4-Nitro­phenyl N-phenyl­carbamate

Xu, Y.-H.; Qu, F.

doi:10.1107/S1600536807068274

organic compounds

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Volume 64| Part 2| February 2008| Page o404

doi:10.1107/S1600536807068274

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4-Nitrophenyl N-phenylcarbamate

Yun-Hua Xu ^a and Fanqi Qu ^b ^*

^aSchool of Science, Beijing Jiaotong University, Beijing 100044, People's Republic of China, and ^bCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, People's Republic of China
^*Correspondence e-mail: fanqiqu@whu.edu.cn

(Received 9 December 2007; accepted 24 December 2007; online 9 January 2008)

The title compound, C₁₃H₁₀N₂O₄, was synthesized as an intermediate for the preparation of ureas. The two aromatic rings are twisted about the central carbamate group with a C—C—N—C torsion angle of 139.6 (2)° and a C—C—O—C torsion angle of 95.9 (2)°. The molecules are linked into one-dimensional chains by N—H⋯O hydrogen bonds along the b axis. Weak interactions between O atoms of the nitro groups (O⋯O = 3.012 Å) connect two adjacent chains.

Related literature

For related literature, see: Allen et al. (1987 ); Izdebski & Pawlak (1989 ); Olma et al. (2006 ); Tye et al. (2002 ).

Experimental

Crystal data

C₁₃H₁₀N₂O₄
M_r = 258.23
Monoclinic, P 2₁
a = 6.0170 (2) Å
b = 5.0650 (1) Å
c = 18.8960 (5) Å
β = 92.538 (1)°
V = 575.31 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 90 (2) K
0.50 × 0.40 × 0.26 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.946, T_max = 0.971
2630 measured reflections
1473 independent reflections
1363 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.104
S = 1.14
1473 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.24 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
N1—H1⋯O1ⁱ	0.88	2.05	2.903 (3)	164
Symmetry code: (i) x, y+1, z.

Data collection: COLLECT (Nonius, 2002 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995 ); software used to prepare material for publication: SHELXL97 and local procedures.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068274/fl2180sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068274/fl2180Isup2.hkl

checkCIF report

Comment top

The title compound (I), along with other 4-nitrophenyl carbamates, are important intermediates for the synthesis of ureas (Olma, et al. 2006; Izdebski & Pawlak, 1989). Although it has been used in organic sythesis for a long time, the crystal structure, as far as we know, is reported here for the first time.

The compound, two aromatic rings connected by a carbamate group, is not planar as would be expected. This is evidenced by the dihedral angles between the nitrophenyl ring and the carbamate, C13—C8—O2—C7=95.9 (2)°, and the benzyl ring and the carbamate, C2—C1—N1—C7=139.6 (2)°. Bond lengths and angles for (I) are within normal ranges (Allen et al., 1987). The molecules form one-dimensional chains formed through N—H···O hydrogen bonds along the b axis (Table 1). In addition, intermolecular O···O interactions exists between nitro groups in neighboring chains (Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Izdebski & Pawlak (1989); Olma et al. (2006); Tye et al. (2002).

Experimental top

Aniline (1.0 g, 10.7 mmol) was added dropwise to a round-bottom flask containing 4-nitrophenyl chloroformate (2.2 g, 10.9 mmol) and pyridine (0.9 ml, 11.1 mmol) in 20 ml me thylene chloride cooled with ice water. After the solutuion was warmed to ambient temperature, the mixture was refluxed overnight with stirring. The solution was then washed with 1 N NaHCO₃, water and brine, and then dried with anhydrous Na₂SO₄. After removal of the solvent, the product was recovered as a yellow solid (2.5 g, 90%) (Tye, et al. 2002). Colorless crystals of (I) were obtained by recrystallization from ethyl acetate.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
	Fig. 2. A packing diagram of (I) along a axis.

