supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

kp2217 scheme

Acta Cryst. (2009). E65, o1183    [ doi:10.1107/S160053680901544X ]

Diisopropyl 3-[(E)-2-(3,4-dimethoxyphenyl)ethenyl]-5-oxocyclohex-3-ene-1,1-dicarboxylate

S. Chen, C. Zhang and J. Qi

Abstract top

The title compound, C24H30O7, displays a trans configuration with respect to the C=C bond. The cyclohexenone ring has an envelope conformation; the flap atom (with the isopropoxycarbonyl groups) is displaced by 0.664 (3) Å from the plane of the other five ring atoms and the carbonyl O atom. The dihedral angle between the cyclohexenone ring and the benzene ring is 7.85 (9)°. The meta and para methoxy O atoms are displaced by 0.003 (7) and 0.031 (4) Å, respectively, from the benzene ring to which they are attached.

Comment top

Cyclohex-2-enone derivatives have significant biological activities such as anti-bacterial Stadler et al., 1994), anti-cancer (Correia et al., 2001). In addition, cyclohex-2-enone derivatives can be used as precursors in the synthesis of various compounds such as vitamin E (Hu et al., 2003). We are interested in their pharmaceutical properties. In this paper, we present the X-ray crystal structure analysis of the title compound (I) (Fig. 1). The molecule displays a trans configuration with respect to the C═C. The cyclohexenone ring has an envelope conformation, the plane which is defined by the atoms C1, C2 and C6 (forming the flap) and the plane defined by C2, C3, C4, C5, and C6 form a dihedral angle of 48.95 (0)°. The dihedral angle between the cyclohexenone ring and the benzene ring is 7.85 (9)°. The meta and para O-methoxy atoms are displaced by 0.003 (7)Å and 0.031 (4)Å from the benzene ring to which they are attached. The carbon atom C7 of the C═C is displaced by 0.182 (6)Å from the C2, C3, C4, C5, C6 plane, whereas the carbon atom C8 is displaced by 0.011 (3)Å from the benzene ring.

Related literature top

For the biological activities of cyclohex-2-enone derivatives, see: Correia et al. (2001); Stadler et al. (1994). Cyclohex-2-enone

derivatives can be used as precursors in the synthesis of various compounds such as vitamin E (Hu et al., 2003).

Experimental top

A solution of (R,S)-methyl 3-methyl-5-oxo -1-phenylcyclohex-3-ene-1-carboxylate (0.5 mmol), Veratraldehyde (2 mmol), and piperidine (0.75 mmol) in 4 ml 2-propanol was heated at 373 K for 24 h. The reaction mixture was acidified with dilute aqueous HCl, concentrated, and partitioned between water and ethyl acetate. The pure product was obtained through silica gel chromatography, and diffraction quality crystals were obtained by slow evaporation of an ethyl acetate/petroleum ether/ dichloromethane (1:2:2) solution at room temperature.

