2,2-Dichloro-1-[(2R,5S)-5-ethyl-2-methyl-2-propyl-1,3-oxazolidin-3-yl]ethanone

Fu, Y.; Ye, F.; Wen, X.

doi:10.1107/S1600536810016090

organic compounds

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Volume 66| Part 6| June 2010| Page o1293

https://doi.org/10.1107/S1600536810016090

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2,2-Dichloro-1-[(2R,5S)-5-ethyl-2-methyl-2-propyl-1,3-oxazolidin-3-yl]ethanone

Ying Fu,^a Fei Ye ^a ^* and Xiaotian Wen ^a

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

(Received 23 April 2010; accepted 1 May 2010; online 8 May 2010)

In the title compound, C₁₁H₁₉Cl₂NO₂, the oxazolidine ring is in an envelope conformation with the O atom forming the flap. In the crystal structure, molecules are linked by weak intermolecular C—H⋯O hydrogen bonds, forming chains.

Related literature

For general background to N-dichloroacetyl oxazolidine, see: Agami & Couty (2004 ); Abu-Qare & Duncan (2002 ); Guirado et al. (2003 ); Davies & Caseley (1999 ). For the bioactivity of related compounds, see: Del Buono et al. (2007 ); Hatzios & Burgos (2004 ). For details of the synthesis, see: Fu et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₉Cl₂NO₂
M_r = 268.17
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.4834 (12) Å
b = 10.795 (2) Å
c = 20.030 (4) Å
V = 1401.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 293 K
0.32 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.869, T_max = 0.915
14134 measured reflections
3499 independent reflections
2117 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.258
S = 1.02
3499 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ) 1468 Friedels
Flack parameter: 0.02 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱ	0.98	2.38	3.327 (5)	163
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536810016090/lh5034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016090/lh5034Isup2.hkl

checkCIF report

Comment top

N-dichloroacetyl oxazolidines are becoming increasingly important with their excellent biological activity (Agami & Couty, 2004; Abu-Qare & Duncan, 2002; Guirado et al., 2003; Davies & Caseley, 1999). The discovery of N-dichloroacetyl oxazolidine as a herbicide safener has drawn widespread attention in agricultural biochemistry (Del Buono et al., 2007; Hatzios & Burgos, 2004). As a part of our ongoing investigation of oxazolidine derivatives (Fu et al., 2009) we prepared the title compound.

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 N-dichloroacetyl oxazolidine, see: Agami & Couty (2004); Abu-Qare & Duncan (2002); Guirado et al. (2003); Davies & Caseley (1999). For the bioactivity of related compounds, see: Del Buono et al. (2007); Hatzios & Burgos (2004). For details of the synthesis, see: Fu et al. (2009).

Experimental top

The title compound was prepared according to the literature procedure (Fu et al., 2009). The single crystal suitable for X-ray structural analysis was obtained by slow evaporation in petroleum ether and ethyl acetate at room temperature. The title enantiomer spontaneously resolved from a racemic mixture during the crystallization.

Structure description top

For general background to N-dichloroacetyl oxazolidine, see: Agami & Couty (2004); Abu-Qare & Duncan (2002); Guirado et al. (2003); Davies & Caseley (1999). For the bioactivity of related compounds, see: Del Buono et al. (2007); Hatzios & Burgos (2004). 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. A packing diagram for (I), showing weak hydrogen bonds as dashed lines.

2,2-Dichloro-1-[(2R,5S)-5-ethyl-2-methyl-2-propyl- 1,3-oxazolidin-3-yl]ethanone top

Crystal data top

C₁₁H₁₉Cl₂NO₂	F(000) = 568.0
M_r = 268.17	D_x = 1.271 Mg m⁻³ D_m = 1.271 Mg m⁻³ D_m measured by not measured
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3142 reflections
a = 6.4834 (12) Å	θ = 2.8–20.6°
b = 10.795 (2) Å	µ = 0.45 mm⁻¹
c = 20.030 (4) Å	T = 293 K
V = 1401.8 (5) Å³	Block, colourless
Z = 4	0.32 × 0.24 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	3499 independent reflections
Radiation source: fine-focus sealed tube	2117 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 28.4°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.869, T_max = 0.915	k = −14→14
14134 measured reflections	l = −25→26

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)] = 0.084	H-atom parameters constrained
wR(F²) = 0.258	w = 1/[σ²(F_o²) + (0.165P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3499 reflections	Δρ_max = 0.58 e Å⁻³
148 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints	Absolute structure: Flack (1983) 1468 Friedels
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (15)

