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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1606.
Published online 2009 June 17. doi:  10.1107/S1600536809022600
PMCID: PMC2969509

Phenyl N-(p-tol­yl)carbamate

Abstract

The asymmetric unit of the title compound, C14H13NO2, contains two crystallographically independent mol­ecules, in which the aromatic rings are oriented at dihedral angles of 59.01 (3) and 56.98 (3)°. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds link the mol­ecules into chains.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o1606-scheme1.jpg

Experimental

Crystal data

  • C14H13NO2
  • M r = 227.25
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1606-efi1.jpg
  • a = 8.7790 (18) Å
  • b = 9.7470 (19) Å
  • c = 15.121 (3) Å
  • α = 87.30 (3)°
  • β = 77.07 (3)°
  • γ = 75.00 (3)°
  • V = 1218.0 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 294 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.975, T max = 0.992
  • 4736 measured reflections
  • 4421 independent reflections
  • 2781 reflections with I > 2σ(I)
  • R int = 0.027
  • 3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.172
  • S = 1.01
  • 4421 reflections
  • 308 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022600/hk2710sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022600/hk2710Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

Some derivatives of benzoic acid 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 (C2-C7), B (C9-C14) and C (C16-C21), D (C23-C28) are, of course, planar and the dihedral angles between them are A/B = 59.01 (3)° and C/D = 56.98 (3)°. Intramolecular N-H···O hydrogen bond (Table 1) links the two molecules (Fig. 1).

In the crystal structure, 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.

Experimental

For the preparation of the title compound, to a cold stirring solution of p-toluidine (1.0 g) and triethylamine (0.8 ml) in methylene chloride (10 ml) was added phenyl chloroformate (1.0 ml) slowly keeping the temperature at 273 K. The mixture was then warmed and stirred for 1 h at room temperature. The mixture was washed with water (20 ml), dried over sodium sulfate, and concentrated to near dryness. The crude product was purified by recrystallization from petroleum ether (yield; 1.3 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of a petroleum ether solution.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C14H13NO2Z = 4
Mr = 227.25F(000) = 480
Triclinic, P1Dx = 1.239 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.7790 (18) ÅCell parameters from 25 reflections
b = 9.7470 (19) Åθ = 9–13°
c = 15.121 (3) ŵ = 0.08 mm1
α = 87.30 (3)°T = 294 K
β = 77.07 (3)°Block, colorless
γ = 75.00 (3)°0.30 × 0.20 × 0.10 mm
V = 1218.0 (5) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer2781 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
graphiteθmax = 25.3°, θmin = 1.4°
ω/2θ scansh = 0→10
Absorption correction: ψ scan (North et al., 1968)k = −11→11
Tmin = 0.975, Tmax = 0.992l = −17→18
4736 measured reflections3 standard reflections every 120 min
4421 independent reflections intensity decay: 1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.172w = 1/[σ2(Fo2) + (0.097P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4421 reflectionsΔρmax = 0.22 e Å3
308 parametersΔρmin = −0.13 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (5)

Special details

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)

