Phenyl N-phenyl­carbamate

Shahwar, D.; Tahir, M.N.; Mughal, M.S.; Khan, M.A.; Ahmad, N.

doi:10.1107/S1600536809017887

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1363

doi:10.1107/S1600536809017887

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Phenyl N-phenylcarbamate

Durre Shahwar,^a M. Nawaz Tahir,^b ^* M. Sharif Mughal,^c Muhammad Akmal Khan ^a and Naeem Ahmad ^a

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

(Received 11 May 2009; accepted 12 May 2009; online 23 May 2009)

In the title compound, C₁₃H₁₁NO₂, the aromatic rings are oriented at a dihedral angle of 42.52 (12)°. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds, which form infinite one-dimensional polymeric chains extending along the a axis. C—H⋯π interactions between the aromatic rings are also present.

Related literature

For related structures, see: Haufe et al. (2003 ); Shah et al. (2008 , 2009 ); Xu & Qu (2008 ).

Experimental

Crystal data

C₁₃H₁₁NO₂
M_r = 213.23
Orthorhombic, P n a 2₁
a = 9.4734 (9) Å
b = 19.5825 (17) Å
c = 5.8509 (5) Å
V = 1085.42 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.22 × 0.12 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.985, T_max = 0.988
6579 measured reflections
1505 independent reflections
751 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.086
S = 0.97
1505 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.14	2.976 (3)	165
C3—H3⋯Cg2ⁱⁱ	0.93	2.80	3.673 (4)	156
C10—H10⋯Cg1ⁱⁱⁱ	0.93	2.86	3.599 (4)	137
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-1]$ . Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

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 for Windows (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/S1600536809017887/at2785sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017887/at2785Isup2.hkl

checkCIF report

Comment top

The title compound (I), (Fig. 1), is synthesized for investigation of biological activity like enzyme inhibition and antimicrobial activity. It is one of the members of a series of carbamates being synthesized in our laboratory.

Various crystal structures of N-phenylcarbamates with different attachments have been reported. Examples include (II) 4-nitrophenyl N-phenylcarbamate (Xu & Qu, 2008), (III) cis-4-fluorocyclohexyl N-phenylcarbamate, cis-4-hydroxycyclohexyl N-phenylcarbamate and 4-oxocyclohexyl N-phenylcarbamate (Haufe et al., 2003). The title compound is a N-phenylcarbamate with the simplest type of aromatic ring. In (I), the rings A (C1—C6) and B (C8—C13) are oriented at a dihedral angle of 42.49 (13)°. The title compound is stabilized in the form of infinite one-dimensional polymeric chains due to intermolecular N—H···O H-bonding. These chains extend along the crystallographic a axis (Table 1, Fig. 2). Similar infinite chains also due to intermolecular N—H···O H-bonding have also been found in 3-[(3,4-dichlorophenyl)aminocarbonyl]-propionic acid (Shah et al., 2009), 4-[(2-fluorophenyl)amino]-4-oxobutanoic acid (Shah et al., 2008). The packing may also be stabilized due to C—H···π interactions (Table 1).

Related literature top

For related structures, see: Haufe et al. (2003); Shah et al. (2008, 2009); Xu & Qu (2008).

Experimental top

A solution of aniline (0.913 ml, 0.01 mol) and dichloromethane (20 ml) was prepared. Phenylchloroformate (1.26 ml, 0.01 mol) was added dropwise to the magnetically stirring solution. The mixture turned to a suspension after 1 h due to stirring at room temperature. To obtain the final product, n-hexane (30 ml) was added and a precipitate was formed. The precipitate was filtered and recrystalized from ethylacetate and methanol (9:1).

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 for Windows (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 the title compound with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown as small circles of arbitrary radii.
	Fig. 2. A partial packing diagram showing infinite one-dimensional chains along the a axis.