Crystal data top

C₁₁H₁₉Cl₂NO₂	V = 1401.8 (5) Å³
M_r = 268.17	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.4834 (12) Å	µ = 0.45 mm⁻¹
b = 10.795 (2) Å	T = 293 K
c = 20.030 (4) Å	0.32 × 0.24 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	3499 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2117 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.915	R_int = 0.058
14134 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	H-atom parameters constrained
wR(F²) = 0.258	Δρ_max = 0.58 e Å⁻³
S = 1.02	Δρ_min = −0.39 e Å⁻³
3499 reflections	Absolute structure: Flack (1983) 1468 Friedels
148 parameters	Absolute structure parameter: 0.02 (15)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.5074 (7)	0.9192 (4)	0.2071 (2)	0.0675 (11)
H1	0.4966	0.8365	0.2270	0.081*
C2	0.5889 (7)	1.0103 (3)	0.2598 (2)	0.0638 (10)
C3	0.7886 (9)	0.8326 (4)	0.3065 (3)	0.0789 (13)
H3A	0.6784	0.7758	0.3181	0.095*
H3B	0.8454	0.8089	0.2636	0.095*
C4	0.9470 (13)	0.8334 (4)	0.3575 (3)	0.105 (2)
H4	1.0627	0.8594	0.3293	0.126*
C5	1.0407 (13)	0.7301 (5)	0.3866 (4)	0.122 (3)
H5A	1.0922	0.6801	0.3500	0.147*
H5B	0.9306	0.6828	0.4072	0.147*
C6	1.2052 (13)	0.7357 (6)	0.4353 (3)	0.111 (2)
H6A	1.3358	0.7362	0.4127	0.166*
H6B	1.1976	0.6647	0.4640	0.166*
H6C	1.1915	0.8098	0.4614	0.166*
C7	0.8170 (7)	1.0342 (4)	0.3589 (2)	0.0680 (10)
C8	0.9703 (10)	1.1251 (5)	0.3287 (3)	0.0925 (16)
H8A	1.0635	1.1533	0.3627	0.139*
H8B	0.8973	1.1946	0.3104	0.139*
H8C	1.0470	1.0847	0.2939	0.139*
C9	0.6750 (10)	1.1009 (5)	0.4051 (3)	0.0875 (14)
H9A	0.7550	1.1310	0.4427	0.105*
H9B	0.6205	1.1727	0.3819	0.105*
C10	0.4982 (11)	1.0277 (6)	0.4315 (3)	0.1013 (18)
H10A	0.5481	0.9494	0.4488	0.122*
H10B	0.4023	1.0103	0.3955	0.122*
C11	0.3855 (15)	1.0989 (8)	0.4874 (4)	0.127 (3)
H11A	0.4781	1.1119	0.5242	0.190*
H11B	0.2688	1.0516	0.5023	0.190*
H11C	0.3396	1.1775	0.4707	0.190*
Cl1	0.6885 (3)	0.91462 (14)	0.14073 (7)	0.0996 (5)
Cl2	0.2642 (2)	0.96549 (13)	0.17873 (9)	0.1008 (5)
N1	0.7143 (5)	0.9597 (3)	0.30507 (18)	0.0629 (8)
O1	0.9265 (6)	0.9417 (3)	0.39428 (17)	0.0793 (9)
O2	0.5407 (6)	1.1193 (3)	0.2580 (2)	0.0859 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.072 (2)	0.0401 (18)	0.090 (3)	0.0031 (17)	−0.013 (2)	0.0002 (18)
C2	0.071 (2)	0.0396 (17)	0.081 (3)	0.0077 (17)	0.000 (2)	−0.0023 (17)
C3	0.093 (3)	0.0354 (18)	0.108 (3)	0.014 (2)	−0.021 (3)	−0.0090 (18)
C4	0.154 (5)	0.046 (2)	0.114 (4)	0.033 (3)	−0.043 (4)	−0.013 (3)
C5	0.149 (6)	0.059 (3)	0.160 (6)	0.031 (4)	−0.071 (5)	−0.020 (3)
C6	0.127 (5)	0.070 (3)	0.134 (5)	0.010 (4)	−0.031 (4)	0.013 (3)
C7	0.084 (3)	0.0379 (17)	0.082 (3)	0.0039 (18)	−0.010 (2)	−0.0029 (16)
C8	0.101 (4)	0.052 (2)	0.124 (4)	−0.020 (3)	−0.013 (3)	0.003 (3)
C9	0.109 (4)	0.060 (3)	0.093 (3)	0.006 (3)	0.003 (3)	−0.010 (2)
C10	0.105 (4)	0.075 (3)	0.124 (5)	0.010 (3)	0.006 (3)	0.000 (3)
C11	0.149 (6)	0.124 (6)	0.107 (4)	0.021 (5)	0.035 (4)	−0.005 (4)
Cl1	0.1169 (11)	0.0780 (8)	0.1038 (9)	−0.0063 (8)	0.0152 (9)	−0.0185 (7)
Cl2	0.0899 (8)	0.0761 (8)	0.1365 (12)	0.0154 (7)	−0.0350 (8)	−0.0093 (7)
N1	0.0715 (19)	0.0298 (13)	0.087 (2)	0.0036 (14)	−0.0060 (17)	−0.0042 (13)
O1	0.102 (2)	0.0413 (14)	0.095 (2)	0.0055 (15)	−0.0232 (19)	−0.0079 (14)
O2	0.114 (3)	0.0338 (13)	0.110 (2)	0.0152 (16)	−0.023 (2)	−0.0013 (14)

