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

Kang, T.-R.

doi:10.1107/S1600536810037475

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2628

doi:10.1107/S1600536810037475

Open

access

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

Tai-Ran Kang ^a ^*

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

(Received 5 September 2010; accepted 18 September 2010; online 25 September 2010)

In the title compound, C₁₆H₁₂N₂O₂, both terminal benzene rings are located at the same side of the central epoxide ring, showing a cis conformation. The epoxide ring makes dihedral angles of 76.59 (10) and 62.40 (11)° with the phenyl and cyanophenyl rings, respectively. Intermolecular N—H⋯O and weak C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For the use of epoxide-containing compounds as building blocks in synthesis, see: Meth-Cohn & Chen (1999 ); Porter & Skidmore (2000 ); Righi et al. (1996 ); Thijs et al. (1990 ). For related structures, see: Chen & Kang (2009a ,b ); He (2009 ); He et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₂N₂O₂
M_r = 264.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.459 (2) Å
b = 11.141 (7) Å
c = 21.844 (5) Å
V = 1328.6 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.36 × 0.32 × 0.26 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
9766 measured reflections
2078 independent reflections
1378 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.072
S = 1.00
2078 reflections
181 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H4⋯O1ⁱ	0.86	2.46	3.239 (3)	151 (1)
C11—H11⋯O1ⁱ	0.93	2.56	3.467 (3)	165 (1)
C12—H12⋯O2ⁱⁱ	0.93	2.55	3.302 (3)	139 (1)
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810037475/xu5025sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037475/xu5025Isup2.hkl

checkCIF report

Comment top

α, β-epoxides are key intermediates for synthesizing some natural products (Porter & Skidmore, 2000; 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). Various effective systems have been developed over the years for the preparation of chiral epoxides. As a part of our interest in the synthsis of epoxides ring systems (Chen & Kang, 2009a,b; He, 2009, He et al. (2009)), we synthesis the title compound by using Darzens reaction. 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. The cyanophenyl ring and N-phenylformamide units adopts a cis conformation with respect to the epoxides ring, the dihedral angle between the two phenyl ring is 84.75 (6)°. Epoxide ring makes dihedral angles of 76.59 (10)° and 62.40 (11)° with phenyl rings C1—C6 and C10—C15, respectively. The crystal packing is stabilized by C—H···O and N—H···O hydrogen bonding (Table 1).

Related literature top

For the use of epoxide-containing compounds as building blocks in synthesis, see: Meth-Cohn et al. (1999); Porter & Skidmore (2000); Righi et al. (1996); Thijs et al. (1990). For related structures, see: Chen & Kang (2009a,b); He (2009); He et al. (2009).

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 3-formylbenzonitrile (0.131 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 (0.02 g) in ethyl acetate (2 ml) and evaporating the solvent slowly at room temperature for about 1 d.

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

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

3-(3-Cyanophenyl)-N-phenyloxirane-2-carboxamide top

Crystal data top

C₁₆H₁₂N₂O₂	D_x = 1.321 Mg m⁻³
M_r = 264.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3256 reflections
a = 5.459 (2) Å	θ = 3.3–29.0°
b = 11.141 (7) Å	µ = 0.09 mm⁻¹
c = 21.844 (5) Å	T = 291 K
V = 1328.6 (10) Å³	Block, colorless
Z = 4	0.36 × 0.32 × 0.26 mm
F(000) = 552

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	1378 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.042
Graphite monochromator	θ_max = 29.2°, θ_min = 3.3°
Detector resolution: 15.9149 pixels mm^-1	h = −7→3
ω scans	k = −15→15
9766 measured reflections	l = −29→27
2078 independent reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0322P)²] where P = (F_o² + 2F_c²)/3
2078 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.14 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₂N₂O₂	V = 1328.6 (10) Å³
M_r = 264.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.459 (2) Å	µ = 0.09 mm⁻¹
b = 11.141 (7) Å	T = 291 K
c = 21.844 (5) Å	0.36 × 0.32 × 0.26 mm

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	1378 reflections with I > 2σ(I)
9766 measured reflections	R_int = 0.042
2078 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.072	H-atom parameters constrained
S = 1.00	Δρ_max = 0.14 e Å⁻³
2078 reflections	Δρ_min = −0.18 e Å⁻³
181 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
O2	0.2729 (2)	1.02915 (12)	0.76684 (6)	0.0522 (4)
O1	−0.2382 (2)	0.87594 (13)	0.69492 (6)	0.0540 (4)
N1	0.1739 (3)	0.86142 (13)	0.67637 (7)	0.0416 (4)
H4	0.3135	0.8914	0.6864	0.050*
C4	0.1740 (3)	0.76926 (15)	0.63124 (8)	0.0350 (4)
C3	0.3670 (3)	0.68860 (17)	0.63104 (9)	0.0430 (5)
H3	0.4906	0.6946	0.6602	0.052*
C6	−0.0019 (4)	0.67021 (17)	0.54450 (8)	0.0453 (5)
H6	−0.1252	0.6639	0.5153	0.054*
C10	0.1794 (3)	0.85668 (17)	0.83606 (8)	0.0389 (4)
C2	0.3746 (4)	0.59914 (18)	0.58733 (9)	0.0481 (5)
H2	0.5047	0.5453	0.5866	0.058*
C1	0.1884 (4)	0.58954 (18)	0.54452 (9)	0.0446 (5)
H1	0.1923	0.5282	0.5157	0.053*
C9	0.1163 (3)	0.97731 (17)	0.81328 (9)	0.0429 (5)
H9	0.0615	1.0337	0.8449	0.051*
C5	−0.0106 (3)	0.76092 (17)	0.58780 (8)	0.0423 (5)
H5	−0.1391	0.8157	0.5878	0.051*
C8	0.0212 (4)	1.00240 (16)	0.75099 (9)	0.0442 (4)
H8	−0.0867	1.0724	0.7479	0.053*
C15	0.0302 (3)	0.80528 (19)	0.88008 (9)	0.0470 (5)
H15	−0.1075	0.8466	0.8937	0.056*
C11	0.3875 (4)	0.79694 (18)	0.81664 (9)	0.0491 (5)
H11	0.4905	0.8318	0.7878	0.059*
C14	0.0830 (3)	0.6931 (2)	0.90422 (9)	0.0504 (5)
C7	−0.0260 (4)	0.90608 (17)	0.70496 (8)	0.0397 (4)
C12	0.4420 (4)	0.68306 (19)	0.84092 (10)	0.0567 (6)
H12	0.5803	0.6418	0.8277	0.068*
C16	−0.0707 (4)	0.6410 (2)	0.94879 (11)	0.0735 (7)
C13	0.2917 (4)	0.6330 (2)	0.88396 (10)	0.0552 (5)
H13	0.3292	0.5579	0.8999	0.066*
N2	−0.1971 (5)	0.5975 (2)	0.98491 (12)	0.1095 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0630 (9)	0.0466 (8)	0.0469 (8)	−0.0178 (7)	0.0058 (7)	−0.0050 (6)
O1	0.0430 (7)	0.0614 (10)	0.0576 (9)	−0.0045 (7)	0.0059 (7)	−0.0130 (7)
N1	0.0377 (8)	0.0450 (9)	0.0421 (9)	−0.0068 (7)	0.0002 (7)	−0.0096 (8)
C4	0.0367 (9)	0.0361 (10)	0.0323 (10)	−0.0069 (8)	0.0031 (8)	0.0022 (8)
C3	0.0356 (9)	0.0477 (12)	0.0457 (11)	−0.0025 (9)	−0.0070 (9)	−0.0043 (10)
C6	0.0479 (11)	0.0535 (12)	0.0344 (10)	−0.0047 (10)	−0.0047 (9)	−0.0005 (10)
C10	0.0424 (10)	0.0417 (10)	0.0327 (10)	−0.0036 (9)	−0.0020 (8)	−0.0081 (9)
C2	0.0424 (10)	0.0458 (12)	0.0561 (13)	0.0033 (10)	0.0024 (10)	−0.0049 (10)
C1	0.0531 (12)	0.0429 (11)	0.0376 (11)	−0.0061 (10)	0.0074 (9)	−0.0057 (9)
C9	0.0511 (10)	0.0401 (11)	0.0375 (11)	−0.0015 (9)	0.0085 (9)	−0.0064 (9)
C5	0.0446 (10)	0.0454 (11)	0.0370 (11)	0.0053 (10)	−0.0027 (9)	0.0009 (9)
C8	0.0537 (11)	0.0371 (10)	0.0418 (11)	−0.0009 (9)	0.0034 (9)	−0.0023 (9)
C15	0.0455 (10)	0.0526 (12)	0.0429 (12)	0.0048 (10)	0.0038 (10)	−0.0010 (10)
C11	0.0448 (10)	0.0616 (14)	0.0408 (11)	0.0010 (10)	0.0056 (9)	−0.0048 (11)
C14	0.0535 (12)	0.0542 (13)	0.0435 (12)	0.0022 (11)	−0.0021 (10)	0.0068 (11)
C7	0.0475 (11)	0.0356 (10)	0.0359 (10)	−0.0027 (9)	0.0026 (9)	0.0031 (9)
C12	0.0561 (13)	0.0611 (15)	0.0529 (13)	0.0186 (11)	0.0003 (11)	−0.0095 (12)
C16	0.0719 (16)	0.0759 (16)	0.0726 (17)	0.0088 (14)	0.0115 (14)	0.0317 (15)
C13	0.0690 (14)	0.0470 (12)	0.0496 (12)	0.0069 (12)	−0.0081 (11)	−0.0007 (10)
N2	0.1022 (19)	0.111 (2)	0.115 (2)	0.0091 (16)	0.0281 (17)	0.0571 (17)

Geometric parameters (Å, º) top

O2—C9	1.447 (2)	C2—H2	0.9300
O2—C8	1.448 (2)	C1—H1	0.9300
O1—C7	1.226 (2)	C9—C8	1.483 (3)
N1—C7	1.352 (2)	C9—H9	0.9800
N1—C4	1.423 (2)	C5—H5	0.9300
N1—H4	0.8600	C8—C7	1.493 (3)
C4—C3	1.384 (2)	C8—H8	0.9800
C4—C5	1.387 (2)	C15—C14	1.387 (3)
C3—C2	1.381 (3)	C15—H15	0.9300
C3—H3	0.9300	C11—C12	1.407 (2)
C6—C1	1.374 (3)	C11—H11	0.9300
C6—C5	1.385 (3)	C14—C13	1.394 (3)
C6—H6	0.9300	C14—C16	1.411 (2)
C10—C11	1.383 (3)	C12—C13	1.367 (3)
C10—C15	1.384 (2)	C12—H12	0.9300
C10—C9	1.474 (3)	C16—N2	1.155 (3)
C2—C1	1.385 (3)	C13—H13	0.9300

C9—O2—C8	61.64 (11)	C6—C5—C4	119.40 (18)
C7—N1—C4	125.86 (15)	C6—C5—H5	120.3
C7—N1—H4	117.1	C4—C5—H5	120.3
C4—N1—H4	117.1	O2—C8—C9	59.14 (12)
C3—C4—C5	120.47 (17)	O2—C8—C7	118.21 (15)
C3—C4—N1	118.09 (16)	C9—C8—C7	122.89 (16)
C5—C4—N1	121.43 (16)	O2—C8—H8	115.0
C2—C3—C4	119.58 (17)	C9—C8—H8	115.0
C2—C3—H3	120.2	C7—C8—H8	115.0
C4—C3—H3	120.2	C10—C15—C14	120.97 (18)
C1—C6—C5	120.21 (18)	C10—C15—H15	119.5
C1—C6—H6	119.9	C14—C15—H15	119.5
C5—C6—H6	119.9	C10—C11—C12	119.47 (18)
C11—C10—C15	119.82 (18)	C10—C11—H11	120.3
C11—C10—C9	121.80 (17)	C12—C11—H11	120.3
C15—C10—C9	118.31 (17)	C15—C14—C13	118.82 (19)
C3—C2—C1	120.03 (18)	C15—C14—C16	120.7 (2)
C3—C2—H2	120.0	C13—C14—C16	120.5 (2)
C1—C2—H2	120.0	O1—C7—N1	125.40 (18)
C6—C1—C2	120.31 (17)	O1—C7—C8	118.70 (17)
C6—C1—H1	119.8	N1—C7—C8	115.87 (16)
C2—C1—H1	119.8	C13—C12—C11	120.00 (19)
O2—C9—C10	117.57 (16)	C13—C12—H12	120.0
O2—C9—C8	59.22 (12)	C11—C12—H12	120.0
C10—C9—C8	124.29 (16)	N2—C16—C14	179.4 (3)
O2—C9—H9	114.7	C12—C13—C14	120.9 (2)
C10—C9—H9	114.7	C12—C13—H13	119.5
C8—C9—H9	114.7	C14—C13—H13	119.5

