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Acta Cryst. (2008). E64, o404    [ doi:10.1107/S1600536807068274 ]

4-Nitrophenyl N-phenylcarbamate

Y.-H. Xu and F. Qu

Abstract top

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.

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.

Refinement top

H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained C—H distances of 0.95 Å (CArH), and 0.88 Å (NH1). Uiso(H) values were set to 1.2Ueq for all H atoms. In the absence of significant anomalous scattering effects, Friedel pairs were merged prior to refinement.

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
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. A packing diagram of (I) along a axis.
4-Nitrophenyl N-phenylcarbamate top
Crystal data top
C13H10N2O4F000 = 268
Mr = 258.23Dx = 1.491 Mg m−3
Monoclinic, P21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P2ybCell parameters from 1469 reflections
a = 6.0170 (2) Åθ = 1–27.5º
b = 5.0650 (1) ŵ = 0.11 mm−1
c = 18.8960 (5) ÅT = 90 (2) K
β = 92.538 (1)ºBlock, colorless
V = 575.31 (3) Å30.50 × 0.40 × 0.26 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		1473 independent reflections
Radiation source: fine-focus sealed tube1363 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
Detector resolution: 18 pixels mm-1θmax = 27.5º
T = 90(2) Kθmin = 1.1º
ω scans at fixed χ = 55°h = −7→7
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)		k = −6→6
Tmin = 0.946, Tmax = 0.971l = −24→24
2630 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0582P)2 + 0.1763P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.009
1473 reflectionsΔρmax = 0.24 e Å−3
172 parametersΔρmin = −0.32 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C13H10N2O4V = 575.31 (3) Å3
Mr = 258.23Z = 2
Monoclinic, P21Mo Kα
a = 6.0170 (2) ŵ = 0.11 mm−1
b = 5.0650 (1) ÅT = 90 (2) K
c = 18.8960 (5) Å0.50 × 0.40 × 0.26 mm
β = 92.538 (1)º
Data collection top
Nonius KappaCCD
diffractometer		1473 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)		1363 reflections with I > 2σ(I)
Tmin = 0.946, Tmax = 0.971Rint = 0.020
2630 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.24 e Å−3
S = 1.14Δρmin = −0.32 e Å−3
1473 reflectionsAbsolute structure: ?
172 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
C10.9665 (3)0.7781 (5)0.84935 (11)0.0179 (5)
N10.7888 (3)0.8052 (4)0.79739 (10)0.0185 (4)
H10.74430.96550.78570.022*
N20.0763 (3)−0.1088 (4)0.56535 (9)0.0180 (4)
O10.7161 (3)0.3675 (4)0.77761 (9)0.0227 (4)
O20.5362 (3)0.6890 (3)0.71426 (8)0.0196 (4)
O3−0.1087 (2)−0.1712 (4)0.58598 (9)0.0248 (4)
O40.1657 (3)−0.2175 (4)0.51627 (8)0.0231 (4)
C21.1431 (4)0.9546 (5)0.84631 (12)0.0219 (5)
H21.14141.08830.81100.026*
C31.3226 (4)0.9341 (6)0.89534 (12)0.0248 (5)
H31.44321.05460.89350.030*
C41.3255 (4)0.7399 (6)0.94631 (12)0.0257 (6)
H41.44890.72490.97920.031*
C51.1480 (4)0.5660 (6)0.94961 (12)0.0261 (5)
H51.14980.43300.98510.031*
C60.9670 (4)0.5853 (6)0.90111 (11)0.0214 (5)
H60.84510.46690.90370.026*
C70.6852 (4)0.5994 (5)0.76518 (11)0.0169 (4)
C80.4214 (4)0.4908 (5)0.67556 (11)0.0177 (5)
C90.5166 (3)0.3802 (5)0.61711 (11)0.0190 (5)
H90.65780.43810.60270.023*
C100.4012 (4)0.1825 (5)0.58006 (11)0.0187 (5)
H100.46250.10170.54000.022*
C110.1954 (3)0.1055 (5)0.60271 (11)0.0161 (4)
C120.0975 (4)0.2213 (5)0.65993 (11)0.0189 (5)
H12−0.04570.16720.67350.023*
C130.2135 (4)0.4187 (5)0.69708 (11)0.0198 (5)
H130.15080.50240.73650.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0170 (10)0.0182 (11)0.0183 (9)0.0038 (10)−0.0015 (7)−0.0028 (9)
N10.0191 (9)0.0118 (9)0.0241 (9)0.0013 (8)−0.0045 (7)−0.0005 (8)
N20.0152 (9)0.0161 (10)0.0224 (8)−0.0008 (8)−0.0022 (7)0.0029 (9)