Geometric parameters (Å, º) top

C1—C2	1.536 (6)	C6—H6C	0.9600
C1—Cl2	1.750 (4)	C7—O1	1.416 (5)
C1—Cl1	1.775 (5)	C7—C9	1.491 (7)
C1—H1	0.9800	C7—N1	1.501 (5)
C2—O2	1.218 (5)	C7—C8	1.523 (7)
C2—N1	1.335 (6)	C8—H8A	0.9600
C3—C4	1.448 (8)	C8—H8B	0.9600
C3—N1	1.454 (5)	C8—H8C	0.9600
C3—H3A	0.9700	C9—C10	1.490 (9)
C3—H3B	0.9700	C9—H9A	0.9700
C4—O1	1.388 (6)	C9—H9B	0.9700
C4—C5	1.397 (7)	C10—C11	1.542 (9)
C4—H4	0.9800	C10—H10A	0.9700
C5—C6	1.446 (10)	C10—H10B	0.9700
C5—H5A	0.9700	C11—H11A	0.9600
C5—H5B	0.9700	C11—H11B	0.9600
C6—H6A	0.9600	C11—H11C	0.9600
C6—H6B	0.9600

C2—C1—Cl2	110.5 (3)	O1—C7—N1	101.8 (3)
C2—C1—Cl1	107.8 (3)	C9—C7—N1	115.5 (4)
Cl2—C1—Cl1	111.1 (3)	O1—C7—C8	109.0 (4)
C2—C1—H1	109.1	C9—C7—C8	109.8 (4)
Cl2—C1—H1	109.1	N1—C7—C8	110.5 (4)
Cl1—C1—H1	109.1	C7—C8—H8A	109.5
O2—C2—N1	124.9 (4)	C7—C8—H8B	109.5
O2—C2—C1	120.7 (4)	H8A—C8—H8B	109.5
N1—C2—C1	114.5 (3)	C7—C8—H8C	109.5
C4—C3—N1	104.1 (4)	H8A—C8—H8C	109.5
C4—C3—H3A	110.9	H8B—C8—H8C	109.5
N1—C3—H3A	110.9	C10—C9—C7	116.0 (5)
C4—C3—H3B	110.9	C10—C9—H9A	108.3
N1—C3—H3B	110.9	C7—C9—H9A	108.3
H3A—C3—H3B	108.9	C10—C9—H9B	108.3
O1—C4—C5	119.5 (5)	C7—C9—H9B	108.3
O1—C4—C3	108.1 (4)	H9A—C9—H9B	107.4
C5—C4—C3	126.8 (5)	C9—C10—C11	111.0 (6)
O1—C4—H4	97.9	C9—C10—H10A	109.4
C5—C4—H4	97.9	C11—C10—H10A	109.4
C3—C4—H4	97.9	C9—C10—H10B	109.4
C4—C5—C6	124.7 (6)	C11—C10—H10B	109.4
C4—C5—H5A	106.2	H10A—C10—H10B	108.0
C6—C5—H5A	106.2	C10—C11—H11A	109.5
C4—C5—H5B	106.2	C10—C11—H11B	109.5
C6—C5—H5B	106.2	H11A—C11—H11B	109.5
H5A—C5—H5B	106.3	C10—C11—H11C	109.5
C5—C6—H6A	109.5	H11A—C11—H11C	109.5
C5—C6—H6B	109.5	H11B—C11—H11C	109.5
H6A—C6—H6B	109.5	C2—N1—C3	127.0 (3)
C5—C6—H6C	109.5	C2—N1—C7	122.6 (3)
H6A—C6—H6C	109.5	C3—N1—C7	110.1 (3)
H6B—C6—H6C	109.5	C4—O1—C7	112.1 (3)
O1—C7—C9	109.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.98	2.38	3.327 (5)	163

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₉Cl₂NO₂
M_r	268.17
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.4834 (12), 10.795 (2), 20.030 (4)
V (Å³)	1401.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.32 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.869, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	14134, 3499, 2117
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.258, 1.02
No. of reflections	3499
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.39
Absolute structure	Flack (1983) 1468 Friedels
Absolute structure parameter	0.02 (15)

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
C1—H1···O2ⁱ	0.98	2.38	3.327 (5)	163

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

Acknowledgements

We thank the Heilongjiang Province Foundation for Young Scholars (QC2009C44), the Innovation Foundation for Young Scholars of Harbin (No.2007RFQXN017),the China Postdoctoral Science Foundation (20080430951), the Heilongjiang Province Postdoctoral Science Foundation and the Northeast Agricultural University Doctoral Foundation for generously supporting this study.

References

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