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Acta Cryst. (2009). E65, o1036    [ doi:10.1107/S1600536809013312 ]

Phenyl N-(4-fluorophenyl)carbamate

Z. Yang and Z.-X. Wang

Abstract top

The asymmetric unit of the title compound, C13H10FNO2, contains two crystallographically independent molecules. The aromatic rings are oriented at dihedral angles of 61.77 (3) and 53.94 (3)° in the two molecules. An N-H...O hydrogen bond links the molecules. In the crystal structure, intermolecular N-H...O hydrogen bonds link the molecules into chains. Weak C-H...[pi] interactions are also present.

Comment top

Some derivatives of aniline are important chemical materials. We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (C8-C13) and A' (C14-C19), B' (C21-C26) are, of course, planar, and they are oriented at dihedral angles of A/B = 61.77 (3) and A'/B' = 53.94 (3) °. Intramolecular N-H···O hydrogen bond (Table 1) links the molecules.

In the crystal structure, intra- and intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure. There also exist weak C—H···π interactions (Table 1).

Related literature top

For a related structure, see: Hynes et al. (2008). For bond-length data, see: Allen et al. (1987). Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

Experimental top

For the preparation of the title compound, phenyl chloroformate (1.0 ml) was added slowly to a cold solution of 4-fluorbenzenamine (1.0 g) and triethylamine (0.8 ml) in methylene chloride (10 ml) at 273 K. The mixture was then warmed and stirred for 1 h at room temperature. It was washed with water (20 ml), dried and concentrated to give the title compound (yield; 1.3 g) (Hynes et al., 2008). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Phenyl N-(4-fluorophenyl)carbamate top
Crystal data top
C13H10FNO2Z = 4
Mr = 231.22F(000) = 480
Triclinic, P1Dx = 1.353 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8860 (12) ÅCell parameters from 25 reflections
b = 7.8540 (16) Åθ = 8–12°
c = 24.761 (5) ŵ = 0.10 mm−1
α = 96.62 (3)°T = 294 K
β = 92.82 (3)°Block, colorless
γ = 91.19 (3)°0.10 × 0.10 × 0.08 mm
V = 1135.3 (4) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		1662 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.060
graphiteθmax = 25.3°, θmin = 1.7°
ω/2θ scansh = 0→7
Absorption correction: ψ scan
(North et al., 1968)		k = −9→9
Tmin = 0.990, Tmax = 0.992l = −29→29
4548 measured reflections3 standard reflections every 120 min
4110 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.073Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.052P)2]
where P = (Fo2 + 2Fc2)/3
4110 reflections(Δ/σ)max < 0.001
307 parametersΔρmax = 0.13 e Å−3
0 restraintsΔρmin = −0.13 e Å−3
Crystal data top
C13H10FNO2γ = 91.19 (3)°
Mr = 231.22V = 1135.3 (4) Å3
Triclinic, P1Z = 4
a = 5.8860 (12) ÅMo Kα radiation
b = 7.8540 (16) ŵ = 0.10 mm−1
c = 24.761 (5) ÅT = 294 K
α = 96.62 (3)°0.10 × 0.10 × 0.08 mm
