Phenyl N-[4-chloro-3-(trifluoro­meth­yl)phen­yl]carbamate

Tang, H.-T.; Fang, Z.

doi:10.1107/S1600536809004942

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o537

doi:10.1107/S1600536809004942

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Phenyl N-[4-chloro-3-(trifluoromethyl)phenyl]carbamate

Hai-Tao Tang ^a and Zheng Fang ^a ^*

^aCollege of Life Sciences and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No.5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fzcpu@163.com

(Received 9 February 2009; accepted 11 February 2009; online 18 February 2009)

In the molecule of the title compound, C₁₄H₉ClF₃NO₂, the aromatic rings are oriented at a dihedral angle of 66.49 (3)°. Intramolecular C—H⋯F and C—H⋯O interactions result in the formation of one planar five- and one non-planar six-membered ring. 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 ).

Experimental

Crystal data

C₁₄H₉ClF₃NO₂
M_r = 315.67
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.5680 (17) Å
b = 11.152 (2) Å
c = 14.232 (3) Å
V = 1359.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.32 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 ) T_min = 0.910, T_max = 0.969
2733 measured reflections
2465 independent reflections
1775 reflections with I > 2σ(I)
R_int = 0.034
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.188
S = 1.00
2465 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 1012 Friedel pairs
Flack parameter: −0.1 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O2ⁱ	0.86	2.10	2.943 (5)	168
C9—H9A⋯O2	0.93	2.44	2.950 (5)	114
C13—H13A⋯F2	0.93	2.34	2.687 (5)	102
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004942/hk2623sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004942/hk2623Isup2.hkl

checkCIF report

Comment top

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

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C8-C13) are, of course, planar and the dihedral angle between them is A/B = 66.49 (3)°. The intramolecular C-H···F and C-H···O interactions (Table 1) result in the formations of one planar five- and one nonplanar six-membered rings C (F2/C12-C14/H13A) and D (O2/N/C7-C9/H9A). Ring C is oriented with respect to rings A and B at dihedral angles of 66.33 (3)° and 0.93 (3)°, respectively. So, rings B and C are nearly coplanar.

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.

Related literature top

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

Experimental top

For the preparation of the title compound, phenyl chloroformate (1.0 ml) was added slowly to a cold solution of 4-chloro-3-(trifluoromethyl)benzenamine (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. Then, it was washed with water (20 ml), dried and concentrated to give the title compound (yield; 1.3 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of an methanol solution.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Phenyl N-[4-chloro-3-(trifluoromethyl)phenyl]carbamate top

Crystal data top

C₁₄H₉ClF₃NO₂	F(000) = 640
M_r = 315.67	D_x = 1.542 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 8.5680 (17) Å	θ = 9–13°
b = 11.152 (2) Å	µ = 0.32 mm⁻¹
c = 14.232 (3) Å	T = 294 K
V = 1359.9 (5) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1775 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = −10→0
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
T_min = 0.910, T_max = 0.969	l = 0→17
2733 measured reflections	3 standard reflections every 120 min
2465 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.188	w = 1/[σ²(F_o²) + (0.1P)² + 0.77P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2465 reflections	Δρ_max = 0.31 e Å⁻³
190 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1012 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.1 (2)

Crystal data top

C₁₄H₉ClF₃NO₂	V = 1359.9 (5) Å³
M_r = 315.67	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.5680 (17) Å	µ = 0.32 mm⁻¹
b = 11.152 (2) Å	T = 294 K
c = 14.232 (3) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1775 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.034
T_min = 0.910, T_max = 0.969	3 standard reflections every 120 min
2733 measured reflections	intensity decay: 1%
2465 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.188	Δρ_max = 0.31 e Å⁻³
S = 1.00	Δρ_min = −0.33 e Å⁻³
2465 reflections	Absolute structure: Flack (1983), 1012 Friedel pairs
190 parameters	Absolute structure parameter: −0.1 (2)
0 restraints