Phenyl N-phenylcarbamate top

Crystal data top

C₁₃H₁₁NO₂	F(000) = 448
M_r = 213.23	D_x = 1.305 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2241 reflections
a = 9.4734 (9) Å	θ = 3.0–28.6°
b = 19.5825 (17) Å	µ = 0.09 mm⁻¹
c = 5.8509 (5) Å	T = 296 K
V = 1085.42 (17) Å³	Needle, colourless
Z = 4	0.22 × 0.12 × 0.12 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1505 independent reflections
Radiation source: fine-focus sealed tube	751 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.6°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −26→26
T_min = 0.985, T_max = 0.988	l = −4→7
6579 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.028P)²] where P = (F_o² + 2F_c²)/3
1505 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₃H₁₁NO₂	V = 1085.42 (17) Å³
M_r = 213.23	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.4734 (9) Å	µ = 0.09 mm⁻¹
b = 19.5825 (17) Å	T = 296 K
c = 5.8509 (5) Å	0.22 × 0.12 × 0.12 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1505 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	751 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.988	R_int = 0.071
6579 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.086	H-atom parameters constrained
S = 0.97	Δρ_max = 0.13 e Å⁻³
1505 reflections	Δρ_min = −0.17 e Å⁻³
145 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	0.2597 (2)	0.32604 (11)	0.9484 (4)	0.0567 (9)
O2	0.0419 (2)	0.29274 (9)	0.8340 (5)	0.0516 (8)
N1	0.2427 (3)	0.23828 (12)	0.7187 (5)	0.0452 (10)
C1	0.2055 (3)	0.37847 (16)	1.0868 (7)	0.0443 (14)
C2	0.2411 (4)	0.44407 (15)	1.0327 (7)	0.0510 (14)
C3	0.2016 (4)	0.49574 (16)	1.1764 (7)	0.0573 (15)
C4	0.1281 (4)	0.48187 (15)	1.3717 (7)	0.0553 (14)
C5	0.0927 (4)	0.41549 (16)	1.4235 (7)	0.0550 (14)
C6	0.1333 (4)	0.36338 (15)	1.2818 (7)	0.0489 (13)
C7	0.1675 (3)	0.28518 (15)	0.8343 (7)	0.0422 (11)
C8	0.1863 (3)	0.19143 (14)	0.5605 (7)	0.0414 (13)
C9	0.0627 (3)	0.15661 (14)	0.5992 (6)	0.0486 (13)
C10	0.0146 (4)	0.11085 (16)	0.4366 (8)	0.0633 (18)
C11	0.0904 (5)	0.09913 (18)	0.2388 (8)	0.0700 (16)
C12	0.2135 (5)	0.13340 (19)	0.2040 (7)	0.0667 (18)
C13	0.2617 (4)	0.17989 (15)	0.3606 (7)	0.0548 (13)
H1	0.33213	0.23677	0.74330	0.0544*
H2	0.29156	0.45348	0.90007	0.0616*
H3	0.22491	0.54063	1.14082	0.0689*
H4	0.10216	0.51715	1.46947	0.0664*
H5	0.04108	0.40599	1.55489	0.0657*
H6	0.11184	0.31833	1.31818	0.0584*
H9	0.01197	0.16370	0.73313	0.0581*
H10	−0.06985	0.08773	0.46083	0.0757*
H11	0.05769	0.06814	0.13063	0.0838*
H12	0.26557	0.12516	0.07208	0.0799*
H13	0.34490	0.20372	0.33304	0.0658*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0340 (14)	0.0611 (13)	0.0751 (19)	−0.0041 (12)	0.0042 (13)	−0.0266 (14)
O2	0.0283 (12)	0.0562 (12)	0.0702 (18)	0.0033 (11)	−0.0034 (13)	−0.0119 (12)
N1	0.0287 (15)	0.0489 (15)	0.058 (2)	0.0041 (14)	−0.0041 (15)	−0.0099 (15)
C1	0.032 (2)	0.052 (2)	0.049 (3)	−0.0012 (16)	−0.003 (2)	−0.0058 (19)
C2	0.050 (2)	0.054 (2)	0.049 (3)	−0.0063 (18)	0.000 (2)	0.0073 (19)
C3	0.059 (3)	0.0410 (19)	0.072 (3)	−0.0043 (17)	−0.002 (2)	0.006 (2)
C4	0.053 (2)	0.049 (2)	0.064 (3)	0.0016 (17)	−0.001 (2)	−0.0118 (19)
C5	0.055 (2)	0.059 (2)	0.051 (3)	−0.0031 (17)	0.006 (2)	0.001 (2)
C6	0.048 (2)	0.0386 (17)	0.060 (3)	−0.0006 (16)	−0.002 (2)	0.0033 (19)
C7	0.040 (2)	0.0385 (15)	0.048 (2)	−0.0018 (17)	−0.007 (2)	0.0020 (17)
C8	0.039 (2)	0.0362 (17)	0.049 (3)	0.0063 (15)	−0.006 (2)	−0.0044 (17)
C9	0.043 (2)	0.0437 (17)	0.059 (3)	−0.0001 (16)	−0.0045 (19)	−0.0024 (18)
C10	0.049 (3)	0.053 (2)	0.088 (4)	−0.0040 (18)	−0.021 (3)	−0.008 (2)
C11	0.079 (3)	0.062 (2)	0.069 (3)	0.014 (2)	−0.024 (3)	−0.022 (2)
C12	0.077 (4)	0.069 (2)	0.054 (3)	0.019 (2)	−0.002 (3)	−0.012 (2)
C13	0.052 (2)	0.0485 (18)	0.064 (3)	0.0044 (17)	0.007 (2)	−0.004 (2)

