Methyl N-(4-chloro­phen­yl)carbamate

Abstract

In the title compound, C₈H₈ClNO₂, the dihedral angle between the chloro­benzene ring and the side chain is 8.79 (11)°. In the crystal, mol­ecules are linked by N—H⋯O hydrogen bonds into a C(4) chain propagating in the b-axis direction.

Related literature

For related structures, see: Li (2011a ▶,b ▶).

Experimental

Crystal data

• C₈H₈ClNO₂

• M _r = 185.60

• Monoclinic,

• a = 11.126 (2) Å

• b = 9.833 (2) Å

• c = 8.0076 (16) Å

• β = 99.34 (3)°

• V = 864.5 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.40 mm⁻¹

• T = 293 K

• 0.23 × 0.20 × 0.18 mm

Data collection

• Bruker SMART CCD diffractometer

• 8281 measured reflections

• 1987 independent reflections

• 1011 reflections with I > 2σ(I)

• R _int = 0.036

Refinement

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.159

• S = 1.06

• 1987 reflections

• 109 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811037123/hb6394Isup3.cml

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
N1—H1A⋯O2i	0.86	2.22	3.069 (2)	168

Symmetry code: (i) .

supplementary crystallographic information

Experimental

A mixture of methanol (0.06 mol), and (4-chlorophenyl)carbamic chloride (0.06 mol) was stirred in refluxing ethanol (15 ml) for 4 h to afford the title compound (0.05 mol, yield 83%). Colourless blocks of the title compound were obtained by recrystallization from ethanol at room temperature.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93–0.97 Å; N—H = 0.86Å and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Figures

Fig. 1.

The molecular structure of the title compound showing 50% probability displacement ellipsoids.

Crystal data

C8H8ClNO2	F(000) = 384
Mr = 185.60	Dx = 1.426 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1987 reflections
a = 11.126 (2) Å	θ = 3.0–27.2°
b = 9.833 (2) Å	µ = 0.40 mm−1
c = 8.0076 (16) Å	T = 293 K
β = 99.34 (3)°	Block, colorless
V = 864.5 (3) Å3	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	1011 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
graphite	θmax = 27.5°, θmin = 3.3°
φ and ω scans	h = −14→13
8281 measured reflections	k = −12→12
1987 independent reflections	l = −10→10

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.081P)2 + 0.0499P] where P = (Fo2 + 2Fc2)/3
1987 reflections	(Δ/σ)max < 0.001
109 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.51185 (8)	0.66723 (9)	0.21431 (13)	0.1092 (4)
N1	0.95328 (17)	0.52547 (19)	0.6982 (3)	0.0611 (5)
H1A	0.9543	0.4420	0.7304	0.073*
O2	1.06775 (16)	0.71949 (15)	0.7364 (2)	0.0699 (5)
C8	0.8511 (2)	0.56561 (19)	0.5821 (3)	0.0527 (6)
O1	1.12660 (16)	0.52441 (16)	0.8735 (2)	0.0749 (5)
C2	1.0498 (2)	0.6012 (2)	0.7656 (3)	0.0570 (6)
C7	0.8409 (2)	0.6894 (2)	0.4978 (3)	0.0628 (6)
H7A	0.9042	0.7521	0.5166	0.075*
C6	0.7360 (2)	0.7191 (2)	0.3855 (3)	0.0660 (7)
H6A	0.7294	0.8021	0.3290	0.079*
C5	0.6422 (2)	0.6283 (2)	0.3568 (3)	0.0665 (7)
C4	0.6513 (2)	0.5048 (2)	0.4395 (3)	0.0715 (7)
H4A	0.5878	0.4423	0.4195	0.086*
C3	0.7548 (2)	0.4750 (2)	0.5514 (3)	0.0644 (6)
H3A	0.7604	0.3920	0.6079	0.077*
C1	1.2359 (3)	0.5899 (3)	0.9546 (4)	0.0819 (8)
H1B	1.2841	0.5264	1.0282	0.123*
H1C	1.2151	0.6659	1.0196	0.123*
H1D	1.2817	0.6212	0.8703	0.123*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0837 (6)	0.1053 (7)	0.1253 (8)	−0.0005 (4)	−0.0225 (5)	0.0310 (5)
N1	0.0645 (12)	0.0440 (10)	0.0726 (14)	−0.0029 (8)	0.0044 (10)	0.0032 (8)
O2	0.0731 (11)	0.0436 (9)	0.0893 (13)	−0.0026 (7)	0.0018 (9)	−0.0033 (8)
C8	0.0568 (13)	0.0435 (11)	0.0582 (14)	0.0003 (9)	0.0104 (11)	−0.0046 (9)
O1	0.0764 (12)	0.0545 (9)	0.0866 (13)	−0.0024 (8)	−0.0085 (10)	0.0031 (8)
C2	0.0626 (14)	0.0463 (12)	0.0608 (15)	0.0040 (10)	0.0063 (11)	−0.0061 (10)
C7	0.0694 (16)	0.0509 (12)	0.0679 (16)	−0.0083 (10)	0.0106 (13)	0.0044 (10)
C6	0.0761 (17)	0.0530 (13)	0.0683 (17)	−0.0025 (11)	0.0105 (13)	0.0114 (11)
C5	0.0677 (16)	0.0597 (13)	0.0713 (17)	0.0040 (12)	0.0086 (13)	0.0046 (11)
C4	0.0665 (16)	0.0555 (13)	0.0897 (19)	−0.0079 (11)	0.0045 (14)	0.0013 (13)
C3	0.0683 (15)	0.0418 (11)	0.0811 (17)	−0.0030 (10)	0.0059 (13)	0.0041 (10)
C1	0.0753 (19)	0.0700 (16)	0.091 (2)	−0.0008 (13)	−0.0140 (15)	−0.0020 (14)

Geometric parameters (Å, °)

Cl1—C5	1.736 (3)	C7—H7A	0.9300
N1—C2	1.345 (3)	C6—C5	1.364 (4)
N1—C8	1.404 (3)	C6—H6A	0.9300
N1—H1A	0.8600	C5—C4	1.379 (3)
O2—C2	1.209 (3)	C4—C3	1.371 (3)
C8—C3	1.385 (3)	C4—H4A	0.9300
C8—C7	1.388 (3)	C3—H3A	0.9300
O1—C2	1.345 (3)	C1—H1B	0.9600
O1—C1	1.435 (3)	C1—H1C	0.9600
C7—C6	1.384 (4)	C1—H1D	0.9600
C2—N1—C8	128.2 (2)	C6—C5—C4	120.1 (2)
C2—N1—H1A	115.9	C6—C5—Cl1	120.07 (19)
C8—N1—H1A	115.9	C4—C5—Cl1	119.9 (2)
C3—C8—C7	118.6 (2)	C3—C4—C5	119.4 (2)
C3—C8—N1	117.20 (19)	C3—C4—H4A	120.3
C7—C8—N1	124.2 (2)	C5—C4—H4A	120.3
C2—O1—C1	116.3 (2)	C4—C3—C8	121.5 (2)
O2—C2—O1	123.8 (2)	C4—C3—H3A	119.3
O2—C2—N1	126.9 (2)	C8—C3—H3A	119.3
O1—C2—N1	109.2 (2)	O1—C1—H1B	109.5
C6—C7—C8	119.7 (2)	O1—C1—H1C	109.5
C6—C7—H7A	120.2	H1B—C1—H1C	109.5
C8—C7—H7A	120.2	O1—C1—H1D	109.5
C5—C6—C7	120.8 (2)	H1B—C1—H1D	109.5
C5—C6—H6A	119.6	H1C—C1—H1D	109.5
C7—C6—H6A	119.6

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2i	0.86	2.22	3.069 (2)	168

Symmetry codes: (i) −x+2, y−1/2, −z+3/2.