C7—N1—C4—C3	−143.99 (18)	C10—C9—C8—C7	1.4 (3)
C7—N1—C4—C5	37.1 (3)	C11—C10—C15—C14	−1.4 (3)
C5—C4—C3—C2	−0.2 (3)	C9—C10—C15—C14	−178.62 (18)
N1—C4—C3—C2	−179.08 (17)	C15—C10—C11—C12	1.5 (3)
C4—C3—C2—C1	−0.8 (3)	C9—C10—C11—C12	178.54 (18)
C5—C6—C1—C2	−0.8 (3)	C10—C15—C14—C13	0.8 (3)
C3—C2—C1—C6	1.3 (3)	C10—C15—C14—C16	−179.6 (2)
C8—O2—C9—C10	115.39 (18)	C4—N1—C7—O1	−2.2 (3)
C11—C10—C9—O2	3.5 (3)	C4—N1—C7—C8	179.70 (15)
C15—C10—C9—O2	−179.39 (15)	O2—C8—C7—O1	174.09 (18)
C11—C10—C9—C8	73.5 (3)	C9—C8—C7—O1	104.4 (2)
C15—C10—C9—C8	−109.4 (2)	O2—C8—C7—N1	−7.6 (2)
C1—C6—C5—C4	−0.2 (3)	C9—C8—C7—N1	−77.4 (2)
C3—C4—C5—C6	0.7 (3)	C10—C11—C12—C13	−0.9 (3)
N1—C4—C5—C6	179.55 (16)	C11—C12—C13—C14	0.3 (3)
C9—O2—C8—C7	−113.41 (19)	C15—C14—C13—C12	−0.2 (3)
C10—C9—C8—O2	−104.2 (2)	C16—C14—C13—C12	−179.8 (2)
O2—C9—C8—C7	105.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O1ⁱ	0.86	2.46	3.239 (3)	151 (1)
C11—H11···O1ⁱ	0.93	2.56	3.467 (3)	165 (1)
C12—H12···O2ⁱⁱ	0.93	2.55	3.302 (3)	139 (1)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂N₂O₂
M_r	264.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	5.459 (2), 11.141 (7), 21.844 (5)
V (Å³)	1328.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.36 × 0.32 × 0.26

Data collection
Diffractometer	Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9766, 2078, 1378
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.072, 1.00
No. of reflections	2078
No. of parameters	181
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), 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
N1—H4···O1ⁱ	0.86	2.46	3.239 (3)	150.8 (2)
C11—H11···O1ⁱ	0.93	2.56	3.467 (3)	165.4 (3)
C12—H12···O2ⁱⁱ	0.93	2.55	3.302 (3)	138.7 (1)

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

Acknowledgements

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

References

Chen, L.-M. & Kang, T.-R. (2009a). Acta Cryst. E65, o3126. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chen, L.-M. & Kang, T.-R. (2009b). Acta Cryst. E65, o3137. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
He, L. (2009). Acta Cryst. E65, o2052. Web of Science CSD CrossRef IUCr Journals Google Scholar
He, L., Qin, H.-M. & Chen, L.-M. (2009). Acta Cryst. E65, o2999. Web of Science CSD CrossRef IUCr Journals Google Scholar
Meth-Cohn, O. & Chen, Y. (1999). Tetrahedron Lett. 40, 6069–6072. Web of Science CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Porter, M. J. & Skidmore, J. (2000). Chem. Commun. pp. 1215–1225. Web of Science CrossRef Google Scholar
Righi, G., Rumboldt, G. & Bonini, C. (1996). J. Org. Chem. 61, 3557–3560. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thijs, L., Porskamp, J. J. M., van Loon, A. A. W. M., Derks, M. P. W., Feenstra, R. W., Legters, J. & Zwanenburg, B. (1990). Tetrahedron, 46, 2611–2614. CrossRef CAS Web of Science Google Scholar