Geometric parameters (Å, º) top

O1—C1	1.405 (4)	C9—C10	1.384 (5)
O1—C7	1.360 (4)	C10—C11	1.381 (6)
O2—C7	1.199 (3)	C11—C12	1.361 (6)
N1—C7	1.345 (4)	C12—C13	1.370 (5)
N1—C8	1.409 (4)	C2—H2	0.9300
N1—H1	0.8600	C3—H3	0.9300
C1—C2	1.365 (4)	C4—H4	0.9300
C1—C6	1.363 (5)	C5—H5	0.9300
C2—C3	1.368 (5)	C6—H6	0.9300
C3—C4	1.365 (6)	C9—H9	0.9300
C4—C5	1.376 (4)	C10—H10	0.9300
C5—C6	1.370 (5)	C11—H11	0.9300
C8—C13	1.389 (5)	C12—H12	0.9300
C8—C9	1.374 (4)	C13—H13	0.9300

O2···C6	3.087 (5)	C10···H3^ix	3.0700
O2···C9	3.005 (4)	C13···H6ⁱⁱⁱ	3.0700
O2···N1ⁱ	2.976 (3)	H1···H13	2.4900
O1···H9ⁱⁱ	2.7100	H1···O2ⁱⁱ	2.1400
O2···H5ⁱⁱⁱ	2.7500	H1···H9ⁱⁱ	2.5900
O2···H9	2.6100	H3···C9^x	3.0400
O2···H1ⁱ	2.1400	H3···C10^x	3.0700
N1···O2ⁱⁱ	2.976 (3)	H4···H12^xi	2.5300
C1···C10^iv	3.579 (5)	H5···O2^v	2.7500
C5···C7^v	3.576 (5)	H5···C3^xii	3.0800
C6···O2	3.087 (5)	H6···C7	2.9500
C6···C7^v	3.592 (6)	H6···C8^v	2.9500
C7···C6ⁱⁱⁱ	3.592 (6)	H6···C13^v	3.0700
C7···C5ⁱⁱⁱ	3.576 (5)	H6···H13^viii	2.5700
C9···O2	3.005 (4)	H9···O2	2.6100
C10···C1^vi	3.579 (5)	H9···C7	2.8600
C2···H11^iv	3.0600	H9···O1ⁱ	2.7100
C3···H5^vii	3.0800	H9···H1ⁱ	2.5900
C6···H13^viii	3.0500	H11···C2^vi	3.0600
C7···H9	2.8600	H12···H4^xiii	2.5300
C7···H6	2.9500	H13···H1	2.4900
C8···H6ⁱⁱⁱ	2.9500	H13···C6^xiv	3.0500
C9···H3^ix	3.0400	H13···H6^xiv	2.5700