Refinement top

All H atoms were placed in calculated positions, with C—H distances in the range 0.93–0.98Å and included in the final cycles of refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with atom labels showing the 50% probability displacement ellipsoids.
Diisopropyl 3-[(E)-2-(3,4-dimethoxyphenyl)ethenyl]-5-oxocyclohex-3-ene- 1,1-dicarboxylate top
Crystal data top
C24H30O7F000 = 920.00
Mr = 430.50Dx = 1.222 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71075 Å
Hall symbol: -P 2ynCell parameters from 11134 reflections
a = 8.9228 (6) Åθ = 3.0–27.4º
b = 13.3886 (7) ŵ = 0.09 mm−1
c = 20.2009 (11) ÅT = 296 K
β = 104.2488 (14)ºPlatelet, yellow
V = 2339.0 (2) Å30.38 × 0.30 × 0.06 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2404 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.050
ω scansθmax = 27.4º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −11→11
Tmin = 0.952, Tmax = 0.995k = −17→16
22350 measured reflectionsl = −26→26
5332 independent reflections
Refinement top
Refinement on F2  w = 1/[σ2(Fo2) + (0.0371P)2 + 2P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.062(Δ/σ)max < 0.001
wR(F2) = 0.169Δρmax = 0.40 e Å−3
S = 1.00Δρmin = −0.32 e Å−3
5332 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008)
282 parametersExtinction coefficient: 0.0087 (8)
H-atom parameters constrained
Crystal data top
C24H30O7V = 2339.0 (2) Å3
Mr = 430.50Z = 4
Monoclinic, P21/nMo Kα
a = 8.9228 (6) ŵ = 0.09 mm−1
b = 13.3886 (7) ÅT = 296 K
c = 20.2009 (11) Å0.38 × 0.30 × 0.06 mm
β = 104.2488 (14)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5332 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2404 reflections with F2 > 2σ(F2)
Tmin = 0.952, Tmax = 0.995Rint = 0.050
22350 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.062? restraints
wR(F2) = 0.169H-atom parameters constrained
S = 1.00Δρmax = 0.40 e Å−3
5332 reflectionsΔρmin = −0.32 e Å−3
282 parameters
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1−0.0208 (2)0.25454 (16)0.26220 (12)0.0861 (7)
O21.1752 (2)0.54715 (16)0.43247 (12)0.0769 (6)
O31.0310 (2)0.70068 (13)0.37276 (12)0.0775 (6)
O40.1738 (3)0.4751 (2)0.10365 (13)0.1100 (10)
O5−0.0202 (2)0.37309 (14)0.10638 (11)0.0750 (6)
O6−0.0166 (2)0.67279 (16)0.18181 (13)0.0957 (8)
O7−0.1964 (2)0.56180 (14)0.13391 (13)0.0922 (8)
C10.0411 (2)0.49558 (19)0.19360 (14)0.0544 (7)
C2−0.0489 (3)0.4253 (2)0.22908 (14)0.0599 (7)
C30.0432 (3)0.3344 (2)0.25655 (16)0.0622 (7)
C40.2096 (3)0.3458 (2)0.27832 (16)0.0652 (8)
C50.2829 (3)0.4331 (2)0.27522 (14)0.0558 (7)
C60.1953 (2)0.5246 (2)0.24290 (14)0.0586 (7)
C70.4482 (3)0.4387 (2)0.30523 (14)0.0597 (7)
C80.5383 (2)0.5190 (2)0.31062 (13)0.0544 (7)
C90.7036 (2)0.5223 (2)0.34373 (13)0.0519 (6)
