Ethyl 3-(4-geranyl­oxy-3-methoxy­phenyl)-2-propenoate

The title compound, C₂₂H₃₀O₄, is known as a chemopreventive agent against colon tumor development. The molecular structure is nearly planar, showing a trans arrangement with respect to the C=C bond of the phenyl­propenoate moiety.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.059
• wR factor = 0.120
• Data-to-parameter ratio = 10.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           68.23
         From the CIF: _reflns_number_total               3429
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3750
         Completeness (_total/calc)             91.44%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The title compound, (I), is known as a chemopreventive agent against colon tumor development (Tsuda et al., 1999). It was prepared from ferulic acid, which was easily prepared in large quantities from the oily component of rice bran (Taniguchi et al., 1996).

The molecular structure of (I) is shown in Fig. 1, confirming the trans arrangement with respect to the C7═C8 double bond, similar to ferulic acid (Nethaji et al., 1988). The orientations of the phenyl ring and the geranyl group are defined by the torsion angles in Table 1. The molecule is nearly planar. The molecules in the crystal lattice are in a conventional herring-bone-type arrangement (Fig. 2). No close contacts were found that indicated any relevant intermolecular interaction.

S2. Experimental

To a solution of 1.0 g (4.5 mmol) of ethyl ferulate, ethyl ester of ferulic acid, 1.2 g (4.6 mmol) of triphenylphosphine and 0.69 g (4.5 mmol) of geraniol in 10 ml anhydrous tetrahydrofuran was added 0.93 g (4.6 mmol) diisopropyl azodicarboxylate. The mixture was stirred for 5 min at room temperature and the solvent then removed under reduced pressure. After the residue was extructed with 30 ml of hexane, hexane was moved under reduced pressure. Recrystallization from methanol gave the pure title compound (I) (1.37 g, 85%). Crystals of (I) were obtained by slow evaporation of an ethanol solution at 277–279 K.

S3. Refinement

The measured fraction (θ_max = 68.2°) of 0.917 is relatively low, which may be ascribed to a short exposure time of the imaging plate.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids
	Fig. 2. Projection down the c axis of the unit cell of (I)

(I)

Crystal data

C22H30O4	Z = 2
Mr = 358.48	Dx = 1.164 Mg m^−3
Triclinic, P1	Melting point: 30 K
a = 11.094 (1) Å	Cu Kα radiation, λ = 1.5418 Å
b = 11.943 (1) Å	Cell parameters from 2787 reflections
c = 9.3399 (9) Å	θ = 4.1–67.5°
α = 110.864 (5)°	µ = 0.63 mm^−1
β = 113.510 (5)°	T = 193 K
γ = 68.358 (4)°	Prism, colorless
V = 1022.5 (2) Å^3	0.60 × 0.58 × 0.30 mm

Data collection

Rigaku R-AXIS-RAPID Imaging Plate diffractometer	3094 reflections with F^2 > 2.0σ(F^2)
ω scans	Rint = 0.028
Absorption correction: multi-scan (Higashi, 1995)	θmax = 68.2°
Tmin = 0.587, Tmax = 0.828	h = −13→13
5896 measured reflections	k = −14→14
3429 independent reflections	l = −11→11

Refinement

Refinement on F	w = 1/[σ^2(Fo) + 0.00403|Fo|^2]
R[F^2 > 2σ(F^2)] = 0.059	(Δ/σ)max = 0.0003
wR(F^2) = 0.121	Δρmax = 0.51 e Å^−3
S = 1.65	Δρmin = −0.28 e Å^−3
3429 reflections	Extinction correction: Zachariasen (1967) type 2 Gaussian isotropic
326 parameters	Extinction coefficient: 0.39 (6)
H-atom parameters constrained

