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Acta Cryst. (2009). E65, o2999    [ doi:10.1107/S1600536809045929 ]

3-(2-Bromophenyl)-N-phenyloxirane-2-carboxamide

L. He, H.-M. Qin and L.-M. Chen

Abstract top

In the molecule of the title compound, C15H12BrNO2, the two benzene rings adopt a syn configuration with respect to the epoxy ring; the dihedral angles between the epoxy ring and the two benzene rings are 59.90 (13) and 68.01 (12)°. Intermolecular N-H...O and C-H...O hydrogen bonding is present in the crystal structure.

Comment top

Epoxides are important intermediates in organic synthesis. Glycidic esters and amides are particularly useful as they can be further transformed to key intermediates of several pharmaceutical products (Flisak et al. 1993; Watanabe et al. 1998). The Darzens reaction, is one of the most powerful methodologies for the synthesis of α, β-epoxy carbonyl and related compounds (Zhu & Espenson, 1995). We report herein the crystal structure of the title compound.

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. In the molecule, the two phenyl ring adopts a cis configuration about the epoxides ring. The dihedral angle between the C1—C6 and C10—C15 is 77.05 (7)°, O1/C7/C8 epoxide ring makes dihedral angles of 59.90 (13)° and 68.01 (12)° with C6 and C15 phenyl ring, respectively, which is similar to that found in a related structure (He & Chen, 2009). The crystal packing is stabilized by N—H···0 and C—H···0 hydrogen bonding (Table 1).

Related literature top

For epoxide-containing compounds used as building blocks in synthesis, see: Flisak et al. (1993); Watanabe et al. (1998); Zhu & Espenson (1995). For related structures, see: He (2009); He & Chen (2009).

Experimental top

2-Chloro-N-phenylacetamide (0.17 g, 1.0 mmol) and potassium hydroxide (0.112 g, 2.0 mmol) were dissolved in acetonitrile (2 ml). To the solution was added 2-bromophenylaldehyde (0.15 g, 1.0 mmol) at 298 K, the solution was stirred for 60 min and removal of solvent under reduced pressure, the residue was purified through column chromatography. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution at room temperature for 1 d.

Refinement top

Imine H atom was located in a difference Fourier map and refined isotropically. The carbon-bound hydrogen atoms were placed in calculated positions, with C—H = 0.93–0.98 Å, and refined using a riding model with Uiso(H) =1.2Ueq(C).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).
3-(2-Bromophenyl)-N-phenyloxirane-2-carboxamide top
Crystal data top
C15H12BrNO2F(000) = 640
Mr = 318.17Dx = 1.534 Mg m−3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2abCell parameters from 15647 reflections
a = 6.7170 (1) Åθ = 2.2–72.1°
b = 10.0370 (2) ŵ = 4.05 mm−1
c = 20.4287 (3) ÅT = 295 K
V = 1377.27 (4) Å3Block, colorless
Z = 40.40 × 0.40 × 0.36 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer		2701 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source2675 reflections with I > 2σ(I)
mirrorRint = 0.028
Detector resolution: 15.9149 pixels mm-1θmax = 72.3°, θmin = 4.3°
ω scansh = −8→8
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		k = −11→12
Tmin = 0.294, Tmax = 0.324l = −24→25
17721 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.028 w = 1/[σ2(Fo2) + (0.035P)2 + 0.5235P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.069(Δ/σ)max = 0.001
S = 1.00Δρmax = 0.33 e Å−3
2701 reflectionsΔρmin = −0.42 e Å−3
177 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0074 (5)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1104 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.008 (18)
Crystal data top
C15H12BrNO2V = 1377.27 (4) Å3
Mr = 318.17Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 6.7170 (1) ŵ = 4.05 mm−1
b = 10.0370 (2) ÅT = 295 K
c = 20.4287 (3) Å0.40 × 0.40 × 0.36 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer		2701 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)		2675 reflections with I > 2σ(I)
Tmin = 0.294, Tmax = 0.324Rint = 0.028
17721 measured reflectionsθmax = 72.3°
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.069Δρmax = 0.33 e Å−3
S = 1.00Δρmin = −0.42 e Å−3
2701 reflectionsAbsolute structure: Flack (1983), 1104 Friedel pairs
177 parametersFlack parameter: −0.008 (18)
0 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
Br1−0.14003 (5)0.63054 (3)0.557209 (16)0.07563 (15)
O1−0.1933 (3)0.23595 (16)0.66346 (9)0.0567 (4)
O2−0.0059 (3)0.50889 (16)0.76057 (10)0.0637 (5)
N10.1077 (3)0.29560 (18)0.75313 (9)0.0437 (4)
C50.1656 (4)0.2794 (3)0.59008 (13)0.0582 (6)
H50.14800.20150.61400.070*
C60.0186 (3)0.3772 (2)0.59138 (10)0.0470 (5)
C150.3410 (4)0.4080 (2)0.82806 (11)0.0520 (5)
H150.25880.48230.83140.062*
C9−0.0201 (3)0.3947 (2)0.74074 (11)0.0440 (4)
C8−0.1951 (3)0.3600 (2)0.69813 (11)0.0467 (5)
H8−0.32530.38930.71430.056*
C100.2882 (3)0.3016 (2)0.78857 (10)0.0407 (4)
C7−0.1724 (3)0.3564 (2)0.62606 (11)0.0499 (5)
H7−0.29120.38280.60140.060*
C110.4155 (3)0.1931 (2)0.78350 (11)0.0494 (5)
H110.38280.12270.75590.059*
C10.0535 (4)0.4931 (2)0.55591 (11)0.0502 (5)
C120.5905 (4)0.1889 (3)0.81914 (14)0.0607 (6)
H120.67340.11490.81620.073*
C20.2261 (5)0.5119 (3)0.52052 (13)0.0654 (7)
H20.24770.59080.49770.078*
C30.3657 (5)0.4116 (3)0.51958 (14)0.0723 (7)
H30.48150.42270.49520.087*
C130.6420 (4)0.2934 (3)0.85879 (13)0.0655 (7)
H130.75940.29050.88290.079*
C140.5199 (4)0.4020 (3)0.86281 (13)0.0641 (7)
H140.55670.47340.88920.077*
C40.3375 (4)0.2965 (3)0.55369 (14)0.0680 (7)
H40.43340.22970.55250.082*
H10.074 (3)0.225 (3)0.7406 (12)0.037 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0896 (2)0.05464 (17)0.0827 (2)0.01486 (15)0.01432 (17)0.01807 (14)
O10.0611 (10)0.0400 (8)0.0689 (10)−0.0133 (7)−0.0136 (8)0.0087 (7)
O20.0677 (10)0.0342 (8)0.0891 (12)0.0036 (8)−0.0200 (10)−0.0011 (8)
N10.0487 (10)0.0311 (8)0.0515 (9)−0.0032 (8)−0.0056 (8)−0.0002 (7)
C50.0618 (15)0.0547 (13)0.0581 (13)0.0042 (12)−0.0126 (12)−0.0037 (11)
C60.0500 (11)0.0458 (11)0.0453 (10)−0.0031 (11)−0.0122 (8)−0.0024 (9)
C150.0584 (13)0.0455 (11)0.0520 (11)0.0046 (10)−0.0047 (11)−0.0052 (9)
C90.0473 (10)0.0332 (10)0.0515 (11)−0.0039 (8)−0.0011 (9)0.0071 (8)
C80.0418 (10)0.0375 (10)0.0609 (12)−0.0063 (9)−0.0036 (8)0.0089 (10)
C100.0442 (10)0.0386 (10)0.0392 (9)−0.0030 (8)0.0020 (8)0.0079 (8)
C70.0459 (11)0.0448 (11)0.0589 (12)−0.0055 (10)−0.0150 (9)0.0106 (10)
C110.0517 (12)0.0425 (11)0.0541 (12)0.0011 (9)0.0042 (9)0.0029 (9)
C10.0604 (12)0.0462 (11)0.0441 (10)−0.0012 (9)−0.0009 (10)−0.0020 (10)
C120.0477 (12)0.0615 (14)0.0730 (16)0.0100 (11)0.0029 (11)0.0138 (12)
C20.0782 (17)0.0652 (16)0.0528 (13)−0.0086 (14)0.0095 (12)−0.0001 (12)
C30.0631 (16)0.091 (2)0.0629 (15)−0.0026 (16)0.0099 (14)−0.0143 (14)
C130.0525 (13)0.0838 (19)0.0602 (13)0.0019 (15)−0.0100 (12)0.0111 (13)
C140.0696 (16)0.0679 (16)0.0548 (13)−0.0056 (14)−0.0149 (12)−0.0083 (12)
C40.0624 (15)0.0748 (17)0.0669 (15)0.0141 (13)−0.0095 (15)−0.0156 (14)
Geometric parameters (Å, °) top
Br1—C11.896 (2)C8—H80.9800
O1—C81.433 (3)C10—C111.388 (3)
O1—C71.437 (3)C7—H70.9800
O2—C91.219 (3)C11—C121.384 (4)
N1—C91.338 (3)C11—H110.9300
N1—C101.414 (3)C1—C21.380 (4)
N1—H10.78 (3)C12—C131.370 (4)
C5—C41.384 (4)C12—H120.9300
C5—C61.392 (3)C2—C31.375 (5)
C5—H50.9300C2—H20.9300
C6—C11.390 (3)C3—C41.363 (5)
C6—C71.481 (3)C3—H30.9300
C15—C101.385 (3)C13—C141.366 (4)
C15—C141.397 (4)C13—H130.9300
C15—H150.9300C14—H140.9300
C9—C81.503 (3)C4—H40.9300
C8—C71.481 (3)
C8—O1—C762.11 (14)O1—C7—H7114.9
C9—N1—C10127.97 (19)C6—C7—H7114.9
C9—N1—H1115.1 (18)C8—C7—H7114.9
C10—N1—H1116.8 (18)C12—C11—C10120.6 (2)
C4—C5—C6121.0 (3)C12—C11—H11119.7
C4—C5—H5119.5C10—C11—H11119.7
C6—C5—H5119.5C2—C1—C6121.9 (2)
C1—C6—C5117.4 (2)C2—C1—Br1118.96 (19)
C1—C6—C7120.9 (2)C6—C1—Br1119.09 (17)
C5—C6—C7121.7 (2)C13—C12—C11120.1 (2)
C10—C15—C14118.9 (2)C13—C12—H12119.9
C10—C15—H15120.6C11—C12—H12119.9
C14—C15—H15120.6C3—C2—C1118.7 (3)
O2—C9—N1125.9 (2)C3—C2—H2120.6
O2—C9—C8118.1 (2)C1—C2—H2120.6
N1—C9—C8116.05 (19)C4—C3—C2121.2 (3)
O1—C8—C759.09 (14)C4—C3—H3119.4
O1—C8—C9118.74 (18)C2—C3—H3119.4
C7—C8—C9120.07 (19)C14—C13—C12119.7 (2)
O1—C8—H8115.7C14—C13—H13120.2
C7—C8—H8115.7C12—C13—H13120.2
C9—C8—H8115.7C13—C14—C15121.3 (2)
C15—C10—C11119.4 (2)C13—C14—H14119.3
C15—C10—N1123.5 (2)C15—C14—H14119.3
C11—C10—N1117.1 (2)C3—C4—C5119.7 (3)
O1—C7—C6117.2 (2)C3—C4—H4120.1
O1—C7—C858.80 (14)C5—C4—H4120.1
C6—C7—C8124.15 (18)
C4—C5—C6—C1−1.3 (3)C9—C8—C7—O1107.5 (2)
C4—C5—C6—C7175.4 (2)O1—C8—C7—C6−103.6 (2)
C10—N1—C9—O2−3.1 (4)C9—C8—C7—C63.9 (4)
C10—N1—C9—C8176.5 (2)C15—C10—C11—C122.1 (3)
C7—O1—C8—C9−109.7 (2)N1—C10—C11—C12−176.9 (2)
O2—C9—C8—O1167.2 (2)C5—C6—C1—C20.1 (3)
N1—C9—C8—O1−12.5 (3)C7—C6—C1—C2−176.7 (2)
O2—C9—C8—C798.3 (3)C5—C6—C1—Br1−178.98 (16)
N1—C9—C8—C7−81.4 (3)C7—C6—C1—Br14.2 (3)
C14—C15—C10—C11−1.2 (3)C10—C11—C12—C13−1.4 (4)
C14—C15—C10—N1177.8 (2)C6—C1—C2—C31.1 (4)
C9—N1—C10—C1514.1 (3)Br1—C1—C2—C3−179.8 (2)
C9—N1—C10—C11−166.9 (2)C1—C2—C3—C4−1.2 (4)
C8—O1—C7—C6115.3 (2)C11—C12—C13—C14−0.2 (4)
C1—C6—C7—O1−177.83 (19)C12—C13—C14—C151.1 (4)
C5—C6—C7—O15.5 (3)C10—C15—C14—C13−0.4 (4)
C1—C6—C7—C8−108.6 (2)C2—C3—C4—C50.0 (4)
C5—C6—C7—C874.7 (3)C6—C5—C4—C31.3 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.79 (3)2.22 (3)2.971 (2)161 (2)
C15—H15···O1ii0.932.593.442 (3)153
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.79 (3)2.22 (3)2.971 (2)161 (2)
C15—H15···O1ii0.932.593.442 (3)153
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.
Acknowledgements top

The diffraction data were collected at The Centre for Testing and Analysis, Sichuan University. We acknowledge financial support from China West Normal University.

references
References top

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