C100.7840 (3)0.4414 (2)0.37748 (14)0.0618 (7)
C110.9407 (3)0.4469 (2)0.40793 (16)0.0639 (8)
C121.0205 (2)0.5343 (2)0.40526 (14)0.0579 (7)
C130.9414 (3)0.6176 (2)0.37214 (14)0.0559 (7)
C140.7853 (2)0.6114 (2)0.34175 (13)0.0548 (7)
C151.2624 (3)0.4625 (2)0.46223 (19)0.0837 (10)
C160.9583 (3)0.7883 (2)0.3402 (2)0.0840 (10)
C170.0745 (3)0.4477 (2)0.12976 (16)0.0606 (7)
C18−0.0112 (4)0.3231 (2)0.04279 (18)0.0806 (10)
C190.0580 (4)0.2226 (2)0.0621 (2)0.1038 (13)
C20−0.1745 (5)0.3175 (3)−0.0010 (2)0.1269 (17)
C21−0.0570 (3)0.5888 (2)0.16937 (16)0.0640 (8)
C22−0.3203 (3)0.6375 (2)0.1150 (2)0.0826 (10)
C23−0.4640 (4)0.5853 (3)0.1200 (2)0.1157 (14)
C24−0.3221 (5)0.6699 (3)0.0460 (2)0.1302 (17)
H40.26890.29010.29530.078*
H70.49660.37940.32260.072*
H80.49220.57810.29170.065*
H100.73160.38190.37980.074*
H110.99230.39150.43030.077*
H140.73340.66700.31970.066*
H180.05390.36180.01950.097*
H22−0.29920.69410.14670.099*
H610.25790.56070.21790.070*
H620.17470.56710.27850.070*
H1511.21640.43400.49610.100*
H1521.36660.48260.48320.100*
H1531.26320.41380.42740.100*
H1610.92250.77650.29200.101*
H1621.03120.84240.34800.101*
H1630.87220.80520.35870.101*
H1910.16210.23020.08910.125*
H192−0.00210.18750.08800.125*
H1930.05850.18540.02150.125*
H201−0.21190.3837−0.01380.152*
H202−0.23950.28610.02430.152*
H203−0.17600.2792−0.04130.152*
H221−0.14280.40460.19650.072*
H222−0.07540.46060.26660.072*
H231−0.54740.63250.11330.139*
H232−0.44870.55530.16430.139*
H233−0.48880.53450.08550.139*
H241−0.38630.72800.03480.156*
H242−0.36240.61720.01440.156*
H243−0.21870.68570.04340.156*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0713 (15)0.0646 (13)0.1168 (19)−0.0242 (11)0.0124 (13)0.0059 (13)
O20.0417 (11)0.0712 (13)0.1039 (16)−0.0005 (10)−0.0083 (10)0.0168 (12)
O30.0498 (11)0.0530 (11)0.1163 (18)−0.0075 (9)−0.0049 (11)0.0131 (11)
O40.104 (2)0.131 (2)0.113 (2)−0.0563 (18)0.0592 (17)−0.0351 (17)
O50.0790 (15)0.0680 (13)0.0850 (15)−0.0222 (11)0.0339 (12)−0.0240 (11)
O60.0630 (14)0.0491 (12)0.154 (2)−0.0057 (10)−0.0133 (14)−0.0040 (13)
O70.0500 (12)0.0593 (12)0.142 (2)0.0089 (10)−0.0239 (13)−0.0159 (13)
C10.0424 (14)0.0469 (14)0.0709 (18)−0.0037 (12)0.0080 (13)−0.0053 (13)
C20.0481 (16)0.0607 (17)0.0698 (18)−0.0081 (13)0.0123 (14)−0.0103 (15)
C30.0539 (17)0.0587 (17)0.0725 (19)−0.0127 (14)0.0128 (14)−0.0055 (15)
C40.0499 (17)0.0549 (16)0.085 (2)−0.0041 (13)0.0064 (15)0.0004 (15)
C50.0458 (15)0.0519 (15)0.0669 (17)−0.0029 (12)0.0081 (13)−0.0029 (13)
C60.0438 (15)0.0527 (15)0.0743 (19)−0.0078 (12)0.0048 (13)−0.0062 (14)
C70.0432 (15)0.0552 (16)0.0760 (19)−0.0012 (13)0.0057 (13)0.0001 (14)
C80.0432 (14)0.0535 (15)0.0640 (17)0.0005 (12)0.0081 (12)−0.0030 (13)
C90.0394 (14)0.0523 (15)0.0611 (16)0.0004 (12)0.0067 (12)0.0000 (13)