Special details

Refinement. Refinement using reflections with F² > 0.0 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 (Ų)

	x	y	z	Uiso*/Ueq
O(1)	0.8530 (1)	0.0444 (1)	0.1403 (1)	0.0467 (3)
O(2)	0.8930 (1)	0.1259 (1)	0.4481 (1)	0.0546 (4)
O(3)	0.4090 (2)	0.8420 (1)	0.3123 (2)	0.0794 (5)
O(4)	0.4986 (1)	0.7857 (1)	0.5440 (1)	0.0526 (4)
C(1)	0.7934 (2)	0.1665 (2)	0.1929 (2)	0.0432 (4)
C(2)	0.8137 (2)	0.2121 (2)	0.3608 (2)	0.0449 (4)
C(3)	0.7531 (2)	0.3341 (2)	0.4220 (2)	0.0458 (4)
C(4)	0.6724 (2)	0.4171 (2)	0.3226 (2)	0.0450 (4)
C(5)	0.6548 (2)	0.3710 (2)	0.1584 (2)	0.0471 (4)
C(6)	0.7126 (2)	0.2481 (2)	0.0935 (2)	0.0468 (4)
C(7)	0.6104 (2)	0.5454 (2)	0.3925 (2)	0.0469 (5)
C(8)	0.5412 (2)	0.6349 (2)	0.3152 (2)	0.0542 (5)
C(9)	0.4762 (2)	0.7634 (2)	0.3867 (2)	0.0526 (5)
C(10)	0.4400 (2)	0.9110 (2)	0.6243 (2)	0.0519 (5)
C(11)	0.4846 (2)	0.9127 (2)	0.7981 (2)	0.0586 (5)
C(12)	0.9212 (2)	0.1682 (2)	0.6191 (2)	0.0635 (6)
C(13)	0.8307 (2)	−0.0011 (2)	−0.0299 (2)	0.0451 (4)
C(14)	0.9001 (2)	−0.1374 (1)	−0.0652 (2)	0.0440 (4)
C(15)	0.8992 (2)	−0.2079 (2)	−0.2113 (2)	0.0435 (4)
C(16)	0.9717 (2)	−0.3443 (2)	−0.2479 (2)	0.0484 (5)
C(17)	1.0555 (2)	−0.4029 (2)	−0.1053 (2)	0.0492 (5)
C(18)	1.1279 (2)	−0.5374 (2)	−0.1583 (2)	0.0551 (5)
C(19)	1.2220 (2)	−0.6099 (2)	−0.0640 (2)	0.0522 (5)
C(20)	1.2869 (2)	−0.7440 (2)	−0.1314 (3)	0.0650 (6)
C(21)	0.8271 (2)	−0.1563 (2)	−0.3576 (2)	0.0550 (5)
C(22)	1.2703 (2)	−0.5676 (2)	0.1145 (3)	0.0688 (6)
H(3)	0.7656	0.3631	0.5345	0.0559*
H(5)	0.6013	0.4253	0.0888	0.0573*
H(6)	0.6979	0.2190	−0.0197	0.0564*
H(7)	0.6199	0.5666	0.5034	0.0570*
H(8)	0.5332	0.6146	0.2041	0.0663*
H(10a)	0.3431	0.9310	0.5828	0.0626*
H(10b)	0.4719	0.9688	0.6110	0.0626*
H(11a)	0.5811	0.8947	0.8396	0.0709*
H(11b)	0.4458	0.9926	0.8564	0.0709*
H(11c)	0.4552	0.8520	0.8101	0.0709*
H(12a)	0.8395	0.1961	0.6453	0.0768*
H(12b)	0.9634	0.2344	0.6582	0.0768*
H(12c)	0.9821	0.1016	0.6673	0.0768*
H(13a)	0.8674	0.0413	−0.0646	0.0552*
H(13b)	0.7356	0.0120	−0.0850	0.0552*
H(14)	0.9476	−0.1754	0.0228	0.0537*
H(16a)	1.0320	−0.3556	−0.3046	0.0589*
H(16b)	0.9049	−0.3883	−0.3161	0.0589*
H(17a)	1.1213	−0.3589	−0.0343	0.0600*
H(17b)	0.9964	−0.3977	−0.0515	0.0600*
H(18)	1.1032	−0.5740	−0.2708	0.0672*
H(20a)	1.3829	−0.7579	−0.0969	0.0783*