O10.0238 (8)0.0150 (9)0.0286 (8)0.0000 (7)−0.0060 (6)0.0001 (7)
O20.0188 (8)0.0154 (8)0.0240 (7)−0.0009 (7)−0.0058 (6)−0.0014 (7)
O30.0153 (7)0.0257 (10)0.0334 (8)−0.0076 (8)0.0006 (6)0.0016 (8)
O40.0207 (8)0.0215 (9)0.0269 (8)0.0002 (8)−0.0016 (6)−0.0052 (8)
C20.0230 (11)0.0208 (13)0.0218 (10)−0.0031 (10)−0.0008 (8)0.0009 (10)
C30.0205 (11)0.0267 (14)0.0269 (11)−0.0036 (10)−0.0020 (8)−0.0045 (10)
C40.0218 (11)0.0264 (14)0.0280 (11)0.0036 (11)−0.0076 (9)−0.0041 (11)
C50.0303 (13)0.0235 (13)0.0238 (10)0.0022 (12)−0.0061 (9)0.0027 (11)
C60.0215 (11)0.0204 (12)0.0221 (10)−0.0020 (11)−0.0017 (8)0.0002 (10)
C70.0163 (10)0.0155 (11)0.0190 (9)0.0017 (9)0.0008 (7)−0.0003 (9)
C80.0188 (10)0.0130 (11)0.0209 (10)−0.0012 (10)−0.0049 (8)0.0010 (9)
C90.0127 (9)0.0196 (12)0.0244 (10)−0.0032 (10)−0.0012 (8)0.0019 (10)
C100.0151 (10)0.0198 (11)0.0212 (9)−0.0010 (9)0.0013 (8)−0.0002 (9)
C110.0133 (10)0.0146 (10)0.0200 (9)−0.0004 (9)−0.0039 (7)0.0013 (9)
C120.0151 (10)0.0201 (13)0.0215 (10)0.0008 (9)0.0004 (8)0.0019 (9)
C130.0191 (10)0.0201 (12)0.0203 (9)0.0011 (10)0.0012 (8)−0.0004 (9)
Geometric parameters (Å, °) top
C1—C61.382 (3)C4—C51.388 (4)
C1—C21.392 (4)C4—H40.9500
C1—N11.426 (3)C5—C61.396 (3)
N1—C71.346 (3)C5—H50.9500
N1—H10.8800C6—H60.9500
N2—O41.224 (3)C8—C131.381 (3)
N2—O31.237 (2)C8—C91.385 (3)
N2—C111.465 (3)C9—C101.390 (3)
O1—C71.210 (3)C9—H90.9500
O2—C71.364 (3)C10—C111.384 (3)
O2—C81.405 (3)C10—H100.9500
C2—C31.395 (3)C11—C121.385 (3)
C2—H20.9500C12—C131.391 (3)
C3—C41.376 (4)C12—H120.9500
C3—H30.9500C13—H130.9500
C6—C1—C2120.4 (2)C1—C6—H6120.3
C6—C1—N1122.2 (2)C5—C6—H6120.3
C2—C1—N1117.4 (2)O1—C7—N1126.8 (2)
C7—N1—C1123.7 (2)O1—C7—O2123.4 (2)
C7—N1—H1118.1N1—C7—O2109.8 (2)
C1—N1—H1118.1C13—C8—C9122.7 (2)
O4—N2—O3123.8 (2)C13—C8—O2117.8 (2)
O4—N2—C11118.45 (18)C9—C8—O2119.5 (2)
O3—N2—C11117.76 (19)C8—C9—C10118.6 (2)
C7—O2—C8114.97 (19)C8—C9—H9120.7
C3—C2—C1119.7 (2)C10—C9—H9120.7
C3—C2—H2120.2C11—C10—C9118.8 (2)
C1—C2—H2120.2C11—C10—H10120.6
C4—C3—C2120.2 (2)C9—C10—H10120.6
C4—C3—H3119.9C10—C11—C12122.7 (2)
C2—C3—H3119.9C10—C11—N2119.0 (2)
C3—C4—C5120.0 (2)C12—C11—N2118.30 (19)
C3—C4—H4120.0C11—C12—C13118.5 (2)
C5—C4—H4120.0C11—C12—H12120.8
C4—C5—C6120.4 (2)C13—C12—H12120.8
C4—C5—H5119.8C8—C13—C12118.8 (2)
C6—C5—H5119.8C8—C13—H13120.6
C1—C6—C5119.4 (2)C12—C13—H13120.6
C6—C1—N1—C7−40.3 (3)C7—O2—C8—C9−85.5 (3)
C2—C1—N1—C7139.6 (2)C13—C8—C9—C10−2.2 (4)
C6—C1—C2—C30.8 (4)O2—C8—C9—C10179.3 (2)
N1—C1—C2—C3−179.1 (2)C8—C9—C10—C110.5 (3)
C1—C2—C3—C40.2 (4)C9—C10—C11—C121.4 (4)
C2—C3—C4—C5−0.9 (4)C9—C10—C11—N2−178.0 (2)
C3—C4—C5—C60.5 (4)O4—N2—C11—C101.8 (3)
C2—C1—C6—C5−1.1 (4)O3—N2—C11—C10−179.0 (2)
N1—C1—C6—C5178.8 (2)O4—N2—C11—C12−177.6 (2)
C4—C5—C6—C10.5 (4)O3—N2—C11—C121.6 (3)
C1—N1—C7—O14.5 (4)C10—C11—C12—C13−1.6 (4)
C1—N1—C7—O2−174.95 (18)N2—C11—C12—C13177.8 (2)
C8—O2—C7—O1−1.1 (3)C9—C8—C13—C122.0 (4)
C8—O2—C7—N1178.43 (18)O2—C8—C13—C12−179.5 (2)
C7—O2—C8—C1395.9 (2)C11—C12—C13—C8−0.1 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.052.903 (3)164
Symmetry codes: (i) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.052.903 (3)164
Symmetry codes: (i) x, y+1, z.
references
References top

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.

Izdebski, J. & Pawlak, D. (1989). Synthesis, 6, 423–425.

Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.

Olma, S., Ermert, J. & Coenen, H. H. (2006). J. Label. Compd. Radiopharm. 49, 1037–1050.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (1995). XP in SHELXTL/PC. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tye, H., Eldred, C. & Wills, M. (2002). Tetrahedron Lett. 43, 155–158.