C100.0475 (16)0.0554 (16)0.079 (2)−0.0050 (13)0.0078 (14)0.0078 (15)
C110.0479 (16)0.0578 (17)0.079 (2)0.0044 (14)0.0020 (14)0.0129 (15)
C120.0363 (14)0.0605 (17)0.0701 (18)0.0011 (12)0.0004 (12)0.0070 (14)
C130.0439 (15)0.0491 (15)0.0701 (18)−0.0023 (12)0.0053 (13)0.0025 (13)
C140.0415 (15)0.0488 (15)0.0687 (18)0.0033 (11)0.0034 (13)0.0021 (13)
C150.0513 (18)0.083 (2)0.103 (2)0.0133 (17)−0.0069 (17)0.016 (2)
C160.072 (2)0.0537 (18)0.117 (2)−0.0051 (16)0.006 (2)0.0135 (18)
C170.0520 (17)0.0572 (17)0.0704 (19)−0.0043 (14)0.0109 (14)−0.0038 (15)
C180.099 (2)0.068 (2)0.086 (2)−0.0129 (19)0.044 (2)−0.0218 (18)
C190.093 (2)0.094 (2)0.121 (3)0.021 (2)0.020 (2)−0.022 (2)
C200.137 (4)0.120 (3)0.098 (3)0.025 (3)−0.021 (2)−0.023 (2)
C210.0441 (16)0.0577 (17)0.085 (2)−0.0044 (13)0.0054 (15)−0.0073 (16)
C220.056 (2)0.068 (2)0.109 (2)0.0014 (16)−0.0084 (18)−0.0013 (19)
C230.074 (2)0.146 (4)0.125 (3)0.008 (2)0.019 (2)0.003 (3)
C240.134 (4)0.135 (4)0.142 (4)0.045 (3)0.072 (3)0.031 (3)
Geometric parameters (Å, °) top
O1—C31.231 (3)C22—C241.456 (6)
O2—C121.366 (3)C2—H2210.970
O2—C151.421 (3)C2—H2220.970
O3—C131.368 (3)C4—H40.930
O3—C161.421 (3)C6—H610.970
O4—C171.195 (4)C6—H620.970
O5—C171.318 (3)C7—H70.930
O5—C181.468 (4)C8—H80.930
O6—C211.189 (3)C10—H100.930
O7—C211.323 (3)C11—H110.930
O7—C221.479 (3)C14—H140.930
C1—C21.526 (4)C15—H1510.960
C1—C61.536 (3)C15—H1520.960
C1—C171.534 (4)C15—H1530.960
C1—C211.534 (3)C16—H1610.960
C2—C31.497 (3)C16—H1620.960
C3—C41.449 (4)C16—H1630.960
C4—C51.348 (4)C18—H180.980
C5—C61.512 (3)C19—H1910.960
C5—C71.452 (3)C19—H1920.960
C7—C81.331 (3)C19—H1930.960
C8—C91.462 (3)C20—H2010.960
C9—C101.383 (3)C20—H2020.960
C9—C141.404 (3)C20—H2030.960
C10—C111.384 (3)C22—H220.980
C11—C121.377 (4)C23—H2310.960
C12—C131.399 (3)C23—H2320.960
C13—C141.379 (3)C23—H2330.960
C18—C191.492 (5)C24—H2410.960
C18—C201.509 (5)C24—H2420.960
C22—C231.485 (5)C24—H2430.960
C12—O2—C15117.6 (2)C5—C6—H62109.1
C13—O3—C16117.9 (2)H61—C6—H62109.5
C17—O5—C18119.4 (2)C5—C7—H7116.3
C21—O7—C22119.7 (2)C8—C7—H7116.3
C2—C1—C6110.0 (2)C7—C8—H8117.2
C2—C1—C17111.8 (2)C9—C8—H8117.2
C2—C1—C21109.0 (2)C9—C10—H10119.3
C6—C1—C17108.8 (2)C11—C10—H10119.3
C6—C1—C21110.6 (2)C10—C11—H11119.9
C17—C1—C21106.6 (2)C12—C11—H11119.9
C1—C2—C3111.8 (2)C9—C14—H14119.6
O1—C3—C2121.0 (2)C13—C14—H14119.6
O1—C3—C4121.9 (2)O2—C15—H151109.5
C2—C3—C4117.0 (2)O2—C15—H152109.5
C3—C4—C5123.4 (2)O2—C15—H153109.5
C4—C5—C6121.1 (2)H151—C15—H152109.5
C4—C5—C7118.7 (2)H151—C15—H153109.5
C6—C5—C7120.2 (2)H152—C15—H153109.5
C1—C6—C5111.1 (2)O3—C16—H161109.5
C5—C7—C8127.3 (2)O3—C16—H162109.5
C7—C8—C9125.6 (2)O3—C16—H163109.5
C8—C9—C10123.0 (2)H161—C16—H162109.5
C8—C9—C14119.0 (2)H161—C16—H163109.5
C10—C9—C14118.0 (2)H162—C16—H163109.5
