(2E,5E)-2,5-Bis(3,4,5-trimethoxy­benzyl­idene)cyclo­penta­none

Sun, Y.-F.; Liu, Y.; Zhang, F.-Y.; Chen, H.-J.; Cui, Y.-P.

doi:10.1107/S1600536808029474

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1964

doi:10.1107/S1600536808029474

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(2E,5E)-2,5-Bis(3,4,5-trimethoxybenzylidene)cyclopentanone

Yi-Feng Sun,^a,^b ^* Yang Liu,^c Feng-Yu Zhang,^c Hong-Ji Chen ^b and Yi-Ping Cui ^a

^aAdvanced Photonics Center, School of Electronic Science and Engineering, Southeast University, 210096 Nanjing, Jiangsu, People's Republic of China, ^bDepartment of Chemistry, Taishan University, 271021 Taian, Shandong, People's Republic of China, and ^cLibrary, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: sunyf505@hotmail.com

(Received 3 September 2008; accepted 15 September 2008; online 20 September 2008)

The title compound, C₂₅H₂₈O₇, was prepared by the base-catalysed reaction of 3,4,5-trimethoxybenzaldehyde with cyclopentanone. The molecule has crystallographic twofold rotation symmetry and adopts an E-configuration about the central olefinic bonds. The two benzene rings and the central cyclopentanone ring are almost coplanar [dihedral angle = 4.7 (2)°].

Related literature

For background literature, see: Guilford et al. (1999 ); Xue et al. (2008 ); Wu et al. (2008 ); Das et al. (2008 ). For related crystal structures, see: Sun & Cui (2007 ); Du et al. (2007 ); Wei et al. (2008 ).

Experimental

Crystal data

C₂₅H₂₈O₇
M_r = 440.47
Monoclinic, C 2/c
a = 18.573 (4) Å
b = 15.231 (3) Å
c = 8.8460 (18) Å
β = 113.99 (3)°
V = 2286.2 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.982
2123 measured reflections
2058 independent reflections
1422 reflections with I > 2σ(I)
R_int = 0.048
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.164
S = 1.00
2058 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected torsion angles (°)

O1—C1—C2—C4	−2.7 (3)
C1—C2—C4—C5	178.0 (2)
C2—C4—C5—C6	179.6 (3)
C13—O4—C7—C6	1.8 (4)
C12—O3—C8—C7	86.9 (3)
C11—O2—C9—C8	174.8 (3)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: 10.1107/S1600536808029474/fj2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029474/fj2151Isup2.hkl

checkCIF report

Comment top

Bis(arylmethylidene)cycloalkanones are widely used as building blocks for the synthesis of biologically active heterocycles (Guilford et al., 1999), and reported to exhibit promising two-photon absorption (TPA) property (Xue et al., 2008; Wu et al., 2008). Moreover, it has been reported that some compounds containing the 3-(3,4,5-trimethoxyphenyl)-2-propenoyl group displayed potent multidrug resistance (MDR) reversal properties in cancer chemotherapy. In particular, 2,5-bis(3,4,5-trimethoxybenzylidene)cyclopentanone was 31 times more potent than verapamil as a MDR revertant (Das et al., 2008). In this contribution, we report the crystal structure of the title compound, 2,5-bis(3,4,5-trimethoxybenzylidene) cyclopentanone, Fig.1.

The molecule possesses normal geometric parameters and adopts an E configuration about the central olefinic bonds (Fig. 1). The cyclopentanone ring and the two benzene rings are almost coplanar which allows conjugation. Among the six methoxy groups, only O3/C12 and O3A/C12A deviate from the molecule mean plane on the opposite side, the others are nearly coplanar with their attached benzene ring (Table 1).

Similar structures have been observed in the related substituted cyclohexanone and cyclopentanone analogues reported by Sun & Cui (2007), Du et al. (2007) and Wei et al. (2008).

Related literature top

For background literature, see: Guilford et al. (1999); Xue et al. (2008); Wu et al. (2008); Das et al. (2008). For related crystal structures, see: Sun & Cui (2007); Du et al. (2007); Wei et al. (2008).

