2-(2-Chloro­phen­yl)-2-oxo-N-phenyl­acetamide

In the title compound, C₁₄H₁₀ClNO₂, the dihedral angle between the two rings is 59.4 (2)°. The two carbonyl groups are oriented almost anti­periplanar to each other, with a torsion angle of −160.43 (2)°. In the crystal, mol­ecules are linked into inversion dimers by pairs of N—H⋯O hydrogen bonds.

Related literature

The crystal structure of the title compound was determined within a project on the synthesis of new phenylacetamides, see: Li & Wu (2010).

Experimental

Crystal data

• C₁₄H₁₀ClNO₂

• M_r = 259.68

• Monoclinic, P 2₁ /c

• a = 11.3513 (11) Å

• b = 10.4585 (8) Å

• c = 10.2944 (10) Å

• β = 100.954 (10)°

• V = 1199.86 (19) ų

• Z = 4

• Mo Kα radiation

• μ = 0.31 mm⁻¹

• T = 293 K

• 0.48 × 0.39 × 0.25 mm

Data collection

• Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) T_min = 0.860, T_max = 0.928

• 5282 measured reflections

• 2201 independent reflections

• 1562 reflections with I > 2σ(I)

• R_int = 0.021

Refinement

• R[F² > 2σ(F²)] = 0.034

• wR(F²) = 0.095

• S = 1.01

• 2201 reflections

• 163 parameters

• H-atom parameters constrained

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H⋯O1^i	0.86	2.52	3.241 (4)	141
Symmetry code: (i) -x, -y, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); 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: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.

Supporting information

Related literature

The crystal structure of the title compound was determined within a project on the synthesis of new phenylacetamides, see: Li & Wu (2010).

S1. Experimental

A solution of 2-chloroacetophenone (1.0 g, 6.5 mmol) and SeO₂ (1.94 g, 16.8 mmol) in 10 ml of freshly distilled pyridine was heated to 383 K. The reaction mixture was gradually cooled down to 363 K over 1 h and was kept at thistemperature for additional 4 h. The solution was concentrated using a rotary evaporator until a small amount of liquid was present. The black selenium was rinsed several times with ethyl acetate. The combined organic layers were acidified with 10 ml of 0.1 M HC1 and the aqueous layer was extracted three times with ethyl acetate. The organic layers were combined and extracted several times with saturated aqueous NaHC0₃. The aqueous layers were combined, brought to pH 1 with conc. HCl and extracted three times with ethyl acetate. The final organic layers were dried over anhydrous Na₂SO₄ and concentrated, producing (2-chlorophenyl)glyoxylic acid in 85% yield (1.02 g) as a solid.

Into a suspension of (2-chlorophenyl)glyoxylic acid (250 mg, 1.36 mmol) and aniline (116 mg, 1.25 mmol) in methylene chloride (8 ml), N,N'-dicyclohexylcarbodiimide (DCC) (280 mg, 1.36 mmol) and 4-(dimethylamino)pyridine (DMAP) (33 mg, 0.27 mmol) was added respectively at room temperature and continuted stirring for 8 h. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure, the residue was purified by colum chromatography (silica gel, 30% of ethyl acetate in hexane) to afford the title compound in 72% yield (254 mg) as a white solid, m.p. 349–351 K, ¹H NMR (400 MHz, CDCl₃) /d 8.79 (brs, 1H), 7.74 (d, J = 7.6 Hz, 1H), 7.70 (d, J = 8.0 Hz, 2H), 7.53–7.47 (m, 2H), 7.40 (t, J = 8.0 Hz, 3H), 7.21 (t, J = 7.6 Hz, 1H). Single crystals suitable for X-ray diffraction of the title compound were grown in a micture of ethyl acetate and hexane.

S2. Refinement

The H atoms were placed in calculated positions with C—H = 0.93 Å and refined isotropic with U_iso(H) =1.2U_eq of the carrier atom using a riding model.

Structure description

The crystal structure of the title compound was determined within a project on the synthesis of new phenylacetamides, see: Li & Wu (2010).

Computing details

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: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 40% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. The dimer of the title compound linked by two N—H···O hydrogen bonds (dotted lines).

2-(2-Chlorophenyl)-2-oxo-N-phenylacetamide

Crystal data

C14H10ClNO2	F(000) = 536
Mr = 259.68	Dx = 1.438 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1968 reflections
a = 11.3513 (11) Å	θ = 3.5–29.2°
b = 10.4585 (8) Å	µ = 0.31 mm^−1
c = 10.2944 (10) Å	T = 293 K
β = 100.954 (10)°	Block, yellow
V = 1199.86 (19) Å^3	0.48 × 0.39 × 0.25 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	2201 independent reflections
Radiation source: fine-focus sealed tube	1562 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 10.3592 pixels mm^-1	θmax = 25.4°, θmin = 3.6°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→12
Tmin = 0.860, Tmax = 0.928	l = −12→7
5282 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0552P)^2] where P = (Fo^2 + 2Fc^2)/3
2201 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.39169 (4)	0.11424 (5)	0.07892 (5)	0.0671 (2)
O1	0.12583 (11)	0.05846 (11)	−0.01363 (12)	0.0534 (4)
O2	0.04597 (11)	0.32465 (12)	−0.20894 (12)	0.0556 (4)
N	−0.05486 (12)	0.13663 (13)	−0.20367 (13)	0.0438 (4)
H	−0.0482	0.0637	−0.1643	0.053*
C1	0.13889 (17)	0.38201 (17)	0.07314 (17)	0.0505 (5)
H1	0.0609	0.3986	0.0295	0.061*
C2	0.1960 (2)	0.46949 (19)	0.16282 (18)	0.0627 (5)
H2	0.1563	0.5432	0.1811	0.075*
C3	0.3117 (2)	0.4475 (2)	0.2250 (2)	0.0697 (6)
H3	0.3508	0.5067	0.2856	0.084*
C4	0.37045 (18)	0.3389 (2)	0.19889 (19)	0.0637 (6)
H4	0.4495	0.3254	0.2407	0.076*
C5	0.31215 (15)	0.24881 (17)	0.10994 (18)	0.0483 (5)
C6	0.19425 (14)	0.26908 (16)	0.04560 (16)	0.0409 (4)
C7	0.12143 (13)	0.17184 (16)	−0.03847 (16)	0.0404 (4)
C8	0.03285 (14)	0.22088 (16)	−0.16030 (16)	0.0406 (4)
C9	−0.15676 (14)	0.15162 (15)	−0.30543 (16)	0.0386 (4)
C10	−0.24427 (14)	0.05916 (17)	−0.31498 (16)	0.0449 (4)
H10	−0.2331	−0.0109	−0.2583	0.054*
C11	−0.34801 (16)	0.07007 (19)	−0.40792 (19)	0.0572 (5)
H11	−0.4074	0.0080	−0.4135	0.069*
C12	−0.36407 (17)	0.1729 (2)	−0.49283 (19)	0.0609 (5)
H12	−0.4345	0.1806	−0.5553	0.073*
C13	−0.27627 (18)	0.26376 (18)	−0.48528 (18)	0.0567 (5)
H13	−0.2874	0.3326	−0.5436	0.068*
C14	−0.17155 (16)	0.25492 (16)	−0.39263 (17)	0.0480 (5)
H14	−0.1120	0.3166	−0.3884	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0447 (3)	0.0726 (4)	0.0818 (4)	0.0070 (2)	0.0062 (2)	0.0104 (3)
O1	0.0500 (7)	0.0414 (7)	0.0634 (8)	−0.0033 (6)	−0.0028 (6)	0.0056 (6)
O2	0.0601 (8)	0.0440 (8)	0.0578 (8)	−0.0130 (6)	−0.0017 (6)	0.0081 (6)
N	0.0394 (8)	0.0385 (8)	0.0499 (9)	−0.0037 (6)	−0.0002 (7)	0.0092 (6)
C1	0.0499 (11)	0.0514 (11)	0.0501 (11)	−0.0042 (9)	0.0089 (9)	−0.0006 (9)
C2	0.0786 (15)	0.0572 (12)	0.0541 (12)	−0.0067 (11)	0.0174 (11)	−0.0115 (10)
C3	0.0906 (17)	0.0681 (15)	0.0469 (11)	−0.0216 (13)	0.0042 (11)	−0.0083 (10)
C4	0.0551 (12)	0.0788 (15)	0.0501 (11)	−0.0204 (11)	−0.0075 (9)	0.0080 (11)
C5	0.0444 (10)	0.0534 (11)	0.0467 (10)	−0.0062 (8)	0.0077 (8)	0.0080 (8)
C6	0.0405 (9)	0.0438 (10)	0.0384 (9)	−0.0047 (8)	0.0074 (7)	0.0050 (7)
C7	0.0352 (9)	0.0402 (10)	0.0466 (10)	−0.0006 (7)	0.0100 (7)	0.0030 (8)
C8	0.0385 (9)	0.0397 (10)	0.0441 (10)	−0.0034 (8)	0.0087 (7)	0.0006 (8)
C9	0.0367 (9)	0.0397 (9)	0.0390 (9)	0.0038 (7)	0.0063 (7)	−0.0013 (7)
C10	0.0412 (10)	0.0442 (10)	0.0485 (10)	−0.0028 (8)	0.0070 (8)	0.0030 (8)
C11	0.0412 (10)	0.0627 (13)	0.0632 (12)	−0.0080 (9)	−0.0013 (9)	−0.0011 (10)
C12	0.0484 (11)	0.0669 (13)	0.0597 (12)	0.0075 (10)	−0.0091 (9)	−0.0009 (10)
C13	0.0666 (13)	0.0495 (11)	0.0496 (11)	0.0108 (10)	−0.0002 (10)	0.0076 (8)
C14	0.0524 (11)	0.0401 (10)	0.0497 (11)	−0.0034 (8)	0.0053 (9)	0.0023 (8)

Geometric parameters (Å, º)

Cl—C5	1.7342 (19)	C5—C6	1.392 (2)
O1—C7	1.2120 (19)	C6—C7	1.481 (2)
O2—C8	1.2161 (19)	C7—C8	1.539 (2)
N—C8	1.341 (2)	C9—C10	1.376 (2)
N—C9	1.414 (2)	C9—C14	1.394 (2)
N—H	0.8600	C10—C11	1.374 (2)
C1—C2	1.372 (3)	C10—H10	0.9300
C1—C6	1.392 (2)	C11—C12	1.376 (3)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.366 (3)	C12—C13	1.369 (3)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.370 (3)	C13—C14	1.378 (2)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.391 (3)	C14—H14	0.9300
C4—H4	0.9300
C8—N—C9	128.68 (14)	C6—C7—C8	116.93 (14)
C8—N—H	115.7	O2—C8—N	126.20 (15)
C9—N—H	115.7	O2—C8—C7	121.39 (14)
C2—C1—C6	121.93 (18)	N—C8—C7	112.41 (14)
C2—C1—H1	119.0	C10—C9—C14	120.10 (15)
C6—C1—H1	119.0	C10—C9—N	116.92 (14)
C3—C2—C1	119.5 (2)	C14—C9—N	122.98 (15)
C3—C2—H2	120.3	C11—C10—C9	120.19 (17)
C1—C2—H2	120.3	C11—C10—H10	119.9
C2—C3—C4	120.56 (18)	C9—C10—H10	119.9
C2—C3—H3	119.7	C10—C11—C12	119.99 (18)
C4—C3—H3	119.7	C10—C11—H11	120.0
C3—C4—C5	120.16 (19)	C12—C11—H11	120.0
C3—C4—H4	119.9	C13—C12—C11	119.97 (17)
C5—C4—H4	119.9	C13—C12—H12	120.0
C4—C5—C6	120.28 (18)	C11—C12—H12	120.0
C4—C5—Cl	118.15 (15)	C12—C13—C14	121.04 (17)
C6—C5—Cl	121.54 (14)	C12—C13—H13	119.5
C5—C6—C1	117.56 (15)	C14—C13—H13	119.5
C5—C6—C7	123.55 (16)	C13—C14—C9	118.68 (16)
C1—C6—C7	118.56 (14)	C13—C14—H14	120.7
O1—C7—C6	123.52 (14)	C9—C14—H14	120.7
O1—C7—C8	119.50 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H···O1^i	0.86	2.52	3.241 (4)	141

Symmetry code: (i) −x, −y, −z.