(E)-(2,4-Dichloro­benzyl­idene)amino cyclo­propane­carboxyl­ate

Wang, M.-Y.; Zhang, Y.

doi:10.1107/S1600536812018016

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1594

doi:10.1107/S1600536812018016

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(E)-(2,4-Dichlorobenzylidene)amino cyclopropanecarboxylate

Mei-Yi Wang ^a ^* and Ya Zhang ^a

^aCollege of Chemistry and Chemical Engineering, Beifang University of Nationalities, Yinchuan 750021, People's Republic of China
^*Correspondence e-mail: aseonliu@gmail.com

(Received 10 April 2012; accepted 23 April 2012; online 2 May 2012)

In the title compound C₁₁H₉Cl₂NO₂, the dihedral angle between the benzene and cyclopropane ring planes is 89.95 (13)°. The carbonyl–oxime grouping is almost coplanar with the benzene ring [dihedral angle = 4.08 (6)°]. In the crystal, molecules are linked by C—H⋯O interactions into [100] chains.

Related literature

For further synthetic details, see: Liu et al. (2011b , 2012 ). For related structures, see: Liu & Liu (2011 ) Liu et al. (2011d ). For the biological activity of related compounds, see: Liu et al. (2010 , 2011a ,c ).

Experimental

Crystal data

C₁₁H₉Cl₂NO₂
M_r = 258.09
Triclinic, $[P \overline 1]$
a = 6.4381 (13) Å
b = 7.6030 (15) Å
c = 11.956 (2) Å
α = 94.90 (3)°
β = 100.42 (3)°
γ = 102.70 (3)°
V = 556.71 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 113 K
0.24 × 0.20 × 0.10 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.876, T_max = 0.946
3737 measured reflections
1937 independent reflections
1563 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.076
S = 1.03
1937 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O1ⁱ	0.97	2.57	3.5008 (19)	161
Symmetry code: (i) x-1, y, z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812018016/hb6735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018016/hb6735Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812018016/hb6735Isup3.cml

checkCIF report

Related literature top

For further synthetic details, see: Liu et al. (2011b, 2012). For related structures, see: Liu & Liu (2011) Liu et al. (2011d). For the biological activity of related compounds, see: Liu et al. (2010, 2011a,c).

Experimental top

Dropwised the cyclopropanecarbonyl chloride to 2,4-dichlorobenzaldehyde oxime (7.50 mmol in 25 ml THF) and 7.5 mmol Et3N, then vigorously stirred at ambient temperature for overnight. The corresponding product precipitated immediately. Compound was dissolved in hot alcohol and the resulting solution was allowed to stand in air at room temperature to give colourless blocks of the title compound.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: SHELXL97 (Sheldrick, 2008.

Figures top

Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.

(E)-(2,4-Dichlorobenzylidene)amino cyclopropanecarboxylate top

Crystal data top

C₁₁H₉Cl₂NO₂	Z = 2
M_r = 258.09	F(000) = 264
Triclinic, P1	D_x = 1.540 Mg m⁻³
a = 6.4381 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6030 (15) Å	Cell parameters from 1887 reflections
c = 11.956 (2) Å	θ = 1.8–27.9°
α = 94.90 (3)°	µ = 0.57 mm⁻¹
β = 100.42 (3)°	T = 113 K
γ = 102.70 (3)°	Block, coloress
V = 556.71 (19) Å³	0.24 × 0.20 × 0.10 mm

Data collection top

Rigaku Saturn CCD diffractometer	1937 independent reflections
Radiation source: rotating anode	1563 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.030
ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −7→7
T_min = 0.876, T_max = 0.946	k = −9→6
3737 measured reflections	l = −14→14

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0407P)²] where P = (F_o² + 2F_c²)/3
1937 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₉Cl₂NO₂	γ = 102.70 (3)°
M_r = 258.09	V = 556.71 (19) Å³
Triclinic, P1	Z = 2
a = 6.4381 (13) Å	Mo Kα radiation
b = 7.6030 (15) Å	µ = 0.57 mm⁻¹
c = 11.956 (2) Å	T = 113 K
α = 94.90 (3)°	0.24 × 0.20 × 0.10 mm
β = 100.42 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	1937 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1563 reflections with I > 2σ(I)
T_min = 0.876, T_max = 0.946	R_int = 0.030
3737 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.03	Δρ_max = 0.24 e Å⁻³
1937 reflections	Δρ_min = −0.21 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	0.32359 (6)	0.70035 (5)	0.47089 (3)	0.02317 (14)
Cl2	1.15092 (6)	0.98054 (6)	0.68823 (4)	0.02531 (14)
O1	0.08882 (17)	0.30779 (16)	0.94813 (9)	0.0263 (3)
O2	0.00692 (16)	0.37138 (15)	0.76492 (9)	0.0186 (3)
N1	0.2306 (2)	0.46280 (18)	0.78101 (11)	0.0202 (3)
C1	−0.3868 (2)	0.2548 (2)	0.94150 (14)	0.0217 (4)
H1A	−0.2971	0.3293	1.0106	0.026*
H1B	−0.5348	0.2689	0.9234	0.026*
C2	−0.3504 (3)	0.0724 (2)	0.91336 (14)	0.0208 (4)
H2A	−0.4764	−0.0249	0.8783	0.025*
H2B	−0.2388	0.0354	0.9655	0.025*
C3	−0.2777 (2)	0.2198 (2)	0.84222 (14)	0.0198 (4)
H3	−0.3629	0.2113	0.7644	0.024*
C4	−0.0426 (2)	0.3004 (2)	0.86199 (13)	0.0177 (4)
C5	0.2637 (2)	0.5304 (2)	0.69054 (14)	0.0177 (4)
H5	0.1511	0.5129	0.6268	0.021*
C6	0.4823 (2)	0.6365 (2)	0.68810 (14)	0.0164 (4)
C7	0.5265 (3)	0.7218 (2)	0.59348 (13)	0.0168 (4)
C8	0.7305 (2)	0.8271 (2)	0.59131 (13)	0.0188 (4)
H8	0.7566	0.8836	0.5275	0.023*
C9	0.8947 (2)	0.8453 (2)	0.68750 (14)	0.0187 (4)
C10	0.8595 (3)	0.7612 (2)	0.78232 (14)	0.0196 (4)
H10	0.9725	0.7736	0.8453	0.024*
C11	0.6539 (2)	0.6579 (2)	0.78256 (14)	0.0177 (4)
H11	0.6293	0.6016	0.8466	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0227 (2)	0.0314 (3)	0.0143 (2)	0.00420 (18)	0.00140 (17)	0.00786 (18)
Cl2	0.0192 (2)	0.0275 (2)	0.0273 (3)	−0.00120 (17)	0.00716 (17)	0.00581 (18)
O1	0.0182 (6)	0.0425 (8)	0.0166 (7)	0.0021 (5)	0.0021 (5)	0.0121 (6)
O2	0.0123 (5)	0.0267 (6)	0.0165 (6)	0.0012 (5)	0.0038 (4)	0.0082 (5)
N1	0.0117 (6)	0.0267 (8)	0.0213 (8)	0.0005 (6)	0.0039 (5)	0.0072 (6)
C1	0.0179 (8)	0.0266 (9)	0.0221 (10)	0.0051 (7)	0.0073 (7)	0.0061 (7)
C2	0.0191 (8)	0.0226 (9)	0.0198 (9)	0.0004 (7)	0.0059 (7)	0.0054 (7)
C3	0.0151 (8)	0.0264 (9)	0.0160 (9)	0.0002 (7)	0.0027 (7)	0.0059 (7)
C4	0.0187 (8)	0.0201 (8)	0.0162 (9)	0.0045 (7)	0.0070 (7)	0.0059 (7)
C5	0.0178 (8)	0.0218 (9)	0.0145 (9)	0.0048 (7)	0.0041 (7)	0.0056 (7)
C6	0.0184 (8)	0.0158 (8)	0.0162 (9)	0.0042 (6)	0.0061 (7)	0.0031 (6)
C7	0.0185 (8)	0.0193 (8)	0.0134 (9)	0.0070 (6)	0.0019 (6)	0.0024 (6)
C8	0.0244 (9)	0.0189 (9)	0.0165 (10)	0.0057 (7)	0.0100 (7)	0.0071 (7)
C9	0.0181 (8)	0.0170 (8)	0.0223 (9)	0.0038 (7)	0.0082 (7)	0.0024 (7)
C10	0.0189 (8)	0.0226 (9)	0.0183 (9)	0.0077 (7)	0.0022 (7)	0.0040 (7)
C11	0.0194 (8)	0.0206 (9)	0.0166 (9)	0.0079 (7)	0.0065 (7)	0.0073 (7)

Geometric parameters (Å, º) top

Cl1—C7	1.7477 (16)	C3—C4	1.470 (2)
Cl2—C9	1.7394 (16)	C3—H3	0.9800
O1—C4	1.1976 (18)	C5—C6	1.467 (2)
O2—C4	1.3800 (19)	C5—H5	0.9300
O2—N1	1.4253 (16)	C6—C7	1.394 (2)
N1—C5	1.269 (2)	C6—C11	1.401 (2)
C1—C2	1.478 (2)	C7—C8	1.385 (2)
C1—C3	1.517 (2)	C8—C9	1.389 (2)
C1—H1A	0.9700	C8—H8	0.9300
C1—H1B	0.9700	C9—C10	1.378 (2)
C2—C3	1.508 (2)	C10—C11	1.383 (2)
C2—H2A	0.9700	C10—H10	0.9300
C2—H2B	0.9700	C11—H11	0.9300

C4—O2—N1	112.18 (11)	O2—C4—C3	109.31 (12)
C5—N1—O2	109.05 (12)	N1—C5—C6	118.94 (14)
C2—C1—C3	60.45 (11)	N1—C5—H5	120.5
C2—C1—H1A	117.7	C6—C5—H5	120.5
C3—C1—H1A	117.7	C7—C6—C11	117.60 (14)
C2—C1—H1B	117.7	C7—C6—C5	121.71 (14)
C3—C1—H1B	117.7	C11—C6—C5	120.69 (15)
H1A—C1—H1B	114.8	C8—C7—C6	122.37 (14)
C1—C2—C3	61.08 (11)	C8—C7—Cl1	116.74 (13)
C1—C2—H2A	117.7	C6—C7—Cl1	120.89 (12)
C3—C2—H2A	117.7	C7—C8—C9	117.79 (15)
C1—C2—H2B	117.7	C7—C8—H8	121.1
C3—C2—H2B	117.7	C9—C8—H8	121.1
H2A—C2—H2B	114.8	C10—C9—C8	121.89 (15)
C4—C3—C2	116.62 (14)	C10—C9—Cl2	119.36 (12)
C4—C3—C1	115.92 (13)	C8—C9—Cl2	118.75 (13)
C2—C3—C1	58.47 (11)	C9—C10—C11	119.14 (14)
C4—C3—H3	117.5	C9—C10—H10	120.4
C2—C3—H3	117.5	C11—C10—H10	120.4
C1—C3—H3	117.5	C10—C11—C6	121.20 (15)
O1—C4—O2	123.97 (14)	C10—C11—H11	119.4
O1—C4—C3	126.72 (15)	C6—C11—H11	119.4

C4—O2—N1—C5	−177.60 (13)	C5—C6—C7—C8	177.96 (16)
C1—C2—C3—C4	105.44 (16)	C11—C6—C7—Cl1	179.11 (13)
C2—C1—C3—C4	−106.64 (16)	C5—C6—C7—Cl1	−2.0 (2)
N1—O2—C4—O1	−3.1 (2)	C6—C7—C8—C9	0.4 (3)
N1—O2—C4—C3	176.04 (13)	Cl1—C7—C8—C9	−179.65 (12)
C2—C3—C4—O1	−25.6 (3)	C7—C8—C9—C10	0.6 (3)
C1—C3—C4—O1	40.4 (2)	C7—C8—C9—Cl2	−178.69 (13)
C2—C3—C4—O2	155.33 (15)	C8—C9—C10—C11	−1.1 (3)
C1—C3—C4—O2	−138.66 (14)	Cl2—C9—C10—C11	178.24 (13)
O2—N1—C5—C6	178.12 (13)	C9—C10—C11—C6	0.5 (3)
N1—C5—C6—C7	−176.72 (16)	C7—C6—C11—C10	0.5 (2)
N1—C5—C6—C11	2.2 (3)	C5—C6—C11—C10	−178.44 (16)
C11—C6—C7—C8	−1.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.97	2.57	3.5008 (19)	161

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₉Cl₂NO₂
M_r	258.09
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	6.4381 (13), 7.6030 (15), 11.956 (2)
α, β, γ (°)	94.90 (3), 100.42 (3), 102.70 (3)
V (Å³)	556.71 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.24 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.876, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	3737, 1937, 1563
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.076, 1.03
No. of reflections	1937
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.97	2.57	3.5008 (19)	161

Symmetry code: (i) x−1, y, z.

Acknowledgements

This research work was supported by the Research Program of Beifang University of Nationalities (2010Y047) and the Key Laboratory of Chemical Technology of the SEAC (2010SY16).

References

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