xyzUiso*/Ueq
O10.2677 (3)0.48473 (18)0.79602 (12)0.0801 (6)
O20.2281 (2)0.27924 (16)0.86169 (11)0.0605 (5)
O30.2572 (2)0.76205 (16)0.89540 (11)0.0675 (5)
O40.2965 (2)0.94932 (16)0.96266 (10)0.0593 (5)
N10.2453 (3)0.4652 (2)0.94342 (13)0.0641 (6)
H1A0.24560.55340.93830.077*
N20.2903 (2)0.96349 (19)0.81800 (12)0.0537 (5)
H2A0.31011.04360.82550.064*
C10.2787 (4)0.2204 (4)1.2922 (2)0.1085 (12)
H1B0.33820.26731.32130.163*
H1C0.33290.12121.28450.163*
H1D0.17180.23111.32900.163*
C20.2677 (4)0.2855 (3)1.20065 (18)0.0701 (8)
C30.3342 (3)0.3980 (3)1.16953 (19)0.0750 (8)
H3A0.38710.43411.20610.090*
C40.3240 (3)0.4578 (3)1.08582 (17)0.0649 (7)
H4A0.36840.53401.06700.078*
C50.2476 (3)0.4040 (2)1.02999 (16)0.0543 (6)
C60.1754 (3)0.2940 (3)1.06131 (17)0.0677 (7)
H6A0.11910.25971.02590.081*
C70.1882 (4)0.2367 (3)1.14483 (18)0.0728 (8)
H7A0.14130.16221.16450.087*
C80.2428 (3)0.3982 (2)0.86860 (16)0.0552 (6)
C90.2452 (4)0.4455 (2)0.71360 (17)0.0592 (7)
C100.0941 (4)0.4490 (3)0.7028 (2)0.0736 (8)
H10A0.00590.47010.75180.088*
C110.0741 (5)0.4207 (3)0.6182 (3)0.0944 (10)
H11A−0.02790.42160.60980.113*
C120.2045 (6)0.3912 (3)0.5469 (2)0.0998 (12)
H12A0.19020.37340.48990.120*
C130.3554 (5)0.3876 (3)0.5580 (2)0.0927 (10)
H13A0.44390.36590.50920.111*
C140.3751 (4)0.4166 (3)0.6428 (2)0.0744 (8)
H14A0.47690.41640.65130.089*
C150.2199 (4)0.8740 (3)0.45921 (18)0.0983 (11)
H15A0.18400.78950.45680.148*
H15B0.32170.86490.41710.148*
H15C0.14160.95440.44340.148*
C160.2396 (3)0.8946 (3)0.55416 (17)0.0683 (8)
C170.2895 (4)1.0104 (3)0.57645 (18)0.0785 (9)
H17A0.31201.07580.53180.094*
C180.3062 (3)1.0305 (3)0.66276 (17)0.0681 (8)
H18A0.33961.10900.67560.082*
C190.2739 (3)0.9354 (2)0.73064 (15)0.0495 (6)
C200.2257 (4)0.8183 (3)0.70921 (17)0.0675 (7)
H20A0.20450.75210.75350.081*
C210.2095 (4)0.8008 (3)0.62212 (18)0.0751 (8)
H21A0.17690.72200.60900.090*
C220.2787 (3)0.8796 (2)0.89110 (15)0.0483 (6)
C230.2708 (3)0.8880 (2)1.04888 (15)0.0481 (6)
C240.3933 (3)0.8655 (3)1.09414 (17)0.0587 (7)
H24A0.49280.88121.06600.070*
C250.3663 (3)0.8190 (3)1.18239 (17)0.0662 (7)
H25A0.44820.80311.21430.079*
C260.2183 (3)0.7959 (3)1.22356 (17)0.0677 (8)
H26A0.20040.76561.28340.081*
C270.0979 (3)0.8173 (3)1.17687 (17)0.0632 (7)
H27A−0.00100.79981.20460.076*
C280.1224 (3)0.8648 (2)1.08853 (16)0.0543 (6)
