Methyl N-(2-bromo-4-chloro­phen­yl)carbamate

El-Hiti, G.A.; Smith, K.; Hegazy, A.S.; Alshammari, M.B.; Kariuki, B.M.

doi:10.1107/S2414314618000548

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180054

https://doi.org/10.1107/S2414314618000548

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Methyl N-(2-bromo-4-chlorophenyl)carbamate

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Mohammed B. Alshammari ^c and Benson M. Kariuki ^b ‡

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and ^cChemistry Department, College of Sciences and Humanities, Prince Sattam bin Abdulaziz University, PO Box 83, Al-Kharij 11942, Saudi Arabia
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by J. Simpson, University of Otago, New Zealand (Received 5 January 2018; accepted 9 January 2018; online 12 January 2018)

In the title molecule, C₈H₇BrClNO₂, the bromochlorophenyl ring is inclined to the methylcarbamate unit by 32.73 (7)°. In the crystal, N—H⋯O hydrogen bonds form chains of molecules parallel to [100].

Keywords: crystal structure; hydrogen bond; carbamate.

CCDC reference: 1815604

Structure description

Carbamate derivatives show a variety of biological activities (Krátký et al., 2014 ; Smith et al., 2014 ; Yang et al., 2012 ). They can be synthesized using a variety of convenient processes (Blaser et al., 2012 ; Smith et al., 2012 ; Ibrahim et al., 2011 ; Porzelle et al., 2009 ; Lee et al., 2009 ; Lebel & Leogane, 2006 ; Caddick et al., 2003 ). The X-ray crystal structure of the related tert-butyl 2-phenylethylcarbamate was published recently (El-Hiti et al., 2016 ).

In the title molecule (Fig. 1), the dihedral angle between the bromochlorophenyl and methylcarbamate groups is 32.73 (7)°. In the crystal, N—H⋯O hydrogen bonds, Table 1, form chains parallel to [100], (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	2.19	2.885 (2)	135
Symmetry code: (i) x+1, y, z.

Figure 1
An ORTEP representation (50% probability level) of the title molecule.

Figure 2
A segment of the crystal structure, viewed along b, showing the N—H⋯O hydrogen bonds as dotted lines.

Synthesis and crystallization

The title compound was synthesized from the reaction of 2-bromo-4-chloroaniline and dimethyl dicarbonate in dichloromethane in the presence of triethylamine. Recrystallization of the crude product from diethyl ether solution gave the title compound as colourless crystals, m.p. 88–89°C (lit. 86–89 °C; Moghaddam et al., 2016 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₇BrClNO₂
M_r	264.51
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	4.6637 (3), 9.4598 (6), 11.9898 (7)
α, β, γ (°)	111.639 (5), 101.035 (5), 93.712 (5)
V (Å³)	477.25 (5)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	8.19
Crystal size (mm)	0.31 × 0.20 × 0.15

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.776, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	2938, 1847, 1777
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.063, 1.08
No. of reflections	1847
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.61
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1815604

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000548/sj4153sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000548/sj4153Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000548/sj4153Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Methyl N-(2-bromo-4-chlorophenyl)carbamate top

Crystal data top

C₈H₇BrClNO₂	Z = 2
M_r = 264.51	F(000) = 260
Triclinic, P1	D_x = 1.841 Mg m⁻³
a = 4.6637 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.4598 (6) Å	Cell parameters from 2127 reflections
c = 11.9898 (7) Å	θ = 5.1–74.1°
α = 111.639 (5)°	µ = 8.19 mm⁻¹
β = 101.035 (5)°	T = 150 K
γ = 93.712 (5)°	Block, colourless
V = 477.25 (5) Å³	0.31 × 0.20 × 0.15 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	1777 reflections with I > 2σ(I)
ω scans	R_int = 0.019
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	θ_max = 74.0°, θ_min = 4.1°
T_min = 0.776, T_max = 0.891	h = −5→5
2938 measured reflections	k = −10→11
1847 independent reflections	l = −14→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.040P)² + 0.157P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1847 reflections	Δρ_max = 0.30 e Å⁻³
119 parameters	Δρ_min = −0.61 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5832 (4)	0.2508 (2)	0.08977 (18)	0.0178 (4)
C2	0.7774 (4)	0.3658 (2)	0.19208 (19)	0.0189 (4)
C3	0.7777 (5)	0.3806 (2)	0.31131 (19)	0.0226 (4)
H3	0.9115	0.4585	0.3796	0.027*
C4	0.5803 (5)	0.2806 (3)	0.3295 (2)	0.0242 (4)
C5	0.3866 (5)	0.1654 (2)	0.2315 (2)	0.0230 (4)
H5	0.2525	0.0973	0.2455	0.028*
C6	0.3903 (5)	0.1504 (2)	0.1125 (2)	0.0210 (4)
H6	0.2592	0.0704	0.0449	0.025*
C7	0.3560 (5)	0.1832 (2)	−0.12754 (19)	0.0194 (4)
C8	0.2102 (6)	0.1130 (3)	−0.3419 (2)	0.0324 (5)
H8A	0.1401	0.0058	−0.3581	0.049*
H8B	0.2882	0.1174	−0.4110	0.049*
H8C	0.0459	0.1726	−0.3323	0.049*
N1	0.5916 (4)	0.2373 (2)	−0.02987 (16)	0.0204 (3)
H1	0.7618	0.2661	−0.0424	0.024*
O1	0.1036 (3)	0.14673 (18)	−0.12501 (14)	0.0242 (3)
O2	0.4400 (3)	0.17650 (19)	−0.23043 (14)	0.0264 (3)
Cl1	0.57621 (15)	0.30115 (7)	0.47984 (5)	0.03750 (16)
Br1	1.04171 (4)	0.50705 (2)	0.16904 (2)	0.02356 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0170 (9)	0.0181 (9)	0.0196 (10)	0.0047 (7)	0.0063 (7)	0.0075 (7)
C2	0.0177 (9)	0.0181 (9)	0.0223 (10)	0.0019 (7)	0.0058 (8)	0.0091 (8)
C3	0.0241 (10)	0.0215 (9)	0.0200 (10)	−0.0003 (8)	0.0033 (8)	0.0070 (8)
C4	0.0310 (11)	0.0269 (11)	0.0194 (10)	0.0054 (9)	0.0097 (8)	0.0121 (8)
C5	0.0239 (10)	0.0219 (10)	0.0264 (11)	0.0013 (8)	0.0099 (8)	0.0115 (8)
C6	0.0202 (10)	0.0197 (9)	0.0222 (10)	0.0002 (7)	0.0058 (8)	0.0072 (8)
C7	0.0208 (10)	0.0194 (9)	0.0194 (10)	0.0048 (7)	0.0066 (8)	0.0079 (8)
C8	0.0341 (12)	0.0413 (13)	0.0194 (10)	0.0026 (10)	0.0017 (9)	0.0117 (10)
N1	0.0157 (8)	0.0256 (9)	0.0198 (8)	−0.0002 (6)	0.0058 (6)	0.0084 (7)
O1	0.0159 (7)	0.0315 (8)	0.0243 (8)	0.0010 (6)	0.0052 (6)	0.0101 (6)
O2	0.0219 (8)	0.0402 (9)	0.0198 (7)	0.0013 (6)	0.0049 (6)	0.0152 (7)
Cl1	0.0549 (4)	0.0381 (3)	0.0208 (3)	−0.0052 (3)	0.0122 (2)	0.0132 (2)
Br1	0.02532 (14)	0.02146 (14)	0.02454 (14)	−0.00329 (9)	0.00644 (9)	0.01045 (10)

Geometric parameters (Å, º) top

C1—C6	1.400 (3)	C5—H5	0.9500
C1—N1	1.401 (3)	C6—H6	0.9500
C1—C2	1.404 (3)	C7—O1	1.214 (3)
C2—C3	1.384 (3)	C7—O2	1.345 (2)
C2—Br1	1.890 (2)	C7—N1	1.354 (3)
C3—C4	1.381 (3)	C8—O2	1.439 (3)
C3—H3	0.9500	C8—H8A	0.9800
C4—C5	1.381 (3)	C8—H8B	0.9800
C4—Cl1	1.744 (2)	C8—H8C	0.9800
C5—C6	1.384 (3)	N1—H1	0.8800

C6—C1—N1	122.34 (18)	C5—C6—H6	119.3
C6—C1—C2	117.59 (19)	C1—C6—H6	119.3
N1—C1—C2	120.06 (18)	O1—C7—O2	123.82 (19)
C3—C2—C1	121.46 (19)	O1—C7—N1	126.17 (19)
C3—C2—Br1	118.43 (15)	O2—C7—N1	110.00 (17)
C1—C2—Br1	120.11 (15)	O2—C8—H8A	109.5
C4—C3—C2	119.0 (2)	O2—C8—H8B	109.5
C4—C3—H3	120.5	H8A—C8—H8B	109.5
C2—C3—H3	120.5	O2—C8—H8C	109.5
C5—C4—C3	121.44 (19)	H8A—C8—H8C	109.5
C5—C4—Cl1	119.54 (17)	H8B—C8—H8C	109.5
C3—C4—Cl1	119.02 (17)	C7—N1—C1	124.53 (17)
C4—C5—C6	119.14 (19)	C7—N1—H1	117.7
C4—C5—H5	120.4	C1—N1—H1	117.7
C6—C5—H5	120.4	C7—O2—C8	115.05 (17)
C5—C6—C1	121.39 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.19	2.885 (2)	135

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

Footnotes

‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.

Funding information

This project was supported by King Saud University, Deanship of Scientific Research, Research Chairs and Cardiff University.

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