organic papers
o3486
Sunet al. C19H25Cl2NO2 doi:10.1107/S160053680602811X Acta Cryst.(2006). E62, o3486–o3487
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
2,2-Dichloro-1-(4-ethoxyphenyl)cyclopropanyl
2,3-dimethylpiperidin-1-yl ketone
Na-Bo Sun, Cheng-Xia Tan, Jian-Quan Weng and De-Long Shen*
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
Correspondence e-mail: pesticide@zjut.edu.cn
Key indicators
Single-crystal X-ray study T= 298 K
Mean(C–C) = 0.003 A˚ Rfactor = 0.034 wRfactor = 0.085
Data-to-parameter ratio = 18.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 16 July 2006 Accepted 20 July 2006
#2006 International Union of Crystallography All rights reserved
In the title compound, C19H25Cl2NO2, the piperidine ring
shows a normal chair conformation and the cyclopropane ring forms a dihedral angle of 55.68 (17)with the benzene ring.
Comment
Cycloprothrin derivatives have a high potential for biological activity. They are commonly characterized by low toxicity and good environmental compatibility. As part of our ongoing study on the structure–activity relationships for cycloprothrin derivatives and related compounds, we have recently isolated the title compound, (I), and determined its crystal structure.
The molecular structure of (I) is shown in Fig. 1. The piperidine ring shows a normal chair conformation. The cyclopropane ring forms a dihedral angle of 55.68 (17) with
the benzene ring. Weak C—H O hydrogen bonding is observed between neighboring molecules (Table 1).
Experimental
2,3-Dimethylpiperdine (1.0 g, 8.8 mmol) and triethylamine (1.2 g, 11.9 mmol) were dissolved in dichloromethane (15 ml) with stirring. Then 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarbonyl chloride (2.94 g, 10 mmol) was added dropwise to the mixture at room temperature. The mixture was stirred at room temperature for 15 h, washed three times with water and then dried, yielding 2.93 g of a solid product (yield 90.0%). This was recrystallized from ethanol to give single crystals of (I).
Crystal data
C19H25Cl2NO2
Mr= 370.32 Monoclinic,Cc a= 11.662 (5) A˚
b= 16.242 (8) A˚
c= 11.398 (5) A˚
= 115.078 (19)
V= 1955.3 (15) A˚3
Z= 4
Dx= 1.258 Mg m 3
MoKradiation
= 0.34 mm1
T= 298 (1) K Chunk, colorless 0.330.300.20 mm
Data collection
Rigaku R-AXIS RAPID diffractometer
!scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin= 0.888,Tmax= 0.934
9469 measured reflections 4133 independent reflections 3347 reflections withF2> 2(F2)
Rint= 0.024
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.034
wR(F2) = 0.085
S= 1.02 4133 reflections 219 parameters
H-atom parameters constrained
w= 1/[0.0004Fo2+(Fo2)]/(4Fo2)
(/)max< 0.001
max= 0.32 e A˚
3
min=0.37 e A˚
3
Extinction correction: Larson (1970), equation 22 Extinction coefficient: 145 (16) Absolute structure: Flack (1983),
[image:2.610.314.563.73.215.2]1889 Friedel Pairs Flack parameter: 0.009 (4)
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C11—H11 O1i
0.93 2.40 3.322 (3) 170
Symmetry code: (i)xþ1 2;yþ
1 2;zþ
1 2.
Methyl H atoms were placed in calculated positions with C—H = 0.96 A˚ and torsion angles were refined to fit the electron density. Other H atoms were placed in calculated positions with C—H = 0.93 (aromatic), 0.98 (methine) and 0.97 A˚ (methylene), and refined in riding mode, withUiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refine-ment:PROCESS-AUTO; data reduction:CrystalStructure (Rigaku/ MSC, 2004); program(s) used to solve structure:SHELXS97 (Shel-drick, 1997); program(s) used to refine structure: CRYSTALS (Betteridgeet al., 1996); molecular graphics:ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.
The work was supported by the Education Bureau Foun-dation of Zhejiang Province (No. 20030145).
References
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003).J. Appl. Cryst.36, 1487.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Flack, H. D. (1983).Acta Cryst.A39, 876–881.
Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.
Larson, A. C. (1970).Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard.
Rigaku (1998).PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Rigaku/MSC (2004). CrystalStructure. Version 3.7.0. Rigaku/MSC, The
Woodlands, Texas, USA.