H28A0.04050.88081.05660.065*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.1460 (19)0.0512 (11)0.0592 (11)−0.0492 (12)−0.0287 (11)0.0079 (9)
O20.0878 (13)0.0380 (9)0.0662 (11)−0.0274 (8)−0.0262 (9)0.0036 (8)
O30.1163 (15)0.0379 (9)0.0578 (10)−0.0340 (9)−0.0233 (10)0.0068 (8)
O40.0911 (13)0.0498 (9)0.0516 (10)−0.0397 (9)−0.0221 (9)0.0072 (8)
N10.1033 (17)0.0368 (10)0.0604 (13)−0.0304 (11)−0.0202 (12)0.0007 (9)
N20.0792 (14)0.0374 (10)0.0520 (11)−0.0288 (10)−0.0149 (10)0.0062 (9)
C10.124 (3)0.111 (3)0.068 (2)0.001 (2)−0.014 (2)0.0120 (19)
C20.0782 (19)0.0606 (17)0.0556 (16)0.0035 (15)−0.0058 (14)−0.0036 (13)
C30.0718 (19)0.092 (2)0.0628 (17)−0.0202 (16)−0.0164 (14)−0.0093 (16)
C40.0734 (18)0.0625 (17)0.0647 (17)−0.0305 (14)−0.0102 (14)−0.0079 (13)
C50.0695 (16)0.0394 (13)0.0518 (14)−0.0140 (11)−0.0081 (12)−0.0026 (11)
C60.098 (2)0.0527 (15)0.0593 (16)−0.0330 (15)−0.0154 (15)−0.0012 (12)
C70.104 (2)0.0464 (15)0.0622 (17)−0.0221 (15)−0.0031 (16)0.0012 (13)
C80.0731 (17)0.0375 (13)0.0597 (15)−0.0221 (12)−0.0157 (13)0.0058 (11)
C90.085 (2)0.0373 (13)0.0572 (16)−0.0205 (13)−0.0161 (14)0.0082 (11)
C100.083 (2)0.0533 (16)0.082 (2)−0.0169 (15)−0.0160 (17)0.0110 (14)
C110.116 (3)0.078 (2)0.108 (3)−0.034 (2)−0.057 (2)0.025 (2)
C120.178 (4)0.068 (2)0.067 (2)−0.037 (2)−0.049 (3)0.0109 (17)
C130.122 (3)0.073 (2)0.068 (2)−0.020 (2)0.003 (2)0.0026 (16)
C140.082 (2)0.0612 (17)0.078 (2)−0.0220 (15)−0.0114 (17)0.0098 (15)
C150.145 (3)0.087 (2)0.0587 (18)−0.012 (2)−0.0344 (19)−0.0033 (16)
C160.089 (2)0.0528 (16)0.0532 (15)−0.0030 (14)−0.0119 (14)−0.0038 (12)
C170.118 (3)0.0602 (17)0.0537 (16)−0.0259 (17)−0.0112 (16)0.0120 (13)
C180.101 (2)0.0509 (15)0.0568 (16)−0.0327 (15)−0.0123 (14)0.0076 (12)
C190.0624 (15)0.0360 (12)0.0486 (13)−0.0127 (11)−0.0089 (11)−0.0003 (10)
C200.108 (2)0.0471 (14)0.0579 (16)−0.0333 (15)−0.0255 (15)0.0080 (12)
C210.122 (3)0.0504 (15)0.0629 (17)−0.0303 (16)−0.0309 (16)0.0019 (13)
C220.0600 (15)0.0367 (12)0.0510 (13)−0.0179 (11)−0.0113 (11)−0.0010 (10)
C230.0665 (16)0.0354 (12)0.0480 (13)−0.0194 (11)−0.0163 (12)−0.0001 (10)
C240.0585 (16)0.0569 (15)0.0679 (17)−0.0249 (12)−0.0173 (13)0.0042 (12)
C250.0712 (18)0.0742 (18)0.0652 (17)−0.0273 (15)−0.0311 (14)0.0094 (14)
C260.089 (2)0.0717 (18)0.0483 (15)−0.0304 (16)−0.0177 (14)0.0076 (13)
C270.0618 (17)0.0673 (17)0.0601 (16)−0.0225 (13)−0.0063 (13)0.0052 (13)
C280.0555 (15)0.0538 (14)0.0587 (15)−0.0194 (12)−0.0176 (12)0.0039 (11)