Experimental top

The title compound was synthesized from cyclopenthexanone and 3,4,5-trimethoxybenzaldehyde as reported (Sun et al., 2007).Yellow block crystals suitable for an X-ray structural analysis were obtained by slowly evaporating an ethanol solution at room temperature.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii. Suffix A corresponds to symmetry code (-x+1, y, -z+1/2).

(2E,5E)-2,5-Bis(3,4,5-trimethoxybenzylidene)cyclopentanone top

Crystal data top

C₂₅H₂₈O₇	F(000) = 936
M_r = 440.47	D_x = 1.280 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 18.573 (4) Å	θ = 10–13°
b = 15.231 (3) Å	µ = 0.09 mm⁻¹
c = 8.8460 (18) Å	T = 293 K
β = 113.99 (3)°	Block, yellow
V = 2286.2 (10) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1422 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 25.2°, θ_min = 1.8°
ω/2θ scans	h = −22→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→18
T_min = 0.973, T_max = 0.982	l = 0→10
2123 measured reflections	3 standard reflections every 200 reflections
2058 independent reflections	intensity decay: none

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)] = 0.055	Hydrogen site location: difference Fourier map
wR(F²) = 0.164	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.080P)² + 2.P] where P = (F_o² + 2F_c²)/3
2058 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₅H₂₈O₇	V = 2286.2 (10) Å³
M_r = 440.47	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.573 (4) Å	µ = 0.09 mm⁻¹
b = 15.231 (3) Å	T = 293 K
c = 8.8460 (18) Å	0.30 × 0.20 × 0.20 mm
β = 113.99 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1422 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.048
T_min = 0.973, T_max = 0.982	3 standard reflections every 200 reflections
2123 measured reflections	intensity decay: none
2058 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.164	H-atom parameters constrained
S = 1.00	Δρ_max = 0.21 e Å⁻³
2058 reflections	Δρ_min = −0.27 e Å⁻³
146 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
O1	0.5000	0.43398 (16)	0.2500	0.0707 (8)
C1	0.5000	0.3537 (2)	0.2500	0.0510 (8)
C2	0.47174 (14)	0.29645 (15)	0.3510 (3)	0.0480 (6)
O2	0.36310 (14)	0.07554 (11)	0.6941 (3)	0.0806 (7)
O3	0.32676 (10)	0.18198 (11)	0.89316 (19)	0.0592 (5)
C3	0.47864 (15)	0.20225 (14)	0.3086 (3)	0.0512 (6)
