organic compounds
Methyl N-(2-bromo-4-chlorophenyl)carbamate
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
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 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).
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 .
details are summarized in Table 2Structural data
CCDC reference: 1815604
https://doi.org/10.1107/S2414314618000548/sj4153sup1.cif
contains datablock I. DOI: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
Data collection: CrysAlis PRO (Agilent, 2014); cell
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).C8H7BrClNO2 | Z = 2 |
Mr = 264.51 | F(000) = 260 |
Triclinic, P1 | Dx = 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 |
Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer | 1777 reflections with I > 2σ(I) |
ω scans | Rint = 0.019 |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014) | θmax = 74.0°, θmin = 4.1° |
Tmin = 0.776, Tmax = 0.891 | h = −5→5 |
2938 measured reflections | k = −10→11 |
1847 independent reflections | l = −14→11 |
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(Fo2) + (0.040P)2 + 0.157P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
1847 reflections | Δρmax = 0.30 e Å−3 |
119 parameters | Δρmin = −0.61 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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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