O1—C1	0.8 (4)
N1—C3—C8—C7	−179.8 (3)	N1—C2—O1—C1	−179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O2ⁱ	0.93	2.57	3.471 (3)	163
C4—H4···O2	0.93	2.30	2.892 (3)	121
C1—H1B···O4ⁱⁱ	0.96	2.53	3.324 (4)	140
N1—H1···O3ⁱⁱⁱ	0.82 (3)	2.20 (4)	3.016 (3)	170 (3)

Symmetry codes: (i) x, y, z−1; (ii) x, y−1, z+1; (iii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₈H₈N₂O₄
M_r	196.16
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.4269 (11), 8.1003 (12), 8.5376 (12)
α, β, γ (°)	101.634 (2), 97.914 (2), 116.660 (2)
V (Å³)	434.04 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.40 × 0.30 × 0.04

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4507, 1686, 1539
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.162, 1.26
No. of reflections	1686
No. of parameters	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), 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
C7—H7···O2ⁱ	0.93	2.57	3.471 (3)	163
C1—H1B···O4ⁱⁱ	0.96	2.53	3.324 (4)	140
N1—H1···O3ⁱⁱⁱ	0.82 (3)	2.20 (4)	3.016 (3)	170 (3)

Symmetry codes: (i) x, y, z−1; (ii) x, y−1, z+1; (iii) x, y−1, z.

Acknowledgements

The author are grateful to the Central China Normal University for financial support and thank Dr Xiang-Gao Meng for the X-ray data collection.

References

Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Wilshire, J. F. K. (1990). Aust. J. Chem. 43, 1817–1826. CrossRef CAS Google Scholar
Yakimanski, A. V., Kolb, U., Matveeva, G. N., Voigt-Martin, I. G. & Tenkovtsev, A. V. (1997). Acta Cryst. A53, 603–614. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar