3-(4-Nitro­phen­yl)-N-phenyl­oxirane-2-carboxamide

He, L.

doi:10.1107/S1600536809029699

organic compounds

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Volume 65| Part 8| August 2009| Page o2052

doi:10.1107/S1600536809029699

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3-(4-Nitrophenyl)-N-phenyloxirane-2-carboxamide

Long He ^a ^*

^aCollege of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, People's Republic of China
^*Correspondence e-mail: helongcwnu@yahoo.com.cn

(Received 22 July 2009; accepted 25 July 2009; online 31 July 2009)

The molecule of the title compound, C₁₅H₁₂N₂O₄, adopts a syn conformation with the terminal benzene rings located on the same sides of the central epoxide ring. The epoxide ring makes dihedral angles of 71.08 (18) and 60.83 (17)° with the two benzene rings. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For epoxide-containing compounds used as building blocks in synthesis, see: Righi et al. (1996 ); Bhatia et al. (1999 ); Meth-Cohn et al. (1999 ); Thijs et al. (1990 ).

Experimental

Crystal data

C₁₅H₁₂N₂O₄
M_r = 284.27
Monoclinic, P 2₁
a = 5.9800 (3) Å
b = 5.1960 (4) Å
c = 21.503 (5) Å
β = 96.105 (5)°
V = 664.35 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.36 × 0.30 × 0.10 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: none
6118 measured reflections
1515 independent reflections
821 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.042
S = 1.13
1515 reflections
194 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.39	3.267 (4)	158
C15—H15⋯O3ⁱⁱ	0.93	2.53	3.353 (4)	148
Symmetry codes: (i) x-1, y, z; (ii) x+1, y+1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; 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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029699/xu2566sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029699/xu2566Isup2.hkl

checkCIF report

Comment top

Oxiranecarboxamides are the key building blocks in the synthesis of natural products such as the Taxol side chain (Righi et al. 1996). Selective ring-opening reactions of oxiranes also provide powerful and efficient routes to a variety of useful compounds including 2,3-epoxyketone (Meth-Cohn et al. 1999), aziridinecarboxylate (Thijs et al. 1990). isoserine derivatives (Bhatia et al. 1999). The crystal structure of the title compound is reported here.

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The two phenyl ring is the cis conformation, the dihedral angle between the two phenyl ring is 77.34 (8)°. Epoxide ring makes dihedral angles of 71.08 (18)° and 60.83 (17)° with phenyl rings C1—C6 and C10—C15, respectively. The crystal packing is stabilized by C—H···0 hydrogen bonding (Table 1).

Related literature top

For epoxide-containing compounds used as building blocks in synthesis, see: Righi et al. (1996); Bhatia et al. (1999); Meth-Cohn et al. (1999); Thijs et al. (1990).

Experimental top

2-Chloro-N-phenylacetamide (0.17 g, 1.0 mmol) and sodium ethanolate (0.14 g, 2.0 mmol) were dissolved in acetonitrile (2 ml). To the solution was added 4-nitrophenylaldehyde (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 on silica gel to give compound (I). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.01 g) in ethanol (2 ml) and evaporating the solvent slowly at room temperature for about 3 d.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

3-(4-Nitrophenyl)-N-phenyloxirane-2-carboxamide top

Crystal data top

C₁₅H₁₂N₂O₄	F(000) = 296
M_r = 284.27	D_x = 1.421 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1633 reflections
a = 5.9800 (3) Å	θ = 2.9–29.0°
b = 5.1960 (4) Å	µ = 0.11 mm⁻¹
c = 21.503 (5) Å	T = 293 K
β = 96.105 (5)°	Block, colorless
V = 664.35 (17) Å³	0.36 × 0.30 × 0.10 mm
Z = 2

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	821 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.054
Graphite monochromator	θ_max = 26.4°, θ_min = 2.9°
ω scans	h = −7→7
6118 measured reflections	k = −6→5
1515 independent reflections	l = −26→26

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0006P)²] where P = (F_o² + 2F_c²)/3
1515 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.12 e Å⁻³
2 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₅H₁₂N₂O₄	V = 664.35 (17) Å³
M_r = 284.27	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.9800 (3) Å	µ = 0.11 mm⁻¹
b = 5.1960 (4) Å	T = 293 K
c = 21.503 (5) Å	0.36 × 0.30 × 0.10 mm
β = 96.105 (5)°

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	821 reflections with I > 2σ(I)
6118 measured reflections	R_int = 0.054
1515 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	2 restraints
wR(F²) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.12 e Å⁻³
1515 reflections	Δρ_min = −0.13 e Å⁻³
194 parameters

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

	x	y	z	U_iso*/U_eq
O4	0.6579 (3)	0.2311 (5)	0.48448 (11)	0.0686 (8)
O2	0.7928 (4)	1.2561 (5)	0.25607 (9)	0.0691 (7)
N1	0.8102 (5)	0.8270 (6)	0.17913 (12)	0.0573 (8)
O3	0.3472 (3)	0.2679 (5)	0.42342 (10)	0.0766 (8)
N2	0.5421 (5)	0.3314 (6)	0.44030 (13)	0.0566 (9)
C10	0.8251 (5)	0.9283 (6)	0.34170 (14)	0.0437 (9)
C14	0.8515 (4)	0.6302 (6)	0.42748 (13)	0.0459 (9)
H14	0.9301	0.5606	0.4632	0.055*
C4	0.7716 (6)	0.6203 (7)	0.13644 (14)	0.0511 (10)
C15	0.9424 (4)	0.8237 (7)	0.39512 (14)	0.0491 (9)
H15	1.0848	0.8861	0.4090	0.059*
O1	1.1883 (4)	0.7951 (6)	0.20507 (10)	0.0919 (9)
C13	0.6412 (5)	0.5415 (7)	0.40592 (15)	0.0398 (9)
C11	0.6126 (5)	0.8330 (7)	0.32131 (13)	0.0524 (10)
H11	0.5323	0.9008	0.2856	0.063*
C8	1.0022 (6)	1.1420 (7)	0.24713 (14)	0.0596 (10)
H8	1.1214	1.2660	0.2410	0.071*
C12	0.5216 (5)	0.6395 (7)	0.35375 (14)	0.0530 (10)
H12	0.3794	0.5755	0.3403	0.064*
C9	0.9241 (5)	1.1506 (7)	0.30983 (14)	0.0527 (10)
H9	0.9999	1.2786	0.3382	0.063*
C5	0.9264 (5)	0.5501 (8)	0.09757 (14)	0.0604 (11)
H5	1.0639	0.6348	0.0996	0.072*
C7	1.0093 (7)	0.9023 (7)	0.20860 (15)	0.0618 (11)
C6	0.8787 (6)	0.3529 (8)	0.05514 (15)	0.0726 (12)
H6	0.9847	0.3064	0.0285	0.087*
C3	0.5675 (5)	0.4925 (8)	0.13414 (15)	0.0646 (11)
H3	0.4623	0.5382	0.1611	0.078*
C1	0.6773 (6)	0.2246 (7)	0.05169 (15)	0.0703 (12)
H1	0.6462	0.0918	0.0231	0.084*
C2	0.5224 (5)	0.2959 (9)	0.09128 (17)	0.0710 (11)
H2	0.3850	0.2107	0.0892	0.085*
H4	0.678 (3)	0.890 (6)	0.1938 (12)	0.087 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0732 (16)	0.057 (2)	0.0750 (16)	−0.0043 (14)	0.0071 (12)	0.0141 (15)
O2	0.1047 (18)	0.0473 (19)	0.0558 (15)	0.0221 (16)	0.0106 (14)	−0.0014 (16)
N1	0.066 (2)	0.061 (3)	0.0451 (18)	0.019 (2)	0.0055 (17)	−0.004 (2)
O3	0.0612 (15)	0.070 (2)	0.0974 (17)	−0.0300 (15)	0.0046 (12)	−0.0074 (17)
N2	0.062 (2)	0.048 (3)	0.061 (2)	−0.0070 (19)	0.0153 (17)	−0.012 (2)
C10	0.054 (2)	0.040 (3)	0.038 (2)	−0.0007 (18)	0.0097 (17)	−0.0077 (19)
C14	0.047 (2)	0.045 (3)	0.044 (2)	−0.0014 (19)	−0.0018 (16)	−0.003 (2)
C4	0.070 (2)	0.047 (3)	0.036 (2)	0.022 (2)	0.0045 (19)	0.000 (2)
C15	0.0508 (19)	0.055 (3)	0.0412 (19)	−0.003 (2)	0.0016 (17)	−0.005 (2)
O1	0.0763 (16)	0.104 (2)	0.0930 (19)	0.0260 (17)	−0.0025 (14)	−0.047 (2)
C13	0.047 (2)	0.034 (3)	0.040 (2)	−0.0027 (17)	0.0094 (17)	−0.0042 (17)
C11	0.054 (2)	0.056 (3)	0.046 (2)	0.012 (2)	−0.0023 (17)	−0.001 (2)
C8	0.091 (3)	0.039 (3)	0.050 (2)	−0.005 (2)	0.0143 (19)	0.000 (2)
C12	0.046 (2)	0.061 (3)	0.051 (2)	−0.005 (2)	0.0018 (18)	−0.009 (2)
C9	0.074 (2)	0.040 (3)	0.044 (2)	0.003 (2)	0.0054 (19)	−0.007 (2)
C5	0.074 (2)	0.065 (3)	0.044 (2)	0.004 (2)	0.014 (2)	−0.009 (2)
C7	0.084 (3)	0.056 (3)	0.046 (2)	0.007 (2)	0.012 (2)	0.004 (2)
C6	0.085 (3)	0.075 (4)	0.058 (2)	0.004 (3)	0.009 (2)	−0.012 (3)
C3	0.061 (2)	0.069 (3)	0.064 (3)	0.015 (2)	0.008 (2)	0.008 (2)
C1	0.093 (3)	0.052 (3)	0.062 (3)	0.012 (3)	−0.008 (2)	−0.004 (2)
C2	0.068 (3)	0.065 (3)	0.077 (3)	−0.006 (2)	−0.008 (2)	0.004 (3)

Geometric parameters (Å, º) top

O4—N2	1.230 (3)	C13—C12	1.364 (3)
O2—C8	1.417 (3)	C11—C12	1.369 (4)
O2—C9	1.435 (3)	C11—H11	0.9300
N1—C7	1.346 (4)	C8—C9	1.474 (4)
N1—C4	1.416 (4)	C8—C7	1.499 (4)
N1—H4	0.940 (10)	C8—H8	0.9800
O3—N2	1.229 (2)	C12—H12	0.9300
N2—C13	1.477 (4)	C9—H9	0.9800
C10—C11	1.391 (3)	C5—C6	1.381 (4)
C10—C15	1.391 (4)	C5—H5	0.9300
C10—C9	1.497 (4)	C6—C1	1.371 (4)
C14—C15	1.368 (4)	C6—H6	0.9300
C14—C13	1.373 (3)	C3—C2	1.383 (5)
C14—H14	0.9300	C3—H3	0.9300
C4—C5	1.361 (4)	C1—C2	1.374 (4)
C4—C3	1.386 (4)	C1—H1	0.9300
C15—H15	0.9300	C2—H2	0.9300
O1—C7	1.216 (3)

C8—O2—C9	62.22 (18)	C9—C8—H8	114.1
C7—N1—C4	126.9 (3)	C7—C8—H8	114.1
C7—N1—H4	118.2 (19)	C13—C12—C11	119.4 (3)
C4—N1—H4	113.5 (19)	C13—C12—H12	120.3
O3—N2—O4	123.5 (3)	C11—C12—H12	120.3
O3—N2—C13	118.0 (3)	O2—C9—C8	58.28 (18)
O4—N2—C13	118.5 (3)	O2—C9—C10	117.0 (3)
C11—C10—C15	119.0 (3)	C8—C9—C10	125.1 (3)
C11—C10—C9	121.5 (3)	O2—C9—H9	114.7
C15—C10—C9	119.4 (3)	C8—C9—H9	114.7
C15—C14—C13	118.3 (3)	C10—C9—H9	114.7
C15—C14—H14	120.8	C4—C5—C6	119.9 (3)
C13—C14—H14	120.8	C4—C5—H5	120.1
C5—C4—C3	120.2 (3)	C6—C5—H5	120.1
C5—C4—N1	121.8 (4)	O1—C7—N1	125.3 (4)
C3—C4—N1	118.0 (3)	O1—C7—C8	119.5 (4)
C14—C15—C10	120.9 (3)	N1—C7—C8	115.2 (3)
C14—C15—H15	119.5	C1—C6—C5	121.0 (3)
C10—C15—H15	119.5	C1—C6—H6	119.5
C12—C13—C14	122.3 (3)	C5—C6—H6	119.5
C12—C13—N2	119.0 (3)	C2—C3—C4	119.1 (3)
C14—C13—N2	118.7 (3)	C2—C3—H3	120.4
C12—C11—C10	120.0 (3)	C4—C3—H3	120.4
C12—C11—H11	120.0	C6—C1—C2	118.8 (4)
C10—C11—H11	120.0	C6—C1—H1	120.6
O2—C8—C9	59.50 (19)	C2—C1—H1	120.6
O2—C8—C7	120.0 (3)	C1—C2—C3	121.0 (4)
C9—C8—C7	124.1 (3)	C1—C2—H2	119.5
O2—C8—H8	114.1	C3—C2—H2	119.5

C7—N1—C4—C5	−32.3 (5)	C7—C8—C9—C10	−4.9 (6)
C7—N1—C4—C3	149.1 (3)	C11—C10—C9—O2	−1.9 (4)
C13—C14—C15—C10	0.0 (4)	C15—C10—C9—O2	−178.1 (3)
C11—C10—C15—C14	−0.1 (4)	C11—C10—C9—C8	−70.6 (4)
C9—C10—C15—C14	176.2 (3)	C15—C10—C9—C8	113.2 (4)
C15—C14—C13—C12	0.0 (4)	C3—C4—C5—C6	0.8 (5)
C15—C14—C13—N2	179.6 (3)	N1—C4—C5—C6	−177.8 (3)
O3—N2—C13—C12	−6.0 (4)	C4—N1—C7—O1	−3.5 (5)
O4—N2—C13—C12	174.6 (3)	C4—N1—C7—C8	175.0 (3)
O3—N2—C13—C14	174.4 (3)	O2—C8—C7—O1	−174.5 (3)
O4—N2—C13—C14	−5.1 (4)	C9—C8—C7—O1	−103.0 (4)
C15—C10—C11—C12	0.1 (4)	O2—C8—C7—N1	6.9 (4)
C9—C10—C11—C12	−176.1 (3)	C9—C8—C7—N1	78.4 (4)
C9—O2—C8—C7	114.3 (4)	C4—C5—C6—C1	−0.4 (5)
C14—C13—C12—C11	0.1 (4)	C5—C4—C3—C2	−1.0 (5)
N2—C13—C12—C11	−179.6 (3)	N1—C4—C3—C2	177.7 (3)
C10—C11—C12—C13	−0.1 (4)	C5—C6—C1—C2	0.1 (5)
C8—O2—C9—C10	−116.3 (3)	C6—C1—C2—C3	−0.3 (5)
C7—C8—C9—O2	−107.6 (4)	C4—C3—C2—C1	0.7 (5)
O2—C8—C9—C10	102.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.39	3.267 (4)	158
C15—H15···O3ⁱⁱ	0.93	2.53	3.353 (4)	148

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₂O₄
M_r	284.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	5.9800 (3), 5.1960 (4), 21.503 (5)
β (°)	96.105 (5)
V (Å³)	664.35 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.36 × 0.30 × 0.10

Data collection
Diffractometer	Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6118, 1515, 821
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.042, 1.13
No. of reflections	1515
No. of parameters	194
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.13

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.39	3.267 (4)	158.2
C15—H15···O3ⁱⁱ	0.93	2.53	3.353 (4)	148.0

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

Acknowledgements

The diffraction measurements were made at the Centre for Testing and Analysis, Chengdu Branch, Chinese Academy of Sciences. We acknowledge financial support from China West Normal University.

References

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