H3A	0.4268	0.1760	0.2546	0.061*
H3B	0.5085	0.1690	0.4080	0.061*
O4	0.33734 (12)	0.35568 (11)	0.8758 (2)	0.0683 (6)
C4	0.44589 (14)	0.33133 (16)	0.4587 (3)	0.0517 (6)
H4A	0.4489	0.3922	0.4665	0.062*
C5	0.41371 (14)	0.28904 (15)	0.5662 (3)	0.0473 (6)
C6	0.39179 (15)	0.34335 (15)	0.6677 (3)	0.0526 (6)
H6A	0.3979	0.4038	0.6648	0.063*
C7	0.36086 (14)	0.30734 (16)	0.7728 (3)	0.0504 (6)
C8	0.35313 (13)	0.21799 (15)	0.7816 (3)	0.0478 (6)
C9	0.37410 (15)	0.16327 (15)	0.6797 (3)	0.0542 (6)
C10	0.40400 (15)	0.19887 (16)	0.5729 (3)	0.0555 (6)
H10A	0.4177	0.1620	0.5050	0.067*
C11	0.3772 (3)	0.01797 (19)	0.5835 (5)	0.1075 (13)
H11A	0.3679	−0.0414	0.6071	0.161*
H11B	0.4309	0.0240	0.5965	0.161*
H11C	0.3425	0.0323	0.4718	0.161*
C12	0.24333 (17)	0.1766 (2)	0.8306 (4)	0.0739 (8)
H12A	0.2284	0.1507	0.9126	0.111*
H12B	0.2239	0.1410	0.7326	0.111*
H12C	0.2212	0.2345	0.8044	0.111*
C13	0.3430 (2)	0.44758 (18)	0.8706 (4)	0.0886 (11)
H13A	0.3249	0.4735	0.9478	0.133*
H13B	0.3111	0.4681	0.7611	0.133*
H13C	0.3969	0.4639	0.8995	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.118 (2)	0.0480 (15)	0.0791 (18)	0.000	0.0745 (17)	0.000
C1	0.074 (2)	0.048 (2)	0.0498 (18)	0.000	0.0438 (17)	0.000
C2	0.0656 (14)	0.0492 (13)	0.0459 (12)	−0.0033 (10)	0.0397 (11)	−0.0017 (10)
O2	0.1371 (18)	0.0460 (11)	0.0952 (15)	−0.0030 (10)	0.0846 (14)	0.0043 (9)
O3	0.0752 (12)	0.0681 (11)	0.0527 (10)	−0.0055 (9)	0.0450 (9)	0.0105 (8)
C3	0.0719 (16)	0.0494 (13)	0.0494 (13)	−0.0013 (11)	0.0422 (12)	0.0001 (10)
O4	0.1063 (14)	0.0569 (11)	0.0782 (12)	−0.0088 (9)	0.0749 (12)	−0.0123 (9)
C4	0.0734 (16)	0.0497 (14)	0.0515 (13)	0.0006 (11)	0.0452 (12)	0.0011 (10)
C5	0.0631 (14)	0.0482 (13)	0.0463 (12)	−0.0029 (10)	0.0384 (11)	−0.0005 (10)
C6	0.0770 (16)	0.0447 (13)	0.0575 (14)	−0.0010 (11)	0.0493 (13)	0.0004 (10)
C7	0.0666 (15)	0.0550 (14)	0.0474 (12)	−0.0045 (11)	0.0414 (12)	−0.0058 (10)
C8	0.0585 (14)	0.0542 (14)	0.0433 (12)	−0.0037 (11)	0.0336 (11)	0.0049 (10)
C9	0.0779 (17)	0.0449 (13)	0.0564 (14)	−0.0038 (11)	0.0443 (13)	0.0040 (11)
C10	0.0807 (17)	0.0506 (14)	0.0556 (14)	0.0013 (12)	0.0487 (13)	−0.0018 (11)
C11	0.188 (4)	0.0482 (18)	0.130 (3)	−0.005 (2)	0.109 (3)	−0.0127 (18)
C12	0.0775 (19)	0.085 (2)	0.0795 (19)	−0.0150 (15)	0.0526 (16)	0.0035 (16)
C13	0.149 (3)	0.0538 (17)	0.108 (2)	−0.0021 (18)	0.098 (2)	−0.0120 (16)