C1—O1—C7	118.6 (2)	C8—C13—C12	120.0 (3)
C7—N1—C8	125.1 (3)	C1—C2—H2	120.00
C7—N1—H1	117.00	C3—C2—H2	120.00
C8—N1—H1	117.00	C2—C3—H3	120.00
O1—C1—C2	117.6 (3)	C4—C3—H3	120.00
O1—C1—C6	120.5 (3)	C3—C4—H4	120.00
C2—C1—C6	121.5 (3)	C5—C4—H4	120.00
C1—C2—C3	119.1 (4)	C4—C5—H5	120.00
C2—C3—C4	120.5 (3)	C6—C5—H5	120.00
C3—C4—C5	119.8 (3)	C1—C6—H6	120.00
C4—C5—C6	120.1 (4)	C5—C6—H6	120.00
C1—C6—C5	119.1 (3)	C8—C9—H9	120.00
O1—C7—O2	124.4 (3)	C10—C9—H9	120.00
O1—C7—N1	108.0 (2)	C9—C10—H10	120.00
O2—C7—N1	127.5 (3)	C11—C10—H10	120.00
N1—C8—C9	122.6 (3)	C10—C11—H11	120.00
C9—C8—C13	119.8 (3)	C12—C11—H11	120.00
N1—C8—C13	117.7 (3)	C11—C12—H12	120.00
C8—C9—C10	119.3 (3)	C13—C12—H12	120.00
C9—C10—C11	120.8 (3)	C8—C13—H13	120.00
C10—C11—C12	119.3 (4)	C12—C13—H13	120.00
C11—C12—C13	120.9 (4)

C7—O1—C1—C2	−119.0 (3)	C1—C2—C3—C4	0.3 (6)
C7—O1—C1—C6	68.1 (4)	C2—C3—C4—C5	−0.4 (6)
C1—O1—C7—O2	3.9 (5)	C3—C4—C5—C6	1.2 (6)
C1—O1—C7—N1	−178.6 (3)	C4—C5—C6—C1	−1.8 (6)
C8—N1—C7—O1	−172.7 (3)	N1—C8—C9—C10	−179.4 (3)
C7—N1—C8—C13	138.2 (3)	C13—C8—C9—C10	−0.6 (5)
C8—N1—C7—O2	4.7 (6)	N1—C8—C13—C12	178.2 (3)
C7—N1—C8—C9	−43.0 (5)	C9—C8—C13—C12	−0.7 (5)
O1—C1—C2—C3	−173.7 (3)	C8—C9—C10—C11	1.1 (5)
C2—C1—C6—C5	1.6 (6)	C9—C10—C11—C12	−0.3 (6)
C6—C1—C2—C3	−0.9 (6)	C10—C11—C12—C13	−1.0 (6)
O1—C1—C6—C5	174.2 (3)	C11—C12—C13—C8	1.5 (6)

Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z; (iii) x, y, z−1; (iv) x+1/2, −y+1/2, z+1; (v) x, y, z+1; (vi) x−1/2, −y+1/2, z−1; (vii) −x, −y+1, z−1/2; (viii) x−1/2, −y+1/2, z+1; (ix) −x+1/2, y−1/2, z−1/2; (x) −x+1/2, y+1/2, z+1/2; (xi) −x+1/2, y+1/2, z+3/2; (xii) −x, −y+1, z+1/2; (xiii) −x+1/2, y−1/2, z−3/2; (xiv) x+1/2, −y+1/2, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.8600	2.1400	2.976 (3)	165.00
C3—H3···Cg2^x	0.9300	2.8000	3.673 (4)	156.00
C10—H10···Cg1^vi	0.9300	2.8600	3.599 (4)	137.00

Symmetry codes: (ii) x+1/2, −y+1/2, z; (vi) x−1/2, −y+1/2, z−1; (x) −x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁NO₂
M_r	213.23
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	9.4734 (9), 19.5825 (17), 5.8509 (5)
V (Å³)	1085.42 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.12 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.985, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6579, 1505, 751
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.086, 0.97
No. of reflections	1505
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.17

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (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
N1—H1···O2ⁱ	0.8600	2.1400	2.976 (3)	165.00
C3—H3···Cg2ⁱⁱ	0.9300	2.8000	3.673 (4)	156.00
C10—H10···Cg1ⁱⁱⁱ	0.9300	2.8600	3.599 (4)	137.00

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

Acknowledgements

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

References

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