Sheldrick, G. M. (1997).SHELXS97. University of Go¨ttingen, Germany.
Figure 1
supporting information
sup-1 Acta Cryst. (2006). E62, o3486–o3487
supporting information
Acta Cryst. (2006). E62, o3486–o3487 [https://doi.org/10.1107/S160053680602811X]
2,2-Dichloro-1-(4-ethoxyphenyl)cyclopropanyl 2,3-dimethylpiperidin-1-yl
ketone
Na-Bo Sun, Cheng-Xia Tan, Jian-Quan Weng and De-Long Shen
2,2-Dichloro-1-(4-ethoxyphenyl)cyclopropanyl 2,3-dimethylpiperidin-1-yl ketone
Crystal data
C19H25Cl2NO2
Mr = 370.32 Monoclinic, Cc
Hall symbol: C -2yc
a = 11.662 (5) Å
b = 16.242 (8) Å
c = 11.398 (5) Å
β = 115.078 (19)°
V = 1955.3 (15) Å3
Z = 4
F(000) = 784.0
Dx = 1.258 Mg m−3
Melting point: 432-434 K K Mo Kα radiation, λ = 0.71075 Å Cell parameters from 8522 reflections
θ = 3.2–27.5°
µ = 0.34 mm−1
T = 298 K Chunk, colorless 0.33 × 0.30 × 0.20 mm
Data collection
Rigaku R-AXIS RAPID diffractometer
Detector resolution: 10.0 pixels mm-1
ω scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin = 0.888, Tmax = 0.934 9469 measured reflections
4133 independent reflections 3347 reflections with F2 > 2σ(F2)
Rint = 0.024
θmax = 27.5°
h = −14→15
k = −21→21
l = −14→14
Refinement
Refinement on F2
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.085
S = 1.02 4133 reflections 219 parameters
H-atom parameters constrained
w = 1/[0.0004Fo2 + 1σ(Fo2)]/(4Fo2) (Δ/σ)max < 0.001
Δρmax = 0.32 e Å−3 Δρmin = −0.37 e Å−3
Extinction correction: Larson (1970), equation 22
Extinction coefficient: 145 (16)
Absolute structure: Flack (1983), 1889 Friedel Pairs
Absolute structure parameter: 0.009 (4)
Special details
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cl1 0.16170 (6) 0.41375 (4) 0.32210 (8) 0.0761 (2)
Cl2 0.16421 (6) 0.41874 (4) 0.06979 (6) 0.0758 (2)
O1 0.08258 (12) 0.23702 (11) 0.01319 (16) 0.0682 (4)
O2 0.10888 (16) 0.08052 (12) 0.56676 (18) 0.0812 (5)
N1 0.27535 (13) 0.17874 (11) 0.07917 (16) 0.0496 (4)
C1 0.23125 (14) 0.27401 (11) 0.22310 (18) 0.0417 (4)
C2 0.34566 (17) 0.33123 (11) 0.2730 (2) 0.0454 (5)
C3 0.21612 (17) 0.36614 (12) 0.2171 (2) 0.0493 (5)
C4 0.19111 (16) 0.22899 (12) 0.0953 (2) 0.0471 (5)
C5 0.40104 (17) 0.15575 (12) 0.1801 (2) 0.0478 (5)
C6 0.5000 (2) 0.17168 (13) 0.1271 (2) 0.0605 (6)
C7 0.4654 (2) 0.1262 (2) −0.0004 (2) 0.0838 (9)
C8 0.3332 (2) 0.1458 (2) −0.0964 (2) 0.0871 (9)
C9 0.2363 (2) 0.13407 (17) −0.0436 (2) 0.0700 (7)
C10 0.19811 (16) 0.22639 (11) 0.31800 (18) 0.0410 (4)
C11 0.28973 (17) 0.19576 (13) 0.4321 (2) 0.0520 (5)
C12 0.25725 (19) 0.14796 (16) 0.5127 (2) 0.0619 (6)
C13 0.1316 (2) 0.13020 (12) 0.4811 (2) 0.0565 (6)
C14 0.03855 (18) 0.16178 (13) 0.3695 (2) 0.0567 (6)
C15 0.07271 (17) 0.20922 (12) 0.2885 (2) 0.0505 (5)
C16 −0.0141 (2) 0.04778 (17) 0.5293 (2) 0.0796 (9)
C17 −0.0076 (3) −0.0121 (2) 0.6285 (3) 0.1073 (12)
C18 0.3989 (2) 0.06890 (13) 0.2284 (2) 0.0656 (7)
C19 0.6334 (2) 0.15331 (18) 0.2252 (3) 0.0821 (8)
H5 0.4199 0.1931 0.2535 0.057*
H6 0.4966 0.2306 0.1077 0.073*
H11 0.3745 0.2076 0.4547 0.062*
H12 0.3201 0.1274 0.5890 0.074*
H14 −0.0463 0.1514 0.3487 0.068*
H15 0.0098 0.2300 0.2124 0.061*
H21 0.3982 0.3360 0.2263 0.055*
H22 0.3983 0.3355 0.3653 0.055*
H71 0.4721 0.0674 0.0161 0.101*
H72 0.5239 0.1421 −0.0365 0.101*
H81 0.3117 0.1102 −0.1710 0.105*
H82 0.3307 0.2028 −0.1229 0.105*
H91 0.2286 0.0759 −0.0291 0.084*
H92 0.1552 0.1550 −0.1054 0.084*
H161 −0.0419 0.0207 0.4459 0.095*
H162 −0.0728 0.0915 0.5236 0.095*
H171 −0.0913 −0.0312 0.6104 0.129*
H172 0.0286 0.0138 0.7121 0.129*
H173 0.0442 −0.0578 0.6278 0.129*
H181 0.3320 0.0642 0.2560 0.079*
supporting information
sup-3 Acta Cryst. (2006). E62, o3486–o3487
H183 0.3849 0.0304 0.1597 0.079*
H191 0.6525 0.1856 0.3017 0.098*
H192 0.6406 0.0959 0.2471 0.098*
H193 0.6919 0.1667 0.1890 0.098*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cl1 0.0991 (4) 0.0538 (3) 0.0995 (5) 0.0197 (2) 0.0654 (4) 0.0008 (3)
Cl2 0.0770 (3) 0.0750 (4) 0.0733 (4) 0.0235 (3) 0.0299 (3) 0.0331 (3)
O1 0.0336 (6) 0.0980 (12) 0.0572 (9) 0.0115 (7) 0.0038 (6) −0.0132 (8)
O2 0.0746 (11) 0.0917 (12) 0.0785 (11) −0.0144 (9) 0.0336 (9) 0.0262 (9)
N1 0.0416 (8) 0.0587 (10) 0.0420 (9) 0.0091 (7) 0.0114 (7) −0.0051 (7)
C1 0.0315 (7) 0.0429 (9) 0.0500 (10) 0.0072 (6) 0.0166 (7) 0.0035 (8)
C2 0.0392 (9) 0.0411 (10) 0.0529 (11) 0.0033 (7) 0.0166 (8) 0.0022 (8)
C3 0.0485 (10) 0.0454 (10) 0.0569 (11) 0.0142 (8) 0.0252 (9) 0.0106 (9)
C4 0.0363 (9) 0.0505 (11) 0.0522 (12) 0.0040 (7) 0.0165 (9) −0.0002 (8)
C5 0.0380 (8) 0.0455 (10) 0.0541 (11) 0.0090 (7) 0.0138 (8) −0.0018 (8)
C6 0.0529 (11) 0.0543 (12) 0.0824 (16) 0.0099 (9) 0.0365 (11) 0.0016 (10)
C7 0.0851 (17) 0.100 (2) 0.0843 (18) 0.0258 (15) 0.0532 (15) 0.0009 (15)
C8 0.1031 (19) 0.107 (2) 0.0574 (15) 0.0320 (17) 0.0403 (15) −0.0032 (14)
C9 0.0661 (14) 0.0830 (18) 0.0496 (13) 0.0167 (12) 0.0135 (11) −0.0164 (11)
C10 0.0368 (8) 0.0388 (9) 0.0461 (10) 0.0003 (7) 0.0163 (8) −0.0015 (7)
C11 0.0371 (9) 0.0607 (12) 0.0525 (12) −0.0038 (8) 0.0136 (8) 0.0067 (9)
C12 0.0519 (11) 0.0745 (15) 0.0508 (13) −0.0036 (10) 0.0136 (10) 0.0125 (10) C13 0.0596 (12) 0.0534 (12) 0.0607 (13) −0.0061 (10) 0.0295 (10) 0.0044 (10) C14 0.0427 (10) 0.0612 (13) 0.0701 (15) −0.0024 (9) 0.0276 (10) 0.0034 (10)
C15 0.0393 (9) 0.0558 (12) 0.0519 (11) 0.0086 (8) 0.0148 (8) 0.0076 (9)
C16 0.0731 (15) 0.0769 (17) 0.103 (2) −0.0048 (13) 0.0512 (15) 0.0194 (16)
C17 0.103 (2) 0.098 (2) 0.141 (2) −0.0088 (17) 0.070 (2) 0.034 (2)
C18 0.0659 (13) 0.0529 (13) 0.0722 (15) 0.0062 (10) 0.0237 (11) 0.0040 (10)
C19 0.0538 (12) 0.0837 (18) 0.112 (2) 0.0081 (12) 0.0384 (13) −0.0035 (16)
Geometric parameters (Å, º)
Cl1—C3 1.754 (2) C2—H21 0.970
Cl2—C3 1.748 (2) C2—H22 0.970
O1—C4 1.2208 (19) C5—H5 0.980
O2—C13 1.377 (3) C6—H6 0.980
O2—C16 1.415 (3) C7—H71 0.970
N1—C4 1.348 (2) C7—H72 0.970
N1—C5 1.477 (2) C8—H81 0.970
N1—C9 1.467 (3) C8—H82 0.970
C1—C2 1.524 (2) C9—H91 0.970
C1—C3 1.505 (2) C9—H92 0.970
C1—C4 1.516 (2) C11—H11 0.930
C1—C10 1.507 (3) C12—H12 0.930
C5—C6 1.534 (3) C15—H15 0.930
C5—C18 1.518 (3) C16—H161 0.970
C6—C7 1.525 (4) C16—H162 0.970
C6—C19 1.512 (2) C17—H171 0.960
C7—C8 1.498 (3) C17—H172 0.960
C8—C9 1.501 (4) C17—H173 0.960
C10—C11 1.379 (2) C18—H181 0.960
C10—C15 1.383 (2) C18—H182 0.960
C11—C12 1.373 (3) C18—H183 0.960
C12—C13 1.383 (3) C19—H191 0.960
C13—C14 1.374 (2) C19—H192 0.960
C14—C15 1.385 (3) C19—H193 0.960
C16—C17 1.468 (5)
C13—O2—C16 118.79 (18) C7—C6—H6 106.8
C4—N1—C5 125.94 (17) C19—C6—H6 106.8
C4—N1—C9 118.67 (15) C6—C7—H71 109.0
C5—N1—C9 114.97 (18) C6—C7—H72 109.0
C2—C1—C3 58.53 (11) C8—C7—H71 109.0
C2—C1—C4 121.16 (19) C8—C7—H72 109.0
C2—C1—C10 119.68 (15) H71—C7—H72 109.5
C3—C1—C4 116.97 (16) C7—C8—H81 108.5
C3—C1—C10 118.82 (18) C7—C8—H82 108.5
C4—C1—C10 111.93 (15) C9—C8—H81 108.5
C1—C2—C3 60.07 (12) C9—C8—H82 108.5
Cl1—C3—Cl2 111.21 (10) H81—C8—H82 109.5
Cl1—C3—C1 118.48 (17) N1—C9—H91 109.4
Cl1—C3—C2 118.26 (14) N1—C9—H92 109.4
Cl2—C3—C1 121.06 (15) C8—C9—H91 109.4
Cl2—C3—C2 118.37 (18) C8—C9—H92 109.4
C1—C3—C2 61.39 (11) H91—C9—H92 109.5
O1—C4—N1 122.60 (19) C10—C11—H11 119.6
O1—C4—C1 118.85 (19) C12—C11—H11 119.6
N1—C4—C1 118.48 (13) C11—C12—H12 119.8
N1—C5—C6 108.33 (17) C13—C12—H12 119.8
N1—C5—C18 110.73 (15) C13—C14—H14 120.4
C6—C5—C18 115.47 (19) C15—C14—H14 120.4
C5—C6—C7 110.75 (19) C10—C15—H15 119.2
C5—C6—C19 112.7 (2) C14—C15—H15 119.2
C7—C6—C19 112.5 (2) O2—C16—H161 110.0
C6—C7—C8 111.5 (2) O2—C16—H162 110.0
C7—C8—C9 113.4 (2) C17—C16—H161 110.0
N1—C9—C8 109.7 (2) C17—C16—H162 110.0
C1—C10—C11 122.00 (17) H161—C16—H162 109.5
C1—C10—C15 119.68 (15) C16—C17—H171 109.5
C11—C10—C15 118.3 (2) C16—C17—H172 109.5
C10—C11—C12 120.77 (18) C16—C17—H173 109.5
supporting information
sup-5 Acta Cryst. (2006). E62, o3486–o3487
O2—C13—C12 116.04 (18) H171—C17—H173 109.5
O2—C13—C14 124.1 (2) H172—C17—H173 109.5
C12—C13—C14 119.8 (2) C5—C18—H181 109.5
C13—C14—C15 119.2 (2) C5—C18—H182 109.5
C10—C15—C14 121.56 (16) C5—C18—H183 109.5
O2—C16—C17 107.6 (2) H181—C18—H182 109.5
C1—C2—H21 120.0 H181—C18—H183 109.5
C1—C2—H22 120.0 H182—C18—H183 109.5
C3—C2—H21 120.0 C6—C19—H191 109.5
C3—C2—H22 120.0 C6—C19—H192 109.5
H21—C2—H22 109.5 C6—C19—H193 109.5
N1—C5—H5 107.3 H191—C19—H192 109.5
C6—C5—H5 107.3 H191—C19—H193 109.5
C18—C5—H5 107.3 H192—C19—H193 109.5
C5—C6—H6 106.8
C13—O2—C16—C17 171.5 (2) C10—C1—C3—Cl1 0.50 (18)
C16—O2—C13—C12 −168.6 (2) C10—C1—C3—Cl2 −143.32 (14)
C16—O2—C13—C14 11.4 (3) C10—C1—C3—C2 109.02 (17)
C4—N1—C5—C6 −128.6 (2) C4—C1—C10—C11 115.16 (19)
C4—N1—C5—C18 103.8 (2) C4—C1—C10—C15 −61.9 (2)
C5—N1—C4—O1 −170.1 (2) C10—C1—C4—O1 84.8 (2)
C5—N1—C4—C1 6.9 (3) C10—C1—C4—N1 −92.3 (2)
C4—N1—C9—C8 130.1 (2) C1—C2—C3—Cl1 108.87 (18)
C9—N1—C4—O1 2.1 (3) C1—C2—C3—Cl2 −111.92 (17)
C9—N1—C4—C1 179.1 (2) N1—C5—C6—C7 −55.3 (2)
C5—N1—C9—C8 −56.9 (2) N1—C5—C6—C19 177.69 (19)
C9—N1—C5—C6 59.0 (2) C18—C5—C6—C7 69.5 (2)
C9—N1—C5—C18 −68.6 (2) C18—C5—C6—C19 −57.5 (2)
C2—C1—C3—Cl1 −108.52 (16) C5—C6—C7—C8 53.3 (3)
C2—C1—C3—Cl2 107.7 (2) C19—C6—C7—C8 −179.6 (2)
C2—C1—C4—O1 −125.0 (2) C6—C7—C8—C9 −51.9 (3)
C2—C1—C4—N1 57.9 (2) C7—C8—C9—N1 52.0 (3)
C4—C1—C2—C3 104.55 (19) C1—C10—C11—C12 −175.6 (2)
C2—C1—C10—C11 −35.5 (2) C1—C10—C15—C14 176.4 (2)
C2—C1—C10—C15 147.49 (18) C11—C10—C15—C14 −0.8 (3)
C10—C1—C2—C3 −107.6 (2) C15—C10—C11—C12 1.4 (3)
C3—C1—C4—O1 −57.2 (2) C10—C11—C12—C13 −0.5 (3)
C3—C1—C4—N1 125.7 (2) C11—C12—C13—O2 178.8 (2)
C4—C1—C3—Cl1 139.81 (15) C11—C12—C13—C14 −1.2 (3)
C4—C1—C3—Cl2 −4.0 (2) O2—C13—C14—C15 −178.2 (2)
C4—C1—C3—C2 −111.7 (2) C12—C13—C14—C15 1.8 (3)
C3—C1—C10—C11 −103.6 (2) C13—C14—C15—C10 −0.8 (3)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C11—H11···O1i 0.93 2.40 3.322 (3) 170