4-Nitrophenyl N-phenylcarbamate top

Crystal data top

C₁₃H₁₀N₂O₄	F(000) = 268
M_r = 258.23	D_x = 1.491 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2yb	Cell parameters from 1469 reflections
a = 6.0170 (2) Å	θ = 1–27.5°
b = 5.0650 (1) Å	µ = 0.11 mm⁻¹
c = 18.8960 (5) Å	T = 90 K
β = 92.538 (1)°	Block, colorless
V = 575.31 (3) Å³	0.50 × 0.40 × 0.26 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	1473 independent reflections
Radiation source: fine-focus sealed tube	1363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 18 pixels mm^-1	θ_max = 27.5°, θ_min = 1.1°
ω scans at fixed χ = 55°	h = −7→7
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −6→6
T_min = 0.946, T_max = 0.971	l = −24→24
2630 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0582P)² + 0.1763P] where P = (F_o² + 2F_c²)/3
1473 reflections	(Δ/σ)_max = 0.009
172 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₃H₁₀N₂O₄	V = 575.31 (3) Å³
M_r = 258.23	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.0170 (2) Å	µ = 0.11 mm⁻¹
b = 5.0650 (1) Å	T = 90 K
c = 18.8960 (5) Å	0.50 × 0.40 × 0.26 mm
β = 92.538 (1)°

