2-(2-Chloro­phen­yl)-N-cyclo­hexyl-2-oxoacetamide

Jin, X.-D.; Wu, J.-L.

doi:10.1107/S1600536813005904

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o505

doi:10.1107/S1600536813005904

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2-(2-Chlorophenyl)-N-cyclohexyl-2-oxoacetamide

Xiu-Dan Jin ^a and Jin-Long Wu ^a ^*

^aLaboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China
^*Correspondence e-mail: wyz@zju.edu.cn

(Received 29 January 2013; accepted 1 March 2013; online 9 March 2013)

In the title compound, C₁₄H₁₆ClNO₂, the cyclohexyl ring has a chair conformation. The dihedral angle between the benzene ring and the mean plane of the four planar C atoms of the cyclohexyl ring is 45.2 (3)°. The two carbonyl groups are trans to one another, with an O=C—C=O torsion angle of −137.1 (3)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds forming chains propagating along [001]. A region of disordered electron density, situated near the unit-cell corners, was treated using the SQUEEZE routine in PLATON [Spek (2009 ). Acta Cryst. D65, 148–155]. It gave a solvent-accessible void of ca 400 Å³ for only 21 electrons. It is probably due to traces of the solvent of crystallization and was not taken into account during structure refinement.

Related literature

For the crystal structures of substituted phenylglyoxamides, see: Boryczka et al. (1998 ); Dai & Wu (2011 ); Jia & Wu (2012 ).

Experimental

Crystal data

C₁₄H₁₆ClNO₂
M_r = 265.73
Hexagonal, P 6₁
a = 17.075 (3) Å
c = 9.4536 (13) Å
V = 2387.0 (7) Å³
Z = 6
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.48 × 0.26 × 0.20 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.896, T_max = 0.955
15794 measured reflections
3101 independent reflections
2344 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.149
S = 1.01
3101 reflections
163 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 1422 Friedel pairs
Flack parameter: −0.05 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.07	2.864 (3)	153
Symmetry code: (i) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813005904/su2558sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005904/su2558Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813005904/su2558Isup3.cml

checkCIF report

Comment top

The crystal structure of several substituted phenylglyoxamides have been reported (Boryczka, et al., 1998; Dai & Wu, 2011; Jia & Wu, 2012). The differences in their molecular packing depends on the hydrogen bonds present. In our effort to explore the effect of the substituent groups of phenylglyoxamide on the crystal form, we have synthesized the title compound by acetylation of cyclohexylamine with 2-chlorophenylglyoxyl chloride obtained from 2-chlorophenylglyoxic acid with oxalyl dichloride. We report herein on its crystal structure.

In the title molecule (Fig. 1), the cyclohexane ring has a chair conformation. The dihedral angle between the phenyl ring and the mean plane of the four planar C atoms of the cyclohexane ring (C10/C11/C13/C14) is 45.2 (3) °. The two carbonyl groups of the molecule are trans oriented to each other with a torsion angle O1═C7-C8 ═O2 of -137.1 (3) °.

In the crystal, molecules are linked by N—H···O hydrogen bonds forming chains extending in the c axis direction (Table 1 and Fig. 2).

Related literature top

For the crystal structures of substituted phenylglyoxamides, see: Boryczka et al. (1998); Dai & Wu (2011); Jia & Wu (2012).

Experimental top

To a solution of 2-chlorophenylglyoxylic acid (184 mg, 1.0 mmol) in dichloromethane (3 mL), was added oxalyl chloride (0.22 mL, 2.5 mmol) over 5 min. DMF (dimethylformamide) ( 1 drop) was then added and the solution was warmed to room temperature and stirred for 1.5 h. The solvent was removed under reduced pressure to afford 2-chlorophenylglyoxyl chloride which was used for the next step without further purification. To a solution of cyclohexylamine (0.23 mL, 2.0 mmol) and triethylamine (0.83 mL, 6.0 mmol) in dichloromethane (5 mL), was added dropwise the solution of the above glyoxyl chloride in dichloromethane (1 mL) at 273 K under N₂, and the mixture was stirred for 4 h. The reaction was quenched with saturated NH₄Cl solution (2 mL), then the organic layer was separated and the aqueous layer was extracted with dichloromethane (5 mL). The combined organic layers were washed with brine, dried over anhydrous Na₂SO₄ and filtered, the filtrate was concentrated under reduced pressure. The resulting residue was purified by column chromatography (silica gel, 20% ethyl acetate in hexane) to afford the title compound as colourless needles (227 mg, 85% yield from glyoxylic acid), m.p. 375-376 K. Single crystals suitable for X-ray diffraction were grown from a mixture of dichloromethane and hexane (1:1 v/v).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at 40% probability level.
	Fig. 2. A view of the formation of the one-dimensional chain of the title compound via N—H···O hydrogen bonds [dashed lines; symmetry code: (i) -x+1, -y+1, z-1/2; see Table 1 for details].

