Phenyl N-(2-methyl­phen­yl)carbamate

Shahwar, D.; Tahir, M.N.; Ahmad, N.; Yasmeen, A.; Ullah, S.

doi:10.1107/S1600536809022788

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1629

doi:10.1107/S1600536809022788

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Phenyl N-(2-methylphenyl)carbamate

Durre Shahwar,^a M. Nawaz Tahir,^b ^* Naeem Ahmad,^a Asma Yasmeen ^a and Saif Ullah ^a

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 13 June 2009; accepted 13 June 2009; online 20 June 2009)

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, P n a 2₁
a = 10.5736 (9) Å
b = 18.5414 (14) Å
c = 5.9681 (4) Å
V = 1170.04 (15) Å³
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[F² > 2σ(F²)] = 0.039
wR(F²) = 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

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) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ . CgB is the centroid of benzene ring (C8–C13).

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022788/hb5008sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022788/hb5008Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For a related structure, see: Shahwar et al. (2009). CgB is the centroid of benzene ring (C8—C13).

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Spek, 2009).

Figures top

Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small spheres of arbitrary radius.

Phenyl N</>-(2-methylphenyl)carbamate top

Crystal data top

C₁₄H₁₃NO₂	F(000) = 480
M_r = 227.25	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0377P)²] where P = (F_o² + 2F_c²)/3
1585 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₄H₁₃NO₂	V = 1170.04 (15) Å³
M_r = 227.25	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 10.5736 (9) Å	µ = 0.09 mm⁻¹
b = 18.5414 (14) Å	T = 296 K
c = 5.9681 (4) Å	0.25 × 0.14 × 0.14 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1585 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	997 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.989	R_int = 0.037
6929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.13 e Å⁻³
1585 reflections	Δρ_min = −0.15 e Å⁻³
158 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO₂
M_r	227.25
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	10.5736 (9), 18.5414 (14), 5.9681 (4)
V (Å³)	1170.04 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.14 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.984, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	6929, 1585, 997
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.083, 1.01
No. of reflections	1585
No. of parameters	158
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.15

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y+1/2, z+1/2.

Acknowledgements

NA greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing a Scholarship under the Indigenous PhD Program (PIN 042–120599-PS2–156).

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Shahwar, D., Tahir, M. N., Mughal, M. S., Khan, M. A. & Ahmad, N. (2009). Acta Cryst. E65, o1363. Web of Science CSD CrossRef IUCr Journals 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