Geometric parameters (Å, °)

O1—C81.366 (3)C11—H11A0.9300
O1—C91.390 (3)C12—C131.363 (5)
O2—C81.211 (3)C12—H12A0.9300
O3—C221.205 (3)C13—C141.384 (4)
O4—C221.363 (3)C13—H13A0.9300
O4—C231.404 (3)C14—H14A0.9300
N1—C51.415 (3)C15—C161.512 (3)
N1—C81.340 (3)C15—H15A0.9600
N1—H1A0.8600C15—H15B0.9600
N2—C191.407 (3)C15—H15C0.9600
N2—C221.345 (3)C16—C211.370 (4)
N2—H2A0.8600C16—C171.392 (4)
C1—C21.508 (4)C17—C181.374 (4)
C1—H1B0.9600C17—H17A0.9300
C1—H1C0.9600C18—C191.381 (3)
C1—H1D0.9600C18—H18A0.9300
C2—C71.378 (4)C19—C201.390 (3)
C2—C31.387 (4)C20—C211.379 (3)
C3—C41.380 (4)C20—H20A0.9300
C3—H3A0.9300C21—H21A0.9300
C4—C51.383 (3)C23—C241.366 (3)
C4—H4A0.9300C23—C281.377 (3)
C5—C61.395 (3)C24—C251.378 (3)
C6—C71.372 (3)C24—H24A0.9300
C6—H6A0.9300C25—C261.380 (4)
C7—H7A0.9300C25—H25A0.9300
C9—C141.357 (4)C26—C271.366 (3)
C9—C101.364 (4)C26—H26A0.9300
C10—C111.379 (4)C27—C281.382 (3)
C10—H10A0.9300C27—H27A0.9300
C11—C121.365 (5)C28—H28A0.9300
C8—O1—C9118.14 (18)C14—C13—H13A120.5
C22—O4—C23118.29 (16)C9—C14—C13119.7 (3)
C5—N1—H1A117.0C9—C14—H14A120.2
C8—N1—C5125.91 (19)C13—C14—H14A120.2
C8—N1—H1A117.0C16—C15—H15A109.5
C19—N2—H2A116.2C16—C15—H15B109.5
C22—N2—C19127.53 (18)H15A—C15—H15B109.5
C22—N2—H2A116.2C16—C15—H15C109.5
C2—C1—H1B109.5H15A—C15—H15C109.5
C2—C1—H1C109.5H15B—C15—H15C109.5
H1B—C1—H1C109.5C21—C16—C17116.9 (2)
C2—C1—H1D109.5C21—C16—C15121.9 (3)
H1B—C1—H1D109.5C17—C16—C15121.3 (3)
H1C—C1—H1D109.5C18—C17—C16121.6 (2)
C7—C2—C3117.1 (3)C18—C17—H17A119.2
C7—C2—C1121.0 (3)C16—C17—H17A119.2
C3—C2—C1121.9 (3)C17—C18—C19120.8 (2)
C4—C3—C2121.9 (3)C17—C18—H18A119.6
C4—C3—H3A119.1C19—C18—H18A119.6
C2—C3—H3A119.1C18—C19—C20118.4 (2)
C3—C4—C5119.8 (2)C18—C19—N2118.0 (2)
C3—C4—H4A120.1C20—C19—N2123.7 (2)
C5—C4—H4A120.1C21—C20—C19119.8 (2)
C4—C5—C6119.1 (2)C21—C20—H20A120.1
C4—C5—N1117.9 (2)C19—C20—H20A120.1
C6—C5—N1123.0 (2)C16—C21—C20122.7 (3)
C7—C6—C5119.5 (3)C16—C21—H21A118.7
C7—C6—H6A120.3C20—C21—H21A118.7
C5—C6—H6A120.3O3—C22—N2127.6 (2)
C6—C7—C2122.5 (3)O3—C22—O4124.0 (2)
C6—C7—H7A118.8N2—C22—O4108.47 (18)
C2—C7—H7A118.8C24—C23—C28122.0 (2)
O2—C8—N1128.3 (2)C24—C23—O4117.1 (2)
O2—C8—O1123.1 (2)C28—C23—O4120.6 (2)
N1—C8—O1108.56 (19)C23—C24—C25118.6 (2)
C14—C9—C10121.4 (3)C23—C24—H24A120.7
C14—C9—O1117.9 (3)C25—C24—H24A120.7
C10—C9—O1120.4 (3)C24—C25—C26120.3 (2)
C9—C10—C11119.0 (3)C24—C25—H25A119.9
C9—C10—H10A120.5C26—C25—H25A119.9
C11—C10—H10A120.5C27—C26—C25120.3 (2)
C12—C11—C10119.8 (3)C27—C26—H26A119.9
C12—C11—H11A120.1C25—C26—H26A119.9
C10—C11—H11A120.1C26—C27—C28120.2 (2)
C13—C12—C11121.1 (3)C26—C27—H27A119.9
C13—C12—H12A119.5C28—C27—H27A119.9
C11—C12—H12A119.5C23—C28—C27118.5 (2)
C12—C13—C14119.0 (3)C23—C28—H28A120.7
C12—C13—H13A120.5C27—C28—H28A120.7
C7—C2—C3—C4−1.0 (4)C21—C16—C17—C18−0.7 (4)
C1—C2—C3—C4−179.9 (3)C15—C16—C17—C18179.4 (3)
C2—C3—C4—C5−0.9 (4)C16—C17—C18—C190.1 (5)
C3—C4—C5—C62.9 (4)C17—C18—C19—C200.6 (4)
C3—C4—C5—N1−177.7 (2)C17—C18—C19—N2−178.8 (2)
C8—N1—C5—C4149.9 (3)C22—N2—C19—C18−173.8 (2)
C8—N1—C5—C6−30.8 (4)C22—N2—C19—C206.8 (4)
C4—C5—C6—C7−3.1 (4)C18—C19—C20—C21−0.8 (4)
N1—C5—C6—C7177.6 (2)N2—C19—C20—C21178.6 (3)
C5—C6—C7—C21.2 (4)C17—C16—C21—C200.5 (4)
C3—C2—C7—C60.8 (4)C15—C16—C21—C20−179.5 (3)
C1—C2—C7—C6179.7 (3)C19—C20—C21—C160.2 (5)
C5—N1—C8—O26.9 (4)C19—N2—C22—O32.7 (4)
C5—N1—C8—O1−170.2 (2)C19—N2—C22—O4−177.8 (2)
C9—O1—C8—O212.4 (4)C23—O4—C22—O3−7.4 (3)
C9—O1—C8—N1−170.3 (2)C23—O4—C22—N2173.05 (18)
C8—O1—C9—C14−116.7 (3)C22—O4—C23—C24124.8 (2)
C8—O1—C9—C1069.1 (3)C22—O4—C23—C28−61.1 (3)
C14—C9—C10—C110.8 (4)C28—C23—C24—C25−0.4 (4)
O1—C9—C10—C11174.8 (2)O4—C23—C24—C25173.5 (2)
C9—C10—C11—C12−0.7 (4)C23—C24—C25—C260.1 (4)
C10—C11—C12—C130.8 (5)C24—C25—C26—C270.8 (4)
C11—C12—C13—C14−1.1 (5)C25—C26—C27—C28−1.2 (4)
C10—C9—C14—C13−1.1 (4)C24—C23—C28—C270.0 (4)
O1—C9—C14—C13−175.2 (2)O4—C23—C28—C27−173.8 (2)
C12—C13—C14—C91.2 (4)C26—C27—C28—C230.8 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O30.862.132.972 (3)168
N2—H2A···O2i0.862.283.061 (2)152

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2710).

References

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