Data collection top

Nonius KappaCCD diffractometer	1473 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	1363 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.971	R_int = 0.020
2630 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.104	H-atom parameters constrained
S = 1.14	Δρ_max = 0.24 e Å⁻³
1473 reflections	Δρ_min = −0.32 e Å⁻³
172 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	0.9665 (3)	0.7781 (5)	0.84935 (11)	0.0179 (5)
N1	0.7888 (3)	0.8052 (4)	0.79739 (10)	0.0185 (4)
H1	0.7443	0.9655	0.7857	0.022*
N2	0.0763 (3)	−0.1088 (4)	0.56535 (9)	0.0180 (4)
O1	0.7161 (3)	0.3675 (4)	0.77761 (9)	0.0227 (4)
O2	0.5362 (3)	0.6890 (3)	0.71426 (8)	0.0196 (4)
O3	−0.1087 (2)	−0.1712 (4)	0.58598 (9)	0.0248 (4)
O4	0.1657 (3)	−0.2175 (4)	0.51627 (8)	0.0231 (4)
C2	1.1431 (4)	0.9546 (5)	0.84631 (12)	0.0219 (5)
H2	1.1414	1.0883	0.8110	0.026*
C3	1.3226 (4)	0.9341 (6)	0.89534 (12)	0.0248 (5)
H3	1.4432	1.0546	0.8935	0.030*
C4	1.3255 (4)	0.7399 (6)	0.94631 (12)	0.0257 (6)
H4	1.4489	0.7249	0.9792	0.031*
C5	1.1480 (4)	0.5660 (6)	0.94961 (12)	0.0261 (5)
H5	1.1498	0.4330	0.9851	0.031*
C6	0.9670 (4)	0.5853 (6)	0.90111 (11)	0.0214 (5)
H6	0.8451	0.4669	0.9037	0.026*
C7	0.6852 (4)	0.5994 (5)	0.76518 (11)	0.0169 (4)
C8	0.4214 (4)	0.4908 (5)	0.67556 (11)	0.0177 (5)
C9	0.5166 (3)	0.3802 (5)	0.61711 (11)	0.0190 (5)
H9	0.6578	0.4381	0.6027	0.023*
C10	0.4012 (4)	0.1825 (5)	0.58006 (11)	0.0187 (5)
H10	0.4625	0.1017	0.5400	0.022*
C11	0.1954 (3)	0.1055 (5)	0.60271 (11)	0.0161 (4)
C12	0.0975 (4)	0.2213 (5)	0.65993 (11)	0.0189 (5)
H12	−0.0457	0.1672	0.6735	0.023*
C13	0.2135 (4)	0.4187 (5)	0.69708 (11)	0.0198 (5)
H13	0.1508	0.5024	0.7365	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0170 (10)	0.0182 (11)	0.0183 (9)	0.0038 (10)	−0.0015 (7)	−0.0028 (9)
N1	0.0191 (9)	0.0118 (9)	0.0241 (9)	0.0013 (8)	−0.0045 (7)	−0.0005 (8)
N2	0.0152 (9)	0.0161 (10)	0.0224 (8)	−0.0008 (8)	−0.0022 (7)	0.0029 (9)
O1	0.0238 (8)	0.0150 (9)	0.0286 (8)	0.0000 (7)	−0.0060 (6)	0.0001 (7)
O2	0.0188 (8)	0.0154 (8)	0.0240 (7)	−0.0009 (7)	−0.0058 (6)	−0.0014 (7)
O3	0.0153 (7)	0.0257 (10)	0.0334 (8)	−0.0076 (8)	0.0006 (6)	0.0016 (8)
O4	0.0207 (8)	0.0215 (9)	0.0269 (8)	0.0002 (8)	−0.0016 (6)	−0.0052 (8)
C2	0.0230 (11)	0.0208 (13)	0.0218 (10)	−0.0031 (10)	−0.0008 (8)	0.0009 (10)
C3	0.0205 (11)	0.0267 (14)	0.0269 (11)	−0.0036 (10)	−0.0020 (8)	−0.0045 (10)
C4	0.0218 (11)	0.0264 (14)	0.0280 (11)	0.0036 (11)	−0.0076 (9)	−0.0041 (11)
C5	0.0303 (13)	0.0235 (13)	0.0238 (10)	0.0022 (12)	−0.0061 (9)	0.0027 (11)
C6	0.0215 (11)	0.0204 (12)	0.0221 (10)	−0.0020 (11)	−0.0017 (8)	0.0002 (10)
C7	0.0163 (10)	0.0155 (11)	0.0190 (9)	0.0017 (9)	0.0008 (7)	−0.0003 (9)
C8	0.0188 (10)	0.0130 (11)	0.0209 (10)	−0.0012 (10)	−0.0049 (8)	0.0010 (9)
C9	0.0127 (9)	0.0196 (12)	0.0244 (10)	−0.0032 (10)	−0.0012 (8)	0.0019 (10)
C10	0.0151 (10)	0.0198 (11)	0.0212 (9)	−0.0010 (9)	0.0013 (8)	−0.0002 (9)
C11	0.0133 (10)	0.0146 (10)	0.0200 (9)	−0.0004 (9)	−0.0039 (7)	0.0013 (9)
C12	0.0151 (10)	0.0201 (13)	0.0215 (10)	0.0008 (9)	0.0004 (8)	0.0019 (9)
C13	0.0191 (10)	0.0201 (12)	0.0203 (9)	0.0011 (10)	0.0012 (8)	−0.0004 (9)

Geometric parameters (Å, º) top

C1—C6	1.382 (3)	C4—C5	1.388 (4)
C1—C2	1.392 (4)	C4—H4	0.9500
C1—N1	1.426 (3)	C5—C6	1.396 (3)
N1—C7	1.346 (3)	C5—H5	0.9500
N1—H1	0.8800	C6—H6	0.9500
N2—O4	1.224 (3)	C8—C13	1.381 (3)
N2—O3	1.237 (2)	C8—C9	1.385 (3)
N2—C11	1.465 (3)	C9—C10	1.390 (3)
O1—C7	1.210 (3)	C9—H9	0.9500
O2—C7	1.364 (3)	C10—C11	1.384 (3)
O2—C8	1.405 (3)	C10—H10	0.9500
C2—C3	1.395 (3)	C11—C12	1.385 (3)
C2—H2	0.9500	C12—C13	1.391 (3)
C3—C4	1.376 (4)	C12—H12	0.9500
C3—H3	0.9500	C13—H13	0.9500