C9—C10—C11121.4 (2)O5—C18—H18110.2
C10—C11—C12120.2 (2)C19—C18—H18110.2
O2—C12—C11124.9 (2)C20—C18—H18110.2
O2—C12—C13115.7 (2)C18—C19—H191109.5
C11—C12—C13119.4 (2)C18—C19—H192109.5
O3—C13—C12114.8 (2)C18—C19—H193109.5
O3—C13—C14125.2 (2)H191—C19—H192109.5
C12—C13—C14120.0 (2)H191—C19—H193109.5
C9—C14—C13120.9 (2)H192—C19—H193109.5
O4—C17—O5123.6 (3)C18—C20—H201109.5
O4—C17—C1124.1 (2)C18—C20—H202109.5
O5—C17—C1112.2 (2)C18—C20—H203109.5
O5—C18—C19106.9 (2)H201—C20—H202109.5
O5—C18—C20106.4 (3)H201—C20—H203109.5
C19—C18—C20112.7 (3)H202—C20—H203109.5
O6—C21—O7124.7 (2)O7—C22—H22110.5
O6—C21—C1125.6 (2)C23—C22—H22110.5
O7—C21—C1109.7 (2)C24—C22—H22110.5
O7—C22—C23105.2 (2)C22—C23—H231109.5
O7—C22—C24106.4 (3)C22—C23—H232109.5
C23—C22—C24113.5 (3)C22—C23—H233109.5
C1—C2—H221108.9H231—C23—H232109.5
C1—C2—H222108.9H231—C23—H233109.5
C3—C2—H221108.9H232—C23—H233109.5
C3—C2—H222108.9C22—C24—H241109.5
H221—C2—H222109.5C22—C24—H242109.5
C3—C4—H4118.3C22—C24—H243109.5
C5—C4—H4118.3H241—C24—H242109.5
C1—C6—H61109.1H241—C24—H243109.5
C1—C6—H62109.1H242—C24—H243109.5
C5—C6—H61109.1
C15—O2—C12—C114.0 (4)C21—C1—C17—O481.0 (3)
C15—O2—C12—C13−175.5 (2)C21—C1—C17—O5−98.3 (2)
C16—O3—C13—C12−179.8 (2)C1—C2—C3—O1−151.3 (3)
C16—O3—C13—C140.7 (4)C1—C2—C3—C430.9 (3)
C17—O5—C18—C19108.2 (3)O1—C3—C4—C5−177.4 (3)
C17—O5—C18—C20−131.2 (3)C2—C3—C4—C50.3 (4)
C18—O5—C17—O4−3.5 (4)C3—C4—C5—C6−5.1 (5)
C18—O5—C17—C1175.9 (2)C3—C4—C5—C7173.4 (3)
C21—O7—C22—C23−143.5 (3)C4—C5—C6—C1−21.6 (4)
C21—O7—C22—C2495.8 (3)C4—C5—C7—C8−175.9 (3)
C22—O7—C21—O6−8.4 (5)C6—C5—C7—C82.6 (5)
C22—O7—C21—C1169.7 (3)C7—C5—C6—C1160.0 (2)
C2—C1—C6—C551.1 (3)C5—C7—C8—C9177.4 (3)
C6—C1—C2—C3−56.3 (3)C7—C8—C9—C10−4.1 (4)
C2—C1—C17—O4−159.9 (2)C7—C8—C9—C14176.2 (3)
C2—C1—C17—O520.7 (3)C8—C9—C10—C11179.6 (2)
C17—C1—C2—C364.7 (2)C8—C9—C14—C13−179.8 (2)
C2—C1—C21—O6126.9 (3)C10—C9—C14—C130.5 (4)
C2—C1—C21—O7−51.2 (3)C14—C9—C10—C11−0.7 (4)
C21—C1—C2—C3−177.7 (2)C9—C10—C11—C120.1 (4)
C6—C1—C17—O4−38.2 (3)C10—C11—C12—O2−178.8 (3)
C6—C1—C17—O5142.4 (2)C10—C11—C12—C130.7 (4)
C17—C1—C6—C5−71.6 (3)O2—C12—C13—O3−0.9 (4)
C6—C1—C21—O65.8 (4)O2—C12—C13—C14178.6 (2)
C6—C1—C21—O7−172.3 (2)C11—C12—C13—O3179.6 (2)
C21—C1—C6—C5171.6 (2)C11—C12—C13—C14−0.9 (4)
C17—C1—C21—O6−112.3 (3)O3—C13—C14—C9179.7 (2)
C17—C1—C21—O769.6 (3)C12—C13—C14—C90.3 (4)
references
References top

Correia, S. D., David, J. M., David, J. P., Chai, H. B., Pezzuto, J. M. & Cordell, G. A. (2001). Phytochemistry, 56, 781. Final page nuber?

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Hu, B. C., Lv, C. X. & Liu, Z. L. (2003). Yingyong Huaxue, 20, 1012–1014.

Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stadler, M., Anke, H. & Sterner, O. J. (1994). J. Antibiot. 47, 1284–1289.