H(20b)	1.2644	−0.7958	−0.0944	0.0783*
H(20c)	1.2538	−0.7627	−0.2460	0.0783*
H(21a)	0.7697	−0.0755	−0.3305	0.0674*
H(21b)	0.7735	−0.2090	−0.4393	0.0674*
H(21c)	0.8923	−0.1519	−0.3960	0.0674*
H(22a)	1.3641	−0.5717	0.1494	0.0831*
H(22b)	1.2196	−0.4848	0.1468	0.0831*
H(22c)	1.2566	−0.6202	0.1596	0.0831*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O(1)	0.0584 (7)	0.0353 (7)	0.0354 (7)	−0.0012 (5)	0.0150 (5)	0.0062 (5)
O(2)	0.0727 (8)	0.0392 (7)	0.0380 (7)	0.0005 (6)	0.0147 (6)	0.0116 (6)
O(3)	0.116 (1)	0.0439 (8)	0.0431 (8)	0.0140 (8)	0.0183 (8)	0.0135 (6)
O(4)	0.0693 (8)	0.0377 (7)	0.0407 (7)	0.0002 (6)	0.0200 (6)	0.0087 (6)
C(1)	0.0485 (8)	0.0354 (9)	0.0401 (9)	−0.0036 (7)	0.0154 (7)	0.0076 (7)
C(2)	0.0497 (8)	0.0407 (9)	0.0399 (9)	−0.0051 (7)	0.0124 (7)	0.0127 (7)
C(3)	0.0525 (9)	0.0426 (9)	0.0340 (8)	−0.0057 (7)	0.0131 (7)	0.0066 (7)
C(4)	0.0477 (8)	0.0408 (9)	0.0388 (9)	−0.0046 (7)	0.0133 (7)	0.0076 (7)
C(5)	0.0537 (9)	0.0382 (10)	0.0386 (9)	0.0004 (7)	0.0122 (7)	0.0118 (7)
C(6)	0.0541 (9)	0.0411 (9)	0.0368 (8)	−0.0053 (7)	0.0118 (7)	0.0094 (7)
C(7)	0.0517 (9)	0.042 (1)	0.0376 (8)	−0.0048 (8)	0.0132 (7)	0.0061 (7)
C(8)	0.073 (1)	0.041 (1)	0.0352 (8)	−0.0018 (9)	0.0187 (8)	0.0047 (8)
C(9)	0.0633 (10)	0.043 (1)	0.0397 (9)	−0.0036 (8)	0.0138 (7)	0.0089 (8)
C(10)	0.067 (1)	0.0340 (9)	0.0413 (9)	−0.0007 (7)	0.0192 (8)	0.0030 (7)
C(11)	0.072 (1)	0.051 (1)	0.0420 (10)	−0.0076 (9)	0.0202 (8)	0.0040 (8)
C(12)	0.084 (1)	0.051 (1)	0.0372 (10)	−0.0011 (9)	0.0111 (8)	0.0150 (8)
C(13)	0.0524 (8)	0.0381 (9)	0.0369 (8)	−0.0066 (7)	0.0137 (7)	0.0052 (7)
C(14)	0.0502 (8)	0.0379 (10)	0.0385 (9)	−0.0045 (7)	0.0147 (7)	0.0086 (7)
C(15)	0.0459 (8)	0.0387 (9)	0.0428 (9)	−0.0060 (6)	0.0143 (7)	0.0101 (7)
C(16)	0.0572 (9)	0.0432 (10)	0.0417 (9)	−0.0081 (8)	0.0186 (7)	0.0075 (8)
C(17)	0.0610 (10)	0.0379 (9)	0.0455 (9)	−0.0039 (8)	0.0221 (8)	0.0084 (8)
C(18)	0.071 (1)	0.044 (1)	0.0490 (10)	−0.0041 (9)	0.0245 (8)	0.0128 (9)
C(19)	0.0563 (9)	0.047 (1)	0.056 (1)	−0.0064 (8)	0.0230 (8)	0.0153 (8)
C(20)	0.077 (1)	0.048 (1)	0.066 (1)	0.0023 (9)	0.029 (1)	0.0195 (10)
C(21)	0.0637 (10)	0.050 (1)	0.0379 (9)	−0.0020 (8)	0.0141 (7)	0.0097 (8)
C(22)	0.066 (1)	0.065 (1)	0.057 (1)	−0.0044 (9)	0.0103 (9)	0.016 (1)