2-(2-Chlorophenyl)-N-cyclohexyl-2-oxoacetamide top

Crystal data top

C₁₄H₁₆ClNO₂	D_x = 1.109 Mg m⁻³
M_r = 265.73	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₁	Cell parameters from 2933 reflections
Hall symbol: P 61	θ = 3.2–29.4°
a = 17.075 (3) Å	µ = 0.24 mm⁻¹
c = 9.4536 (13) Å	T = 293 K
V = 2387.0 (7) Å³	Needle, colourless
Z = 6	0.48 × 0.26 × 0.20 mm
F(000) = 840

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3101 independent reflections
Radiation source: fine-focus sealed tube	2344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 10.3592 pixels mm^-1	θ_max = 26.1°, θ_min = 3.2°
ω scans	h = −16→21
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −21→19
T_min = 0.896, T_max = 0.955	l = −11→11
15794 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0919P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3101 reflections	Δρ_max = 0.19 e Å⁻³
163 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1422 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (3)

Crystal data top

C₁₄H₁₆ClNO₂	Z = 6
M_r = 265.73	Mo Kα radiation
Hexagonal, P6₁	µ = 0.24 mm⁻¹
a = 17.075 (3) Å	T = 293 K
c = 9.4536 (13) Å	0.48 × 0.26 × 0.20 mm
V = 2387.0 (7) Å³

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3101 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2344 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.955	R_int = 0.047
15794 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.149	Δρ_max = 0.19 e Å⁻³
S = 1.01	Δρ_min = −0.17 e Å⁻³
3101 reflections	Absolute structure: Flack (1983), 1422 Friedel pairs
163 parameters	Absolute structure parameter: −0.05 (3)
1 restraint

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
Cl1	0.69837 (7)	0.67833 (8)	0.10734 (15)	0.1067 (4)
O1	0.43847 (15)	0.60191 (15)	0.0815 (2)	0.0736 (8)
O2	0.52877 (16)	0.55421 (14)	0.3612 (2)	0.0672 (8)
N1	0.48258 (16)	0.46907 (14)	0.1620 (2)	0.0538 (8)
C1	0.6611 (2)	0.7465 (2)	0.1859 (4)	0.0703 (11)
C2	0.7225 (3)	0.8325 (3)	0.2271 (6)	0.1002 (16)
C3	0.6930 (4)	0.8869 (3)	0.2830 (6)	0.1072 (18)
C4	0.6038 (3)	0.8566 (2)	0.2982 (5)	0.0948 (16)
C5	0.5408 (2)	0.7700 (2)	0.2549 (4)	0.0705 (11)
C6	0.5693 (2)	0.71274 (18)	0.2003 (3)	0.0539 (9)
C7	0.5009 (2)	0.61862 (19)	0.1599 (3)	0.0508 (9)
C8	0.50637 (18)	0.54310 (18)	0.2353 (3)	0.0481 (8)
C9	0.4826 (2)	0.38896 (18)	0.2192 (3)	0.0541 (9)
C10	0.5628 (2)	0.3843 (2)	0.1677 (4)	0.0786 (14)
C11	0.5633 (3)	0.3014 (3)	0.2262 (5)	0.0919 (17)
C12	0.4763 (3)	0.2157 (2)	0.1922 (4)	0.0913 (16)
C13	0.3966 (3)	0.2207 (3)	0.2424 (7)	0.112 (2)
C14	0.3952 (2)	0.3033 (2)	0.1816 (6)	0.0897 (14)
H1	0.46610	0.46740	0.07550	0.0650*
H2	0.78410	0.85380	0.21720	0.1210*
H3	0.73480	0.94550	0.31080	0.1280*
H4	0.58450	0.89400	0.33780	0.1140*
H5	0.47930	0.75020	0.26230	0.0840*
H9	0.48640	0.39430	0.32250	0.0650*
H10A	0.61760	0.43850	0.19660	0.0940*
H10B	0.56180	0.38200	0.06510	0.0940*
H11A	0.61380	0.29800	0.18590	0.1100*
H11B	0.57150	0.30720	0.32790	0.1100*
H12A	0.47190	0.20590	0.09070	0.1100*
H12B	0.47680	0.16480	0.23670	0.1100*
H13A	0.39770	0.22400	0.34490	0.1350*
H13B	0.34180	0.16620	0.21460	0.1350*
H14A	0.38860	0.29780	0.07960	0.1080*
H14B	0.34410	0.30640	0.21980	0.1080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0872 (6)	0.1113 (7)	0.1394 (9)	0.0629 (6)	0.0331 (6)	−0.0112 (7)
O1	0.0885 (15)	0.0802 (14)	0.0662 (14)	0.0527 (12)	−0.0205 (12)	−0.0011 (11)
O2	0.1098 (16)	0.0723 (12)	0.0345 (11)	0.0567 (12)	−0.0018 (10)	−0.0010 (9)
N1	0.0815 (16)	0.0613 (13)	0.0317 (11)	0.0455 (13)	−0.0049 (10)	0.0001 (10)
C1	0.078 (2)	0.0719 (19)	0.0720 (19)	0.0458 (17)	0.0126 (16)	0.0028 (16)
C2	0.071 (2)	0.080 (2)	0.134 (4)	0.026 (2)	0.012 (2)	0.000 (2)
C3	0.118 (3)	0.059 (2)	0.131 (4)	0.034 (2)	0.011 (3)	−0.005 (2)
C4	0.125 (3)	0.065 (2)	0.107 (3)	0.057 (2)	0.017 (3)	−0.002 (2)
C5	0.085 (2)	0.0680 (19)	0.075 (2)	0.0507 (17)	0.0183 (18)	0.0131 (17)
C6	0.0733 (18)	0.0610 (16)	0.0410 (15)	0.0437 (15)	0.0088 (12)	0.0106 (12)
C7	0.0668 (16)	0.0663 (16)	0.0346 (13)	0.0448 (14)	0.0051 (12)	0.0015 (11)
C8	0.0634 (15)	0.0629 (15)	0.0294 (14)	0.0402 (13)	0.0065 (11)	0.0036 (11)
C9	0.0799 (18)	0.0569 (15)	0.0362 (13)	0.0422 (14)	0.0037 (12)	0.0053 (11)
C10	0.073 (2)	0.073 (2)	0.101 (3)	0.0449 (17)	0.0086 (18)	0.0180 (19)
C11	0.100 (3)	0.095 (3)	0.109 (3)	0.070 (2)	0.008 (2)	0.019 (2)
C12	0.145 (4)	0.070 (2)	0.078 (2)	0.068 (2)	−0.015 (2)	−0.0055 (19)
C13	0.096 (3)	0.064 (2)	0.161 (5)	0.028 (2)	0.001 (3)	0.040 (3)
C14	0.072 (2)	0.068 (2)	0.128 (3)	0.0342 (18)	0.003 (2)	0.026 (2)

Geometric parameters (Å, º) top

Cl1—C1	1.747 (4)	C12—C13	1.484 (8)
O1—C7	1.210 (4)	C13—C14	1.534 (6)
O2—C8	1.235 (3)	C2—H2	0.9300
N1—C8	1.315 (3)	C3—H3	0.9300
N1—C9	1.471 (4)	C4—H4	0.9300
N1—H1	0.8600	C5—H5	0.9300
C1—C6	1.380 (5)	C9—H9	0.9800
C1—C2	1.367 (6)	C10—H10A	0.9700
C2—C3	1.365 (8)	C10—H10B	0.9700
C3—C4	1.349 (9)	C11—H11A	0.9700
C4—C5	1.386 (5)	C11—H11B	0.9700
C5—C6	1.391 (5)	C12—H12A	0.9700
C6—C7	1.489 (4)	C12—H12B	0.9700
C7—C8	1.517 (4)	C13—H13A	0.9700
C9—C14	1.520 (5)	C13—H13B	0.9700
C9—C10	1.493 (5)	C14—H14A	0.9700
C10—C11	1.524 (6)	C14—H14B	0.9700
C11—C12	1.509 (6)