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
Cl	0.0048 (2)	0.53814 (16)	0.89390 (11)	0.0988 (6)
O1	−0.2368 (5)	0.1837 (4)	0.4272 (2)	0.0826 (12)
O2	−0.0472 (4)	0.3226 (3)	0.4484 (2)	0.0666 (9)
N	−0.2332 (4)	0.2838 (4)	0.5598 (2)	0.0591 (10)
H0A	−0.3230	0.2503	0.5658	0.071*
F1	−0.0639 (5)	0.2695 (4)	0.9446 (2)	0.1080 (13)
F2	−0.2866 (6)	0.2112 (4)	0.8948 (2)	0.1123 (14)
F3	−0.2646 (5)	0.3817 (4)	0.9590 (2)	0.1006 (12)
C1	−0.1803 (11)	0.1852 (9)	0.1733 (4)	0.113 (3)
H1A	−0.2077	0.2306	0.1210	0.135*
C2	−0.2231 (8)	0.2230 (6)	0.2625 (4)	0.0855 (17)
H2A	−0.2801	0.2933	0.2705	0.103*
C3	−0.1805 (6)	0.1559 (5)	0.3380 (3)	0.0640 (12)
C4	−0.0945 (7)	0.0528 (6)	0.3267 (5)	0.0858 (17)
H4A	−0.0635	0.0080	0.3785	0.103*
C5	−0.0551 (8)	0.0171 (7)	0.2366 (7)	0.108 (2)
H5A	0.0023	−0.0528	0.2279	0.129*
C6	−0.0982 (10)	0.0814 (9)	0.1623 (6)	0.107 (3)
H6A	−0.0721	0.0554	0.1023	0.128*
C7	−0.1599 (6)	0.2711 (5)	0.4764 (3)	0.0592 (12)
C8	−0.1749 (5)	0.3473 (4)	0.6376 (3)	0.0552 (10)
C9	−0.0823 (6)	0.4470 (4)	0.6301 (3)	0.0630 (12)
H9A	−0.0551	0.4759	0.5710	0.076*
C10	−0.0296 (6)	0.5046 (5)	0.7093 (4)	0.0701 (14)
H10A	0.0317	0.5731	0.7037	0.084*
C11	−0.0673 (6)	0.4609 (5)	0.7972 (3)	0.0668 (13)
C12	−0.1575 (5)	0.3606 (5)	0.8067 (3)	0.0575 (11)
C13	−0.2113 (6)	0.3025 (4)	0.7261 (3)	0.0575 (11)
H13A	−0.2717	0.2336	0.7316	0.069*
C14	−0.1934 (7)	0.3082 (5)	0.9005 (4)	0.0750 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.1108 (13)	0.0951 (10)	0.0905 (9)	−0.0134 (10)	−0.0136 (9)	−0.0296 (8)
O1	0.076 (2)	0.100 (3)	0.071 (2)	−0.028 (2)	0.0213 (18)	−0.0225 (19)
O2	0.0450 (19)	0.081 (2)	0.0734 (19)	−0.0056 (17)	0.0076 (16)	0.0014 (17)
N	0.041 (2)	0.078 (2)	0.0584 (19)	−0.0034 (19)	0.0061 (17)	−0.0029 (18)
F1	0.112 (3)	0.130 (3)	0.0824 (19)	0.030 (3)	−0.007 (2)	0.027 (2)
F2	0.146 (4)	0.112 (3)	0.0788 (19)	−0.032 (3)	0.025 (2)	0.0049 (19)
F3	0.106 (3)	0.121 (3)	0.0750 (18)	0.010 (2)	0.0225 (19)	−0.0228 (19)
C1	0.120 (6)	0.150 (8)	0.068 (3)	−0.029 (6)	0.003 (4)	0.008 (4)
C2	0.085 (4)	0.088 (4)	0.083 (3)	0.015 (4)	0.005 (3)	0.004 (3)
C3	0.055 (3)	0.078 (3)	0.060 (2)	−0.010 (3)	0.008 (2)	−0.011 (2)
C4	0.068 (4)	0.086 (4)	0.104 (4)	−0.001 (3)	−0.006 (3)	−0.004 (4)
C5	0.078 (4)	0.099 (5)	0.146 (7)	0.000 (4)	0.020 (5)	−0.052 (5)
C6	0.091 (5)	0.131 (7)	0.099 (5)	−0.021 (5)	0.032 (4)	−0.042 (5)
C7	0.045 (3)	0.074 (3)	0.059 (2)	0.011 (3)	−0.003 (2)	−0.004 (2)
C8	0.038 (2)	0.067 (3)	0.060 (2)	0.009 (2)	0.0014 (19)	0.002 (2)
C9	0.062 (3)	0.059 (3)	0.068 (3)	0.001 (2)	0.004 (2)	0.006 (2)
C10	0.069 (3)	0.063 (3)	0.079 (3)	−0.007 (3)	0.005 (3)	−0.005 (2)
C11	0.057 (3)	0.073 (3)	0.071 (3)	0.006 (3)	−0.003 (2)	−0.004 (2)
C12	0.048 (3)	0.064 (3)	0.061 (2)	0.007 (2)	0.000 (2)	−0.002 (2)
C13	0.049 (3)	0.057 (3)	0.066 (2)	0.000 (2)	0.001 (2)	0.004 (2)
C14	0.075 (4)	0.085 (4)	0.065 (3)	0.000 (3)	0.001 (3)	0.001 (3)

Geometric parameters (Å, º) top

Cl—C11	1.738 (5)	C4—C5	1.384 (10)
O1—C7	1.369 (6)	C4—H4A	0.9300
O1—C3	1.393 (6)	C5—C6	1.330 (12)
O2—C7	1.192 (6)	C5—H5A	0.9300
N—C7	1.350 (6)	C6—H6A	0.9300
N—C8	1.406 (6)	C8—C9	1.370 (7)
N—H0A	0.8600	C8—C13	1.390 (6)
F1—C14	1.346 (7)	C9—C10	1.373 (7)
F2—C14	1.347 (7)	C9—H9A	0.9300
F3—C14	1.318 (6)	C10—C11	1.381 (7)
C1—C6	1.363 (12)	C10—H10A	0.9300
C1—C2	1.386 (9)	C11—C12	1.366 (8)
C1—H1A	0.9300	C12—C13	1.395 (7)
C2—C3	1.360 (8)	C12—C14	1.490 (7)
C2—H2A	0.9300	C13—H13A	0.9300
C3—C4	1.375 (9)