β = 92.82 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1662 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.060
Tmin = 0.990, Tmax = 0.992θmax = 25.3°
4548 measured reflections3 standard reflections every 120 min
4110 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.157Δρmax = 0.13 e Å−3
S = 1.00Δρmin = −0.13 e Å−3
4110 reflectionsAbsolute structure: ?
307 parametersFlack parameter: ?
0 restraintsRogers 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
N10.0390 (6)−0.6473 (4)0.26993 (14)0.0831 (11)
H1A−0.0691−0.72130.25990.100*
N20.6939 (5)−0.2644 (4)0.22504 (13)0.0755 (11)
H2C0.6083−0.35070.23000.091*
F1−0.0366 (5)−0.3165 (3)0.47653 (11)0.1065 (9)
F21.1428 (5)−0.3284 (4)0.03482 (12)0.1253 (11)
O10.1510 (5)−0.7508 (4)0.19019 (13)0.1045 (12)
O20.3575 (5)−0.5355 (4)0.23766 (11)0.0916 (10)
O30.5300 (5)−0.1536 (4)0.29759 (12)0.0938 (11)
O40.8164 (4)−0.0021 (3)0.26628 (10)0.0724 (8)
C10.3835 (12)−0.7830 (7)0.0572 (2)0.1033 (18)
H1B0.3416−0.76370.02180.124*
C20.2332 (9)−0.7392 (6)0.0984 (3)0.0934 (16)
H2A0.0941−0.68960.09170.112*
C30.3045 (9)−0.7740 (6)0.1487 (2)0.0763 (14)
C40.5077 (11)−0.8420 (6)0.1599 (2)0.0894 (16)
H4A0.5516−0.86050.19530.107*
C50.6465 (9)−0.8828 (6)0.1186 (3)0.1024 (18)
H5A0.7849−0.93270.12590.123*
C60.5889 (11)−0.8528 (7)0.0673 (3)0.108 (2)
H6A0.6871−0.87920.03940.130*
C70.1980 (8)−0.6340 (6)0.23447 (19)0.0860 (15)
C80.0241 (7)−0.5556 (5)0.32213 (17)0.0698 (12)
C9−0.1636 (7)−0.5849 (5)0.35086 (18)0.0740 (12)
H9A−0.2782−0.66030.33490.089*
C10−0.1859 (8)−0.5051 (6)0.4028 (2)0.0861 (14)
H10A−0.3134−0.52530.42210.103*
C11−0.0157 (8)−0.3963 (5)0.42483 (19)0.0776 (13)
C120.1691 (8)−0.3626 (5)0.39833 (18)0.0772 (13)
H12A0.2818−0.28680.41500.093*
C130.1923 (7)−0.4407 (5)0.34595 (18)0.0784 (13)
H13A0.3192−0.41650.32690.094*
C140.4753 (10)0.1478 (6)0.4438 (2)0.0860 (15)
H14A0.45940.21140.47740.103*
C150.6668 (9)0.0580 (6)0.4346 (2)0.0882 (15)
H15A0.78150.06180.46200.106*
C160.6942 (7)−0.0391 (5)0.3851 (2)0.0744 (13)
H16A0.8265−0.09940.37900.089*
C170.5254 (8)−0.0445 (5)0.34616 (18)0.0647 (11)
C180.3329 (8)0.0490 (6)0.35436 (18)0.0775 (13)
H18A0.22030.04780.32660.093*
C190.3070 (9)0.1455 (6)0.4044 (2)0.0829 (14)
H19A0.17610.20750.41070.099*
C200.6969 (7)−0.1294 (6)0.26345 (17)0.0763 (13)
C210.8171 (7)−0.2801 (5)0.17706 (16)0.0588 (10)
C221.0269 (7)−0.2011 (5)0.17460 (18)0.0738 (12)
H22A1.0954−0.13780.20540.089*
C231.1343 (7)−0.2167 (5)0.12616 (19)0.0798 (13)
H23A1.2738−0.16120.12370.096*
C241.0365 (9)−0.3124 (6)0.08250 (19)0.0840 (14)
C250.8320 (8)−0.3995 (5)0.08437 (18)0.0813 (13)
H25A0.7693−0.46810.05400.098*
C260.7227 (7)−0.3818 (5)0.13273 (17)0.0717 (12)
H26A0.5845−0.43930.13520.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.078 (3)0.080 (3)0.086 (3)−0.031 (2)0.023 (2)−0.013 (2)
N20.082 (3)0.062 (2)0.080 (3)−0.038 (2)0.023 (2)−0.0024 (19)
F10.120 (2)0.102 (2)0.094 (2)−0.0065 (17)0.0279 (17)−0.0139 (16)
F20.140 (3)0.121 (2)0.112 (2)−0.0283 (19)0.061 (2)−0.0174 (18)
O10.105 (3)0.109 (3)0.091 (2)−0.056 (2)0.030 (2)−0.027 (2)
O20.094 (2)0.085 (2)0.091 (2)−0.0490 (18)0.0269 (18)−0.0119 (17)
O30.099 (2)0.086 (2)0.089 (2)−0.0449 (18)0.0397 (19)−0.0265 (18)
O40.0745 (19)0.0645 (18)0.0752 (19)−0.0264 (15)0.0099 (15)−0.0018 (14)
C10.112 (5)0.125 (5)0.071 (4)−0.036 (4)−0.012 (4)0.014 (3)
C20.081 (4)0.089 (4)0.112 (5)−0.014 (3)−0.010 (4)0.030 (3)
C30.065 (3)0.070 (3)0.090 (4)−0.027 (3)0.014 (3)−0.005 (3)
C40.099 (4)0.083 (4)0.083 (4)−0.035 (3)−0.008 (3)0.008 (3)
C50.080 (4)0.063 (3)0.163 (6)−0.007 (3)−0.009 (5)0.013 (4)
C60.081 (4)0.102 (5)0.134 (6)−0.029 (4)0.032 (4)−0.025 (4)
C70.081 (4)0.093 (4)0.077 (3)−0.033 (3)0.015 (3)−0.015 (3)
C80.069 (3)0.062 (3)0.079 (3)−0.017 (2)0.015 (2)0.008 (2)
C90.066 (3)0.067 (3)0.087 (3)−0.016 (2)0.010 (2)0.002 (2)
C100.083 (3)0.078 (3)0.097 (4)−0.013 (3)0.025 (3)0.006 (3)
C110.081 (4)0.061 (3)0.089 (4)0.005 (3)0.024 (3)−0.007 (3)
C120.081 (3)0.074 (3)0.076 (3)−0.015 (3)0.000 (3)0.009 (3)
C130.075 (3)0.077 (3)0.082 (3)−0.030 (2)0.009 (2)0.006 (3)
C140.093 (4)0.086 (4)0.078 (4)−0.010 (3)0.020 (3)0.002 (3)
C150.090 (4)0.098 (4)0.077 (4)−0.012 (3)0.002 (3)0.018 (3)
C160.055 (3)0.064 (3)0.108 (4)−0.001 (2)0.015 (3)0.020 (3)
C170.065 (3)0.057 (3)0.072 (3)−0.014 (2)0.012 (3)0.005 (2)
C180.077 (4)0.078 (3)0.079 (3)−0.020 (3)−0.004 (3)0.021 (3)
C190.080 (4)0.069 (3)0.102 (4)0.013 (3)0.022 (3)0.008 (3)
C200.081 (3)0.070 (3)0.076 (3)−0.028 (3)0.017 (3)−0.003 (3)
C210.059 (3)0.048 (2)0.068 (3)−0.007 (2)0.003 (2)0.002 (2)
C220.054 (3)0.073 (3)0.090 (3)−0.018 (2)0.002 (2)−0.005 (2)
C230.068 (3)0.070 (3)0.099 (4)−0.010 (2)0.029 (3)−0.007 (3)
C240.099 (4)0.070 (3)0.082 (4)−0.006 (3)0.032 (3)−0.006 (3)
C250.093 (4)0.073 (3)0.074 (3)−0.006 (3)0.009 (3)−0.008 (2)
C260.072 (3)0.065 (3)0.074 (3)−0.018 (2)0.007 (2)−0.007 (2)
Geometric parameters (Å, °) top
N1—C71.325 (5)C9—H9A0.9300
N1—C81.413 (4)C10—C111.354 (5)
N1—H1A0.8600C10—H10A0.9300
N2—C201.340 (4)C11—C121.335 (5)
N2—C211.417 (4)C12—C131.384 (5)
N2—H2C0.8600C12—H12A0.9300
F1—C111.371 (4)C13—H13A0.9300
F2—C241.358 (4)C14—C191.354 (6)
O1—C31.399 (5)C14—C151.357 (6)
O1—C71.359 (4)C14—H14A0.9300
O2—C71.198 (4)C15—C161.385 (6)
O3—C171.396 (5)C15—H15A0.9300
O3—C201.351 (4)C16—C171.347 (5)
O4—C201.204 (4)C16—H16A0.9300
C1—C61.361 (7)C17—C181.374 (5)
C1—C21.400 (6)C18—C191.393 (6)
C1—H1B0.9300C18—H18A0.9300
C2—C31.355 (6)C19—H19A0.9300
C2—H2A0.9300C21—C261.368 (5)
C3—C41.349 (6)C21—C221.377 (5)
C4—C51.353 (6)C22—C231.377 (5)
C4—H4A0.9300C22—H22A0.9300
C5—C61.348 (7)C23—C241.341 (5)
C5—H5A0.9300C23—H23A0.9300
C6—H6A0.9300C24—C251.377 (6)
C8—C91.373 (5)C25—C261.381 (5)
C8—C131.388 (5)C25—H25A0.9300
C9—C101.379 (5)C26—H26A0.9300
C7—N1—C8128.3 (4)C13—C12—H12A120.1
C7—N1—H1A115.8C12—C13—C8119.2 (4)
C8—N1—H1A115.8C12—C13—H13A120.4
C20—N2—C21126.8 (3)C8—C13—H13A120.4
C20—N2—H2C116.6C19—C14—C15120.5 (5)
C21—N2—H2C116.6C19—C14—H14A119.7
C7—O1—C3120.4 (3)C15—C14—H14A119.7
C20—O3—C17118.5 (3)C14—C15—C16121.0 (5)
C6—C1—C2122.3 (5)C14—C15—H15A119.5
C6—C1—H1B118.9C16—C15—H15A119.5
C2—C1—H1B118.9C17—C16—C15118.7 (4)
C3—C2—C1115.4 (5)C17—C16—H16A120.6
C3—C2—H2A122.3C15—C16—H16A120.6
C1—C2—H2A122.3C16—C17—C18120.9 (4)
C4—C3—C2123.5 (5)C16—C17—O3121.9 (5)
C4—C3—O1118.5 (6)C18—C17—O3117.0 (4)
C2—C3—O1117.8 (6)C17—C18—C19119.7 (4)
C3—C4—C5118.9 (5)C17—C18—H18A120.1
C3—C4—H4A120.6C19—C18—H18A120.1
C5—C4—H4A120.6C14—C19—C18119.0 (5)
C6—C5—C4121.5 (6)C14—C19—H19A120.5
C6—C5—H5A119.2C18—C19—H19A120.5
C4—C5—H5A119.2O4—C20—N2127.1 (4)
C5—C6—C1118.4 (6)O4—C20—O3124.4 (4)
C5—C6—H6A120.8N2—C20—O3108.3 (3)
C1—C6—H6A120.8C26—C21—C22120.3 (4)
O2—C7—N1128.5 (4)C26—C21—N2117.4 (3)
O2—C7—O1122.5 (4)C22—C21—N2122.3 (4)
N1—C7—O1109.0 (4)C21—C22—C23119.4 (4)
C9—C8—C13118.8 (4)C21—C22—H22A120.3
C9—C8—N1118.1 (4)C23—C22—H22A120.3
C13—C8—N1123.0 (4)C24—C23—C22119.6 (4)
C8—C9—C10121.4 (4)C24—C23—H23A120.2
C8—C9—H9A119.3C22—C23—H23A120.2
C10—C9—H9A119.3C23—C24—F2119.6 (4)
C11—C10—C9117.7 (4)C23—C24—C25122.3 (4)
C11—C10—H10A121.2F2—C24—C25118.1 (4)
C9—C10—H10A121.2C24—C25—C26118.1 (4)
C12—C11—C10123.0 (4)C24—C25—H25A121.0
C12—C11—F1118.9 (4)C26—C25—H25A121.0
C10—C11—F1118.1 (4)C21—C26—C25120.2 (4)
C11—C12—C13119.8 (4)C21—C26—H26A119.9
C11—C12—H12A120.1C25—C26—H26A119.9
C6—C1—C2—C3−1.2 (7)C19—C14—C15—C16−0.6 (7)
C1—C2—C3—C41.7 (7)C14—C15—C16—C17−0.7 (6)
C1—C2—C3—O1−173.0 (4)C15—C16—C17—C182.3 (6)
C7—O1—C3—C467.3 (6)C15—C16—C17—O3−173.0 (3)
C7—O1—C3—C2−117.7 (5)C20—O3—C17—C16−63.8 (6)
C2—C3—C4—C5−2.0 (7)C20—O3—C17—C18120.8 (4)
O1—C3—C4—C5172.7 (4)C16—C17—C18—C19−2.6 (6)
C3—C4—C5—C61.8 (7)O3—C17—C18—C19172.9 (4)
C4—C5—C6—C1−1.3 (8)C15—C14—C19—C180.3 (7)
C2—C1—C6—C51.1 (8)C17—C18—C19—C141.3 (6)
C8—N1—C7—O2−4.2 (9)C21—N2—C20—O4−5.8 (8)
C8—N1—C7—O1177.7 (4)C21—N2—C20—O3170.2 (4)
C3—O1—C7—O27.6 (8)C17—O3—C20—O4−15.0 (7)
C3—O1—C7—N1−174.2 (4)C17—O3—C20—N2168.9 (4)
C7—N1—C8—C9176.8 (5)C20—N2—C21—C26−150.6 (4)
C7—N1—C8—C13−4.7 (7)C20—N2—C21—C2231.2 (6)
C13—C8—C9—C10−1.1 (7)C26—C21—C22—C234.0 (6)
N1—C8—C9—C10177.5 (4)N2—C21—C22—C23−177.8 (4)
C8—C9—C10—C11−0.1 (7)C21—C22—C23—C24−1.9 (7)
C9—C10—C11—C120.6 (7)C22—C23—C24—F2−179.7 (4)
C9—C10—C11—F1−180.0 (4)C22—C23—C24—C25−1.2 (8)
C10—C11—C12—C130.0 (8)C23—C24—C25—C262.1 (7)
F1—C11—C12—C13−179.4 (4)F2—C24—C25—C26−179.4 (4)
C11—C12—C13—C8−1.1 (7)C22—C21—C26—C25−3.1 (6)
C9—C8—C13—C121.6 (7)N2—C21—C26—C25178.6 (4)
N1—C8—C13—C12−176.9 (4)C24—C25—C26—C210.1 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.862.323.044 (4)142
N2—H2C···O20.862.082.931 (4)171
C19—H19A···Cg2ii0.932.943.644 (4)134
C23—H23A···Cg1iii0.932.973.710 (5)138
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z; (iii) x+1, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.862.323.044 (4)142
N2—H2C···O20.862.082.931 (4)171
C19—H19A···Cg2ii0.932.943.644 (4)134
C23—H23A···Cg1iii0.932.973.710 (5)138
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z; (iii) x+1, y+1, z.
Acknowledgements top

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

references
References top

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