2,2-Dichloro-1-(2-phenyl-1,3-oxazolidin-3-yl)ethanone

Ye, F.; Fu, Y.; Zhao, S.

doi:10.1107/S1600536810002461

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o445

https://doi.org/10.1107/S1600536810002461

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2,2-Dichloro-1-(2-phenyl-1,3-oxazolidin-3-yl)ethanone

Fei Ye,^a Ying Fu ^a ^* and Shuang Zhao ^a

^aCollege of Science, Northeast Agricultural University, Harbin 150030, People's Republic of China
^*Correspondence e-mail: fuying@neau.edu.cn

(Received 11 January 2010; accepted 19 January 2010; online 27 January 2010)

In the title molecule, C₁₁H₁₁Cl₂NO₂, the oxazolidine ring is in an envelope conformation with the O atom forming the flap; the other four essentially planar ring atoms (r.m.s. deviation = 0.012 Å) form a dihedral angle of 91.1 (3)° with the phenyl ring. In the crystal structure, molecules are linked by weak intermolecular C—H⋯O hydrogen bonds, forming one-dimensional chains.

Related literature

For general background to substituted oxazolidines see: Agami et al. (2004 ); Guirado et al. (2003 ); Tararov et al. (2003 ). For the bioactivity of related compounds, see: Hatzios et al. (2004 ); Daniele et al. (2007 ). For details of the synthesis, see: Fu et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₁Cl₂NO₂
M_r = 260.11
Orthorhombic, P c c n
a = 19.1775 (13) Å
b = 10.6165 (7) Å
c = 11.3723 (8) Å
V = 2315.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 298 K
0.46 × 0.38 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.780, T_max = 0.897
16860 measured reflections
2846 independent reflections
2323 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.04
2846 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O2ⁱ	0.98	2.40	3.312 (2)	156
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810002461/lh2978sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002461/lh2978Isup2.hkl

checkCIF report

Comment top

Substituted oxazolidines are important synthetic targets due to their biological activity (Agami et al., 2004), pharmacological activity and their extensive use as chiral auxiliaries for the synthesis of many chiral compounds (Guirado et al., 2003; Tararov et al. 2003). Dichloroacetemide compounds have been shown to act as herbicide safeners (Hatzios, 2004; Daniele et al., 2007). As part of our ongoing investigations of oxazolidine derivatives we prepared the title compound and its crystal structure is reported herein.

The molecular structure of the title compound is shown in Fig.1. In the crystal structure, molecules are linked by weak intermolecular C—H···O hydrogen bonds to form one-dimensional chains (Fig. 2).

Related literature top

For general background to substituted oxazolidines see: Agami et al. (2004); Guirado et al. (2003); Tararov et al. (2003). For the bioactivity of related compounds, see: Hatzios et al. (2004); Daniele et al. (2007). For details of the synthesis, see: Fu et al. (2009).

Experimental top

The title compound was prepared by a slightly modified literature procedure (Fu et al., 2009).

Ethanolamine (4.1 g, 0.067 mol) and 7.1g (0.067mol) of benzaldehyde were mixed with 25mL of benzene. The reaction mixture was stirred for 1h at 306-308K. Then, the mixture was heated to reflux and water was evaporated, followed by cooling to 273K and 7.5 mL of 33% sodium hydroxide solution was added. 11.8 g (0.08mol) of dichloroacetyl chloride was added dropwise with stirring, keeping the temperature at 273-277K. Stirring was continued for 1.5h. The mixture was rinsed with water until the pH=7. The organic phase was dried over anhydrous magnesium sulfate and the benzene was removed under vacuum. The crude product was recrystallized with ethyl acetate and light petroleum, white crystals wre obtained. The yield was 58.2%. m.p. 374-377K.

The single-crystal suitable for X-ray structural analysis was obtained by slow evaporation of a solution of the title compound in petroleum ether and ethyl acetate at room temperature.

Structure description top

For general background to substituted oxazolidines see: Agami et al. (2004); Guirado et al. (2003); Tararov et al. (2003). For the bioactivity of related compounds, see: Hatzios et al. (2004); Daniele et al. (2007). For details of the synthesis, see: Fu et al. (2009).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom-labelling scheme.Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of the title compound showing C-H···O hydrogen bonds as dashed lines.