C7—O1—C3	117.2 (4)	C9—C8—C13	119.5 (4)
C7—N—C8	125.5 (4)	C9—C8—N	123.5 (4)
C7—N—H0A	117.3	C13—C8—N	116.9 (4)
C8—N—H0A	117.3	C8—C9—C10	120.4 (4)
C6—C1—C2	120.0 (7)	C8—C9—H9A	119.8
C6—C1—H1A	120.0	C10—C9—H9A	119.8
C2—C1—H1A	120.0	C9—C10—C11	120.1 (5)
C3—C2—C1	119.0 (7)	C9—C10—H10A	120.0
C3—C2—H2A	120.5	C11—C10—H10A	120.0
C1—C2—H2A	120.5	C12—C11—C10	120.7 (5)
C2—C3—C4	120.7 (5)	C12—C11—Cl	121.9 (4)
C2—C3—O1	120.3 (5)	C10—C11—Cl	117.3 (4)
C4—C3—O1	118.6 (5)	C11—C12—C13	119.1 (4)
C3—C4—C5	118.7 (6)	C11—C12—C14	121.7 (5)
C3—C4—H4A	120.6	C13—C12—C14	119.1 (5)
C5—C4—H4A	120.6	C8—C13—C12	120.2 (4)
C6—C5—C4	120.9 (7)	C8—C13—H13A	119.9
C6—C5—H5A	119.6	C12—C13—H13A	119.9
C4—C5—H5A	119.6	F3—C14—F1	106.6 (5)
C5—C6—C1	120.7 (7)	F3—C14—F2	105.3 (5)
C5—C6—H6A	119.7	F1—C14—F2	105.0 (5)
C1—C6—H6A	119.7	F3—C14—C12	114.7 (5)
O2—C7—N	128.4 (5)	F1—C14—C12	111.9 (5)
O2—C7—O1	124.2 (4)	F2—C14—C12	112.5 (4)
N—C7—O1	107.5 (4)

C6—C1—C2—C3	0.7 (11)	C8—C9—C10—C11	1.2 (8)
C1—C2—C3—C4	0.9 (10)	C9—C10—C11—C12	−0.2 (8)
C1—C2—C3—O1	−172.5 (6)	C9—C10—C11—Cl	179.6 (4)
C7—O1—C3—C2	−83.3 (7)	C10—C11—C12—C13	0.0 (7)
C7—O1—C3—C4	103.2 (6)	Cl—C11—C12—C13	−179.8 (4)
C2—C3—C4—C5	−1.5 (9)	C10—C11—C12—C14	177.0 (5)
O1—C3—C4—C5	172.0 (5)	Cl—C11—C12—C14	−2.8 (7)
C3—C4—C5—C6	0.5 (10)	C9—C8—C13—C12	1.8 (7)
C4—C5—C6—C1	1.0 (12)	N—C8—C13—C12	179.9 (4)
C2—C1—C6—C5	−1.6 (12)	C11—C12—C13—C8	−0.8 (7)
C8—N—C7—O2	−11.4 (8)	C14—C12—C13—C8	−177.8 (4)
C8—N—C7—O1	167.3 (4)	C11—C12—C14—F3	58.4 (7)
C3—O1—C7—O2	−1.4 (7)	C13—C12—C14—F3	−124.6 (5)
C3—O1—C7—N	179.8 (4)	C11—C12—C14—F1	−63.3 (7)
C7—N—C8—C9	32.4 (7)	C13—C12—C14—F1	113.7 (5)
C7—N—C8—C13	−145.7 (5)	C11—C12—C14—F2	178.7 (5)
C13—C8—C9—C10	−2.0 (7)	C13—C12—C14—F2	−4.4 (7)
N—C8—C9—C10	180.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2ⁱ	0.86	2.10	2.943 (5)	168
C9—H9A···O2	0.93	2.44	2.950 (5)	114
C13—H13A···F2	0.93	2.34	2.687 (5)	102

Symmetry code: (i) x−1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₉ClF₃NO₂
M_r	315.67
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	8.5680 (17), 11.152 (2), 14.232 (3)
V (Å³)	1359.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.910, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	2733, 2465, 1775
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.188, 1.00
No. of reflections	2465
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.33
Absolute structure	Flack (1983), 1012 Friedel pairs
Absolute structure parameter	−0.1 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2ⁱ	0.86	2.10	2.943 (5)	168.00
C9—H9A···O2	0.93	2.44	2.950 (5)	114.00
C13—H13A···F2	0.93	2.34	2.687 (5)	102.00

Symmetry code: (i) x−1/2, −y+1/2, −z+1.

Acknowledgements

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

References

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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar