Phenyl N-(2-methyl­phen­yl)carbamate

Abstract

In the title compound, C₁₄H₁₃NO₂, the aromatic rings attached to the O and N atoms make dihedral angles of 62.65 (9) and 38.28 (11)°, respectively, with the central carbamate group. The benzene rings are oriented at a dihedral angle of 39.22 (10)°. In the crystal, a very weak C—H⋯π inter­action occurs.

Related literature

For a related structure, see: Shahwar et al. (2009 ▶).

Experimental

Crystal data

• C₁₄H₁₃NO₂

• M _r = 227.25

• Orthorhombic,

• a = 10.5736 (9) Å

• b = 18.5414 (14) Å

• c = 5.9681 (4) Å

• V = 1170.04 (15) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 296 K

• 0.25 × 0.14 × 0.14 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.984, T _max = 0.989

• 6929 measured reflections

• 1585 independent reflections

• 997 reflections with I > 2σ(I)

• R _int = 0.037

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.083

• S = 1.01

• 1585 reflections

• 158 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.13 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯CgBi	0.93	2.95	3.714 (3)	140

Symmetry code: (i) . CgB is the centroid of benzene ring (C8–C13).

supplementary crystallographic information

Comment

We have recently published the crystal structure of (II), phenyl N-phenylcarbamate (Shahwar et al., 2009), which differs from the title compound, (I), due to an attachement of CH₃ at ortho-position of benzene ring attached with N-atom.

In (I), the benzene rings A (C1—C6) and B (C8—C13) are of course planar. The central portion containing carbamate group C (C7/O1/O2/N1) is also planar. The benzene rings A & B are oriented at a dihedral angle of 39.22 (10)°. The dihedral angles between A/C and B/C have values of of 62.65 (9)° and 38.28 (11)°, respectively. The H-atom attached with N-atom does not form any intera or inter-molecular H-bonding due to the attachement of methyl group. There exists a weak C–H···π interaction (Table 1).

Experimental

A solution of o-toluidine (1.08 ml, 0.01 mol) in dichloromethane (20 ml) was prepared. Phenylchloroformate (1.26 ml, 0.01 mol) was added drop-wise to the magnetically stirring solution. The mixture turned to suspension after one hour. To get complete product, n-hexane (30 ml) was added and the precipitate were obtained. The precipitate were filtered out and recrystalized from ethylacetate and methanol (9:1) to yield colourless blocks of (I).

Refinement

In the absence of significant anomalous scattering effects, Friedel pairs were merged before refinement.

The coordinates of the N-bound H atom were refined. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding with U_iso(H) = 1.2U_eq(C, N) or 1.5U_eq(methyl C).

Figures

Fig. 1.

View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small spheres of arbitrary radius.

Crystal data

C14H13NO2	F(000) = 480
Mr = 227.25	Dx = 1.290 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2241 reflections
a = 10.5736 (9) Å	θ = 3.0–28.6°
b = 18.5414 (14) Å	µ = 0.09 mm−1
c = 5.9681 (4) Å	T = 296 K
V = 1170.04 (15) Å3	Block, colourless
Z = 4	0.25 × 0.14 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	1585 independent reflections
Radiation source: fine-focus sealed tube	997 reflections with I > 2σ(I)
graphite	Rint = 0.037
Detector resolution: 7.40 pixels mm-1	θmax = 28.3°, θmin = 2.9°
ω scans	h = −14→13
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→24
Tmin = 0.984, Tmax = 0.989	l = −7→7
6929 measured reflections

Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0377P)2] where P = (Fo2 + 2Fc2)/3
1585 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.13 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.27882 (15)	0.33744 (9)	0.6965 (3)	0.0594 (6)
O2	0.48038 (14)	0.30458 (9)	0.6133 (3)	0.0585 (6)
N1	0.30983 (19)	0.24161 (11)	0.4867 (3)	0.0547 (7)
C1	0.31727 (19)	0.39161 (13)	0.8463 (4)	0.0459 (8)
C2	0.3813 (2)	0.37450 (12)	1.0394 (4)	0.0492 (8)
C3	0.4089 (2)	0.42831 (13)	1.1897 (4)	0.0550 (9)
C4	0.3718 (2)	0.49827 (14)	1.1487 (5)	0.0610 (9)
C5	0.3068 (2)	0.51391 (15)	0.9561 (4)	0.0657 (10)
C6	0.2797 (2)	0.46077 (14)	0.8027 (4)	0.0580 (9)
C7	0.3691 (2)	0.29463 (12)	0.6005 (4)	0.0472 (8)
C8	0.3694 (2)	0.19088 (12)	0.3442 (4)	0.0479 (7)
C9	0.3097 (2)	0.17293 (13)	0.1431 (4)	0.0508 (8)
C10	0.3682 (3)	0.12288 (15)	0.0089 (4)	0.0683 (10)
C11	0.4814 (3)	0.09134 (15)	0.0662 (6)	0.0783 (12)
C12	0.5378 (3)	0.10948 (16)	0.2643 (6)	0.0746 (11)
C13	0.4824 (2)	0.15870 (14)	0.4054 (5)	0.0599 (9)
C14	0.1842 (2)	0.20522 (15)	0.0812 (5)	0.0670 (10)
H1	0.233 (2)	0.2453 (13)	0.486 (5)	0.0657*
H2	0.40570	0.32718	1.06787	0.0590*
H3	0.45290	0.41743	1.32027	0.0660*
H4	0.39062	0.53459	1.25089	0.0732*
H5	0.28080	0.56101	0.92870	0.0787*
H6	0.23641	0.47170	0.67139	0.0696*
H10	0.33000	0.10987	−0.12545	0.0820*
H11	0.51913	0.05797	−0.02901	0.0938*
H12	0.61432	0.08830	0.30394	0.0895*
H13	0.52051	0.17034	0.54111	0.0718*
H14A	0.12302	0.19369	0.19447	0.1006*
H14B	0.15695	0.18596	−0.06011	0.1006*
H14C	0.19249	0.25665	0.06956	0.1006*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0456 (10)	0.0665 (11)	0.0662 (11)	0.0037 (8)	−0.0135 (9)	−0.0153 (10)
O2	0.0448 (10)	0.0669 (11)	0.0638 (10)	−0.0087 (8)	−0.0047 (9)	−0.0083 (9)
N1	0.0419 (11)	0.0632 (13)	0.0591 (12)	−0.0031 (11)	−0.0084 (12)	−0.0090 (11)
C1	0.0369 (12)	0.0511 (14)	0.0497 (14)	−0.0005 (10)	−0.0010 (11)	0.0007 (12)
C2	0.0439 (13)	0.0417 (13)	0.0620 (15)	−0.0029 (11)	−0.0062 (11)	0.0052 (12)
C3	0.0509 (15)	0.0604 (16)	0.0538 (14)	−0.0063 (12)	−0.0084 (12)	−0.0008 (14)
C4	0.0625 (15)	0.0521 (15)	0.0683 (18)	−0.0070 (12)	0.0069 (14)	−0.0096 (14)
C5	0.0692 (19)	0.0490 (15)	0.079 (2)	0.0116 (13)	0.0064 (15)	0.0095 (15)
C6	0.0577 (16)	0.0621 (17)	0.0541 (16)	0.0100 (13)	−0.0013 (13)	0.0092 (14)
C7	0.0484 (14)	0.0513 (14)	0.0418 (11)	−0.0019 (12)	−0.0080 (12)	0.0035 (11)
C8	0.0445 (13)	0.0489 (13)	0.0503 (12)	−0.0100 (12)	−0.0001 (12)	0.0023 (12)
C9	0.0479 (14)	0.0562 (14)	0.0484 (14)	−0.0180 (11)	0.0020 (11)	0.0013 (13)
C10	0.0679 (19)	0.0809 (19)	0.0562 (16)	−0.0237 (16)	0.0076 (15)	−0.0113 (15)
C11	0.070 (2)	0.072 (2)	0.093 (2)	−0.0072 (16)	0.0194 (18)	−0.0196 (17)
C12	0.0536 (17)	0.0682 (19)	0.102 (2)	0.0007 (15)	0.0057 (17)	−0.0014 (18)
C13	0.0509 (16)	0.0598 (17)	0.0689 (16)	−0.0023 (12)	−0.0067 (13)	0.0042 (14)
C14	0.0568 (15)	0.084 (2)	0.0601 (14)	−0.0133 (14)	−0.0147 (13)	0.0003 (15)

Geometric parameters (Å, °)

O1—C1	1.405 (3)	C10—C11	1.375 (4)
O1—C7	1.367 (3)	C11—C12	1.366 (5)
O2—C7	1.194 (3)	C12—C13	1.373 (4)
N1—C7	1.349 (3)	C2—H2	0.9300
N1—C8	1.416 (3)	C3—H3	0.9300
N1—H1	0.82 (2)	C4—H4	0.9300
C1—C6	1.367 (3)	C5—H5	0.9300
C1—C2	1.374 (3)	C6—H6	0.9300
C2—C3	1.373 (3)	C10—H10	0.9300
C3—C4	1.377 (4)	C11—H11	0.9300
C4—C5	1.370 (4)	C12—H12	0.9300
C5—C6	1.375 (4)	C13—H13	0.9300
C8—C13	1.385 (3)	C14—H14A	0.9600
C8—C9	1.396 (3)	C14—H14B	0.9600
C9—C10	1.373 (4)	C14—H14C	0.9600
C9—C14	1.502 (3)
C1—O1—C7	118.67 (17)	C1—C2—H2	121.00
C7—N1—C8	125.43 (19)	C3—C2—H2	120.00
C8—N1—H1	119.7 (19)	C2—C3—H3	120.00
C7—N1—H1	113.9 (18)	C4—C3—H3	120.00
O1—C1—C6	117.7 (2)	C3—C4—H4	120.00
C2—C1—C6	121.3 (2)	C5—C4—H4	120.00
O1—C1—C2	120.8 (2)	C4—C5—H5	120.00
C1—C2—C3	119.0 (2)	C6—C5—H5	120.00
C2—C3—C4	120.5 (2)	C1—C6—H6	121.00
C3—C4—C5	119.4 (2)	C5—C6—H6	120.00
C4—C5—C6	120.8 (2)	C9—C10—H10	119.00
C1—C6—C5	119.0 (2)	C11—C10—H10	119.00
O1—C7—N1	108.04 (18)	C10—C11—H11	120.00
O2—C7—N1	127.1 (2)	C12—C11—H11	120.00
O1—C7—O2	124.9 (2)	C11—C12—H12	120.00
C9—C8—C13	120.9 (2)	C13—C12—H12	120.00
N1—C8—C9	118.26 (19)	C8—C13—H13	120.00
N1—C8—C13	120.8 (2)	C12—C13—H13	120.00
C10—C9—C14	121.6 (2)	C9—C14—H14A	109.00
C8—C9—C10	117.3 (2)	C9—C14—H14B	109.00
C8—C9—C14	121.1 (2)	C9—C14—H14C	109.00
C9—C10—C11	122.3 (3)	H14A—C14—H14B	109.00
C10—C11—C12	119.4 (3)	H14A—C14—H14C	109.00
C11—C12—C13	120.5 (3)	H14B—C14—H14C	109.00
C8—C13—C12	119.5 (3)
C7—O1—C1—C2	−60.4 (3)	C3—C4—C5—C6	−0.8 (3)
C7—O1—C1—C6	124.9 (2)	C4—C5—C6—C1	0.8 (3)
C1—O1—C7—O2	−9.1 (3)	N1—C8—C9—C10	−179.1 (2)
C1—O1—C7—N1	172.51 (19)	N1—C8—C9—C14	−1.3 (3)
C8—N1—C7—O1	172.7 (2)	C13—C8—C9—C10	−0.6 (4)
C8—N1—C7—O2	−5.7 (4)	C13—C8—C9—C14	177.2 (2)
C7—N1—C8—C9	−139.0 (2)	N1—C8—C13—C12	179.8 (2)
C7—N1—C8—C13	42.5 (3)	C9—C8—C13—C12	1.3 (4)
O1—C1—C2—C3	−175.14 (19)	C8—C9—C10—C11	−0.4 (4)
C6—C1—C2—C3	−0.7 (3)	C14—C9—C10—C11	−178.2 (3)
O1—C1—C6—C5	174.57 (19)	C9—C10—C11—C12	0.7 (5)
C2—C1—C6—C5	−0.1 (3)	C10—C11—C12—C13	0.0 (5)
C1—C2—C3—C4	0.7 (3)	C11—C12—C13—C8	−1.0 (4)
C2—C3—C4—C5	0.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···CgBi	0.93	2.95	3.714 (3)	140

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