2,2-Dichloro-1-(2-phenyl-1,3-oxazolidin-3-yl)ethanone top

Crystal data top

C₁₁H₁₁Cl₂NO₂	F(000) = 1072.0
M_r = 260.11	D_x = 1.492 Mg m⁻³ D_m = 1.492 Mg m⁻³ D_m measured by not measured
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 5877 reflections
a = 19.1775 (13) Å	θ = 2.8–27.9°
b = 10.6165 (7) Å	µ = 0.54 mm⁻¹
c = 11.3723 (8) Å	T = 298 K
V = 2315.4 (3) Å³	Block, colourless
Z = 8	0.46 × 0.38 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	2846 independent reflections
Radiation source: fine-focus sealed tube	2323 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
T_min = 0.780, T_max = 0.897	k = −14→14
16860 measured reflections	l = −15→15

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0473P)² + 1.2513P] where P = (F_o² + 2F_c²)/3
2846 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₁₁Cl₂NO₂	V = 2315.4 (3) Å³
M_r = 260.11	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 19.1775 (13) Å	µ = 0.54 mm⁻¹
b = 10.6165 (7) Å	T = 298 K
c = 11.3723 (8) Å	0.46 × 0.38 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	2846 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2323 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.897	R_int = 0.022
16860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
2846 reflections	Δρ_min = −0.29 e Å⁻³
145 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
Cl1	0.43189 (3)	0.78273 (5)	0.61104 (4)	0.05385 (16)
Cl2	0.38622 (3)	0.67345 (6)	0.83020 (5)	0.06457 (19)
N1	0.54978 (8)	0.77484 (13)	0.88700 (13)	0.0370 (3)
O1	0.60625 (8)	0.77362 (14)	1.06154 (12)	0.0555 (4)
C11	0.46001 (9)	0.72103 (16)	0.74626 (16)	0.0398 (4)
H11	0.4904	0.6483	0.7323	0.048*
C10	0.49952 (9)	0.82044 (15)	0.81777 (15)	0.0372 (4)
O2	0.48479 (8)	0.93204 (12)	0.81157 (14)	0.0554 (4)
C9	0.56836 (10)	0.64244 (17)	0.90877 (18)	0.0468 (4)
H9A	0.5882	0.6034	0.8393	0.056*
H9B	0.5283	0.5940	0.9347	0.056*
C5	0.65059 (10)	0.91874 (17)	0.91330 (18)	0.0469 (4)
C7	0.58735 (10)	0.85716 (17)	0.96905 (16)	0.0431 (4)
H7	0.5557	0.9221	0.9992	0.052*
C6	0.67948 (11)	0.8764 (2)	0.8089 (2)	0.0549 (5)
H6	0.6588	0.8094	0.7696	0.066*
C8	0.62234 (13)	0.65601 (19)	1.0063 (2)	0.0593 (6)
H8A	0.6187	0.5872	1.0620	0.071*
H8B	0.6692	0.6571	0.9741	0.071*
C1	0.73902 (12)	0.9323 (2)	0.7616 (3)	0.0722 (7)
H1	0.7579	0.9027	0.6915	0.087*
C2	0.76916 (14)	1.0306 (3)	0.8190 (3)	0.0880 (10)
H2	0.8087	1.0684	0.7873	0.106*
C3	0.74266 (15)	1.0743 (2)	0.9217 (3)	0.0859 (10)
H3	0.7644	1.1408	0.9602	0.103*
C4	0.68205 (13)	1.0194 (2)	0.9706 (3)	0.0687 (7)
H4	0.6635	1.0503	1.0404	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0541 (3)	0.0720 (4)	0.0354 (2)	−0.0010 (2)	−0.00397 (19)	0.0028 (2)
Cl2	0.0712 (4)	0.0745 (4)	0.0481 (3)	−0.0336 (3)	0.0014 (2)	0.0033 (2)
N1	0.0418 (7)	0.0300 (7)	0.0392 (8)	0.0004 (5)	−0.0036 (6)	−0.0011 (6)
O1	0.0760 (9)	0.0524 (8)	0.0380 (7)	0.0039 (7)	−0.0131 (7)	0.0019 (6)
C11	0.0440 (9)	0.0380 (9)	0.0374 (9)	0.0004 (7)	−0.0043 (7)	−0.0017 (7)
C10	0.0404 (8)	0.0332 (8)	0.0379 (9)	−0.0010 (7)	−0.0017 (7)	0.0010 (7)
O2	0.0669 (9)	0.0311 (6)	0.0684 (9)	0.0031 (6)	−0.0216 (7)	0.0007 (6)
C9	0.0557 (11)	0.0333 (9)	0.0513 (11)	0.0084 (8)	−0.0050 (9)	−0.0002 (7)
C5	0.0479 (10)	0.0323 (8)	0.0604 (12)	0.0007 (7)	−0.0221 (9)	0.0043 (8)
C7	0.0518 (10)	0.0380 (9)	0.0394 (9)	0.0051 (8)	−0.0115 (8)	−0.0054 (7)
C6	0.0491 (10)	0.0543 (12)	0.0614 (13)	−0.0079 (9)	−0.0096 (9)	0.0089 (10)
C8	0.0771 (14)	0.0455 (11)	0.0552 (12)	0.0101 (10)	−0.0184 (11)	0.0056 (9)
C1	0.0502 (12)	0.0794 (16)	0.0871 (18)	−0.0083 (12)	−0.0058 (12)	0.0259 (14)
C2	0.0569 (14)	0.0697 (17)	0.138 (3)	−0.0160 (13)	−0.0268 (17)	0.0369 (19)
C3	0.0719 (16)	0.0409 (11)	0.145 (3)	−0.0149 (11)	−0.0536 (19)	0.0079 (15)
C4	0.0716 (14)	0.0397 (10)	0.0948 (18)	0.0036 (10)	−0.0389 (14)	−0.0066 (11)

Geometric parameters (Å, º) top

Cl1—C11	1.7563 (18)	C5—C4	1.389 (3)
Cl2—C11	1.7803 (19)	C5—C7	1.517 (3)
N1—C10	1.335 (2)	C7—H7	0.9800
N1—C7	1.468 (2)	C6—C1	1.395 (3)
N1—C9	1.471 (2)	C6—H6	0.9300
O1—C7	1.423 (2)	C8—H8A	0.9700
O1—C8	1.431 (3)	C8—H8B	0.9700
C11—C10	1.533 (2)	C1—C2	1.360 (4)
C11—H11	0.9800	C1—H1	0.9300
C10—O2	1.220 (2)	C2—C3	1.355 (5)
C9—C8	1.524 (3)	C2—H2	0.9300
C9—H9A	0.9700	C3—C4	1.414 (4)
C9—H9B	0.9700	C3—H3	0.9300
C5—C6	1.385 (3)	C4—H4	0.9300

C10—N1—C7	120.89 (14)	O1—C7—H7	109.7
C10—N1—C9	128.35 (15)	N1—C7—H7	109.7
C7—N1—C9	110.07 (14)	C5—C7—H7	109.7
C7—O1—C8	105.92 (14)	C5—C6—C1	121.4 (2)
C10—C11—Cl1	111.07 (12)	C5—C6—H6	119.3
C10—C11—Cl2	107.69 (12)	C1—C6—H6	119.3
Cl1—C11—Cl2	109.34 (10)	O1—C8—C9	104.80 (16)
C10—C11—H11	109.6	O1—C8—H8A	110.8
Cl1—C11—H11	109.6	C9—C8—H8A	110.8
Cl2—C11—H11	109.6	O1—C8—H8B	110.8
O2—C10—N1	123.59 (16)	C9—C8—H8B	110.8
O2—C10—C11	121.57 (16)	H8A—C8—H8B	108.9
N1—C10—C11	114.83 (14)	C2—C1—C6	119.2 (3)
N1—C9—C8	101.35 (15)	C2—C1—H1	120.4
N1—C9—H9A	111.5	C6—C1—H1	120.4
C8—C9—H9A	111.5	C3—C2—C1	121.2 (3)
N1—C9—H9B	111.5	C3—C2—H2	119.4
C8—C9—H9B	111.5	C1—C2—H2	119.4
H9A—C9—H9B	109.3	C2—C3—C4	120.4 (2)
C6—C5—C4	118.5 (2)	C2—C3—H3	119.8
C6—C5—C7	122.59 (17)	C4—C3—H3	119.8
C4—C5—C7	118.9 (2)	C5—C4—C3	119.3 (3)
O1—C7—N1	102.94 (14)	C5—C4—H4	120.3
O1—C7—C5	111.96 (15)	C3—C4—H4	120.3
N1—C7—C5	112.55 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O2ⁱ	0.98	2.40	3.312 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁Cl₂NO₂
M_r	260.11
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	298
a, b, c (Å)	19.1775 (13), 10.6165 (7), 11.3723 (8)
V (Å³)	2315.4 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.46 × 0.38 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.780, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	16860, 2846, 2323
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.04
No. of reflections	2846
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.29

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O2ⁱ	0.98	2.40	3.312 (2)	156

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

Acknowledgements

We thanks the Heilongjiang Province Foundation for Young Scholar (QC2009C44), the China Postdoctoral Science Foundation (20080430951), the Heilongjiang Province Postdoctoral Science Foundation (LBH-Z07012) and the Northeast Agricultural University Doctoral Foundation for generously supporting this study.

References

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