C8—N1—C9	123.8 (2)	C5—C4—H4	120.00
C9—N1—H1	118.00	C4—C5—H5	120.00
C8—N1—H1	118.00	C6—C5—H5	120.00
Cl1—C1—C6	118.7 (2)	N1—C9—H9	108.00
Cl1—C1—C2	119.9 (3)	C10—C9—H9	108.00
C2—C1—C6	121.4 (4)	C14—C9—H9	108.00
C1—C2—C3	119.7 (5)	C9—C10—H10A	109.00
C2—C3—C4	120.7 (4)	C9—C10—H10B	109.00
C3—C4—C5	120.2 (4)	C11—C10—H10A	109.00
C4—C5—C6	120.1 (4)	C11—C10—H10B	109.00
C1—C6—C7	122.7 (3)	H10A—C10—H10B	108.00
C1—C6—C5	117.8 (3)	C10—C11—H11A	109.00
C5—C6—C7	119.5 (3)	C10—C11—H11B	109.00
C6—C7—C8	116.7 (3)	C12—C11—H11A	109.00
O1—C7—C8	120.6 (3)	C12—C11—H11B	109.00
O1—C7—C6	122.4 (3)	H11A—C11—H11B	108.00
O2—C8—N1	125.3 (3)	C11—C12—H12A	109.00
O2—C8—C7	117.9 (2)	C11—C12—H12B	109.00
N1—C8—C7	116.7 (2)	C13—C12—H12A	109.00
N1—C9—C10	110.9 (2)	C13—C12—H12B	109.00
C10—C9—C14	111.0 (3)	H12A—C12—H12B	108.00
N1—C9—C14	110.6 (3)	C12—C13—H13A	109.00
C9—C10—C11	111.3 (3)	C12—C13—H13B	109.00
C10—C11—C12	111.3 (4)	C14—C13—H13A	109.00
C11—C12—C13	111.3 (4)	C14—C13—H13B	109.00
C12—C13—C14	111.7 (4)	H13A—C13—H13B	108.00
C9—C14—C13	109.8 (4)	C9—C14—H14A	110.00
C1—C2—H2	120.00	C9—C14—H14B	110.00
C3—C2—H2	120.00	C13—C14—H14A	110.00
C2—C3—H3	120.00	C13—C14—H14B	110.00
C4—C3—H3	120.00	H14A—C14—H14B	108.00
C3—C4—H4	120.00

C8—N1—C9—C14	133.5 (4)	C1—C6—C7—C8	59.6 (4)
C9—N1—C8—O2	−2.4 (5)	C5—C6—C7—O1	52.5 (4)
C9—N1—C8—C7	−179.1 (3)	C5—C6—C7—C8	−120.4 (3)
C8—N1—C9—C10	−103.0 (3)	O1—C7—C8—N1	39.9 (5)
C6—C1—C2—C3	−0.4 (7)	C6—C7—C8—O2	36.0 (4)
Cl1—C1—C6—C5	−176.0 (3)	C6—C7—C8—N1	−147.0 (3)
Cl1—C1—C6—C7	3.9 (4)	O1—C7—C8—O2	−137.1 (3)
Cl1—C1—C2—C3	177.3 (4)	N1—C9—C10—C11	−179.9 (3)
C2—C1—C6—C5	1.7 (6)	C14—C9—C10—C11	−56.5 (4)
C2—C1—C6—C7	−178.4 (4)	N1—C9—C14—C13	−179.9 (4)
C1—C2—C3—C4	0.1 (8)	C10—C9—C14—C13	56.6 (5)
C2—C3—C4—C5	−1.1 (8)	C9—C10—C11—C12	55.2 (4)
C3—C4—C5—C6	2.4 (6)	C10—C11—C12—C13	−54.8 (5)
C4—C5—C6—C7	177.4 (3)	C11—C12—C13—C14	55.9 (6)
C4—C5—C6—C1	−2.6 (5)	C12—C13—C14—C9	−56.5 (6)
C1—C6—C7—O1	−127.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.07	2.864 (3)	153

Symmetry code: (i) −x+1, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆ClNO₂
M_r	265.73
Crystal system, space group	Hexagonal, P6₁
Temperature (K)	293
a, c (Å)	17.075 (3), 9.4536 (13)
V (Å³)	2387.0 (7)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.48 × 0.26 × 0.20

Data collection
Diffractometer	Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.896, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	15794, 3101, 2344
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.149, 1.01
No. of reflections	3101
No. of parameters	163
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17
Absolute structure	Flack (1983), 1422 Friedel pairs
Absolute structure parameter	−0.05 (3)

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.07	2.864 (3)	153

Symmetry code: (i) −x+1, −y+1, z−1/2.

Acknowledgements

The authors gratefully acknowledge Mr Jiyong Liu and Jianming Gu of Zhejiang University for their assistance with the crystal structure analysis and useful dicussions.

References

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