Geometric parameters (Å, º) top

O1—C1	1.222 (4)	C5—C6	1.398 (3)
C1—C2	1.489 (3)	C6—C7	1.389 (3)
C1—C2ⁱ	1.489 (3)	C6—H6A	0.9300
C2—C4	1.339 (3)	C7—C8	1.374 (3)
C2—C3	1.501 (3)	C8—C9	1.395 (3)
O2—C9	1.365 (3)	C9—C10	1.386 (3)
O2—C11	1.415 (3)	C10—H10A	0.9300
O3—C8	1.381 (2)	C11—H11A	0.9600
O3—C12	1.420 (3)	C11—H11B	0.9600
C3—C3ⁱ	1.541 (4)	C11—H11C	0.9600
C3—H3A	0.9700	C12—H12A	0.9600
C3—H3B	0.9700	C12—H12B	0.9600
O4—C7	1.373 (3)	C12—H12C	0.9600
O4—C13	1.406 (3)	C13—H13A	0.9600
C4—C5	1.462 (3)	C13—H13B	0.9600
C4—H4A	0.9300	C13—H13C	0.9600
C5—C10	1.390 (3)

O1—C1—C2	125.87 (13)	C7—C8—O3	120.62 (19)
O1—C1—C2ⁱ	125.87 (13)	C7—C8—C9	119.49 (19)
C2—C1—C2ⁱ	108.3 (3)	O3—C8—C9	119.9 (2)
C4—C2—C1	120.7 (2)	O2—C9—C10	124.2 (2)
C4—C2—C3	130.4 (2)	O2—C9—C8	115.7 (2)
C1—C2—C3	108.86 (18)	C10—C9—C8	120.1 (2)
C9—O2—C11	117.7 (2)	C9—C10—C5	120.7 (2)
C8—O3—C12	113.10 (19)	C9—C10—H10A	119.7
C2—C3—C3ⁱ	106.72 (11)	C5—C10—H10A	119.7
C2—C3—H3A	110.4	O2—C11—H11A	109.5
C3ⁱ—C3—H3A	110.4	O2—C11—H11B	109.5
C2—C3—H3B	110.4	H11A—C11—H11B	109.5
C3ⁱ—C3—H3B	110.4	O2—C11—H11C	109.5
H3A—C3—H3B	108.6	H11A—C11—H11C	109.5
C7—O4—C13	117.66 (19)	H11B—C11—H11C	109.5
C2—C4—C5	130.4 (2)	O3—C12—H12A	109.5
C2—C4—H4A	114.8	O3—C12—H12B	109.5
C5—C4—H4A	114.8	H12A—C12—H12B	109.5
C10—C5—C6	118.77 (19)	O3—C12—H12C	109.5
C10—C5—C4	123.87 (19)	H12A—C12—H12C	109.5
C6—C5—C4	117.4 (2)	H12B—C12—H12C	109.5
C7—C6—C5	120.3 (2)	O4—C13—H13A	109.5
C7—C6—H6A	119.9	O4—C13—H13B	109.5
C5—C6—H6A	119.9	H13A—C13—H13B	109.5
O4—C7—C8	115.13 (18)	O4—C13—H13C	109.5
O4—C7—C6	124.2 (2)	H13A—C13—H13C	109.5
C8—C7—C6	120.7 (2)	H13B—C13—H13C	109.5

O1—C1—C2—C4	−2.7 (3)	O4—C7—C8—O3	−2.8 (3)
C2ⁱ—C1—C2—C4	177.3 (3)	C6—C7—C8—O3	176.1 (2)
O1—C1—C2—C3	177.49 (12)	O4—C7—C8—C9	178.8 (2)
C2ⁱ—C1—C2—C3	−2.51 (12)	C6—C7—C8—C9	−2.2 (4)
C4—C2—C3—C3ⁱ	−173.4 (3)	C12—O3—C8—C7	86.9 (3)
C1—C2—C3—C3ⁱ	6.4 (3)	C12—O3—C8—C9	−94.7 (3)
C1—C2—C4—C5	178.0 (2)	C11—O2—C9—C10	−5.3 (4)
C3—C2—C4—C5	−2.2 (5)	C11—O2—C9—C8	174.8 (3)
C2—C4—C5—C10	−0.3 (4)	C7—C8—C9—O2	−178.8 (2)
C2—C4—C5—C6	179.6 (3)	O3—C8—C9—O2	2.9 (4)
C10—C5—C6—C7	0.0 (4)	C7—C8—C9—C10	1.3 (4)
C4—C5—C6—C7	−180.0 (2)	O3—C8—C9—C10	−177.0 (2)
C13—O4—C7—C8	−179.2 (3)	O2—C9—C10—C5	−179.7 (2)
C13—O4—C7—C6	1.8 (4)	C8—C9—C10—C5	0.2 (4)
C5—C6—C7—O4	−179.6 (2)	C6—C5—C10—C9	−0.8 (4)
C5—C6—C7—C8	1.6 (4)	C4—C5—C10—C9	179.1 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₈O₇
M_r	440.47
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.573 (4), 15.231 (3), 8.8460 (18)
β (°)	113.99 (3)
V (Å³)	2286.2 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	2123, 2058, 1422
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.164, 1.00
No. of reflections	2058
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected torsion angles (º) top

O1—C1—C2—C4	−2.7 (3)	C13—O4—C7—C6	1.8 (4)
C1—C2—C4—C5	178.0 (2)	C12—O3—C8—C7	86.9 (3)
C2—C4—C5—C6	179.6 (3)	C11—O2—C9—C8	174.8 (3)

Acknowledgements

This project was supported by the Jiangsu Planned Projects for Postdoctoral Research Funds (No.0701001B) and the Foundation of Taishan University.

References

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