C6—C1—C2	120.4 (2)	C1—C6—H6	120.3
C6—C1—N1	122.2 (2)	C5—C6—H6	120.3
C2—C1—N1	117.4 (2)	O1—C7—N1	126.8 (2)
C7—N1—C1	123.7 (2)	O1—C7—O2	123.4 (2)
C7—N1—H1	118.1	N1—C7—O2	109.8 (2)
C1—N1—H1	118.1	C13—C8—C9	122.7 (2)
O4—N2—O3	123.8 (2)	C13—C8—O2	117.8 (2)
O4—N2—C11	118.45 (18)	C9—C8—O2	119.5 (2)
O3—N2—C11	117.76 (19)	C8—C9—C10	118.6 (2)
C7—O2—C8	114.97 (19)	C8—C9—H9	120.7
C3—C2—C1	119.7 (2)	C10—C9—H9	120.7
C3—C2—H2	120.2	C11—C10—C9	118.8 (2)
C1—C2—H2	120.2	C11—C10—H10	120.6
C4—C3—C2	120.2 (2)	C9—C10—H10	120.6
C4—C3—H3	119.9	C10—C11—C12	122.7 (2)
C2—C3—H3	119.9	C10—C11—N2	119.0 (2)
C3—C4—C5	120.0 (2)	C12—C11—N2	118.30 (19)
C3—C4—H4	120.0	C11—C12—C13	118.5 (2)
C5—C4—H4	120.0	C11—C12—H12	120.8
C4—C5—C6	120.4 (2)	C13—C12—H12	120.8
C4—C5—H5	119.8	C8—C13—C12	118.8 (2)
C6—C5—H5	119.8	C8—C13—H13	120.6
C1—C6—C5	119.4 (2)	C12—C13—H13	120.6

C6—C1—N1—C7	−40.3 (3)	C7—O2—C8—C9	−85.5 (3)
C2—C1—N1—C7	139.6 (2)	C13—C8—C9—C10	−2.2 (4)
C6—C1—C2—C3	0.8 (4)	O2—C8—C9—C10	179.3 (2)
N1—C1—C2—C3	−179.1 (2)	C8—C9—C10—C11	0.5 (3)
C1—C2—C3—C4	0.2 (4)	C9—C10—C11—C12	1.4 (4)
C2—C3—C4—C5	−0.9 (4)	C9—C10—C11—N2	−178.0 (2)
C3—C4—C5—C6	0.5 (4)	O4—N2—C11—C10	1.8 (3)
C2—C1—C6—C5	−1.1 (4)	O3—N2—C11—C10	−179.0 (2)
N1—C1—C6—C5	178.8 (2)	O4—N2—C11—C12	−177.6 (2)
C4—C5—C6—C1	0.5 (4)	O3—N2—C11—C12	1.6 (3)
C1—N1—C7—O1	4.5 (4)	C10—C11—C12—C13	−1.6 (4)
C1—N1—C7—O2	−174.95 (18)	N2—C11—C12—C13	177.8 (2)
C8—O2—C7—O1	−1.1 (3)	C9—C8—C13—C12	2.0 (4)
C8—O2—C7—N1	178.43 (18)	O2—C8—C13—C12	−179.5 (2)
C7—O2—C8—C13	95.9 (2)	C11—C12—C13—C8	−0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.05	2.903 (3)	164

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀N₂O₄
M_r	258.23
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	90
a, b, c (Å)	6.0170 (2), 5.0650 (1), 18.8960 (5)
β (°)	92.538 (1)
V (Å³)	575.31 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.50 × 0.40 × 0.26

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.946, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	2630, 1473, 1363
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.104, 1.14
No. of reflections	1473
No. of parameters	172
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.32

Computer programs: COLLECT (Nonius, 2002), SCALEPACK (Otwinowski & Minor, 1997), DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL/PC (Sheldrick, 1995), SHELXL97 (Sheldrick, 2008) and local procedures.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.05	2.903 (3)	163.6

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

Acknowledgements

FQ and Y-HX thank Dr Sihui Long for helpful discussions during the preparation of this paper.

References

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