Geometric parameters (Å, º)

O(1)—C(1)	1.357 (2)	C(12)—H(12b)	0.953
O(1)—C(13)	1.432 (2)	C(12)—H(12c)	0.953
O(2)—C(2)	1.362 (2)	C(13)—C(14)	1.499 (2)
O(2)—C(12)	1.431 (2)	C(13)—H(13a)	0.950
O(3)—C(9)	1.207 (2)	C(13)—H(13b)	0.952
O(4)—C(9)	1.330 (2)	C(14)—C(15)	1.323 (3)
O(4)—C(10)	1.449 (2)	C(14)—H(14)	0.950
C(1)—C(2)	1.417 (2)	C(15)—C(16)	1.508 (2)
C(1)—C(6)	1.397 (2)	C(15)—C(21)	1.500 (2)
C(2)—C(3)	1.375 (2)	C(16)—C(17)	1.525 (2)
C(3)—C(4)	1.409 (2)	C(16)—H(16a)	0.955
C(3)—H(3)	0.951	C(16)—H(16b)	0.950
C(4)—C(5)	1.389 (2)	C(17)—C(18)	1.507 (3)
C(4)—C(7)	1.455 (3)	C(17)—H(17a)	0.948
C(5)—C(6)	1.384 (3)	C(17)—H(17b)	0.947
C(5)—H(5)	0.951	C(18)—C(19)	1.325 (3)
C(6)—H(6)	0.952	C(18)—H(18)	0.950
C(7)—C(8)	1.326 (3)	C(19)—C(20)	1.508 (3)
C(7)—H(7)	0.945	C(19)—C(22)	1.486 (3)
C(8)—C(9)	1.469 (3)	C(20)—H(20a)	0.949
C(8)—H(8)	0.952	C(20)—H(20b)	0.948
C(10)—C(11)	1.492 (2)	C(20)—H(20c)	0.952
C(10)—H(10a)	0.952	C(21)—H(21a)	0.951
C(10)—H(10b)	0.946	C(21)—H(21b)	0.950
C(11)—H(11a)	0.949	C(21)—H(21c)	0.950
C(11)—H(11b)	0.951	C(22)—H(22a)	0.946
C(11)—H(11c)	0.952	C(22)—H(22b)	0.947
C(12)—H(12a)	0.943	C(22)—H(22c)	0.952
O(1)···C(12)^i	3.558 (2)	C(1)···C(15)^iii	3.552 (2)
O(2)···O(2)^i	3.255 (2)	C(1)···C(11)^iv	3.582 (3)
O(2)···C(12)^i	3.332 (2)	C(11)···C(11)^v	3.547 (4)
O(3)···C(6)^ii	3.381 (2)	C(13)···C(13)^iii	3.578 (3)
O(3)···C(13)^ii	3.448 (2)	C(13)···C(14)^iii	3.595 (2)
C(1)—O(1)—C(13)	116.3 (1)	O(1)—C(13)—C(14)	108.5 (1)
C(2)—O(2)—C(12)	116.8 (1)	O(1)—C(13)—H(13a)	109.9
C(9)—O(4)—C(10)	116.6 (1)	O(1)—C(13)—H(13b)	109.7
O(1)—C(1)—C(2)	116.7 (1)	C(14)—C(13)—H(13a)	109.7
O(1)—C(1)—C(6)	124.7 (2)	C(14)—C(13)—H(13b)	109.6
C(2)—C(1)—C(6)	118.6 (2)	H(13a)—C(13)—H(13b)	109.4
O(2)—C(2)—C(1)	114.5 (1)	C(13)—C(14)—C(15)	124.0 (1)
O(2)—C(2)—C(3)	125.7 (1)	C(13)—C(14)—H(14)	118.0
C(1)—C(2)—C(3)	119.8 (1)	C(15)—C(14)—H(14)	118.0
C(2)—C(3)—C(4)	121.9 (1)	C(14)—C(15)—C(16)	124.5 (1)
C(2)—C(3)—H(3)	119.1	C(14)—C(15)—C(21)	121.9 (2)
C(4)—C(3)—H(3)	119.0	C(16)—C(15)—C(21)	113.6 (1)
C(3)—C(4)—C(5)	117.4 (2)	C(15)—C(16)—C(17)	117.3 (1)
C(3)—C(4)—C(7)	120.0 (1)	C(15)—C(16)—H(16a)	107.6
C(5)—C(4)—C(7)	122.5 (2)	C(15)—C(16)—H(16b)	107.8
C(4)—C(5)—C(6)	121.8 (1)	C(17)—C(16)—H(16a)	107.3
C(4)—C(5)—H(5)	119.1	C(17)—C(16)—H(16b)	107.6
C(6)—C(5)—H(5)	119.1	H(16a)—C(16)—H(16b)	109.1
C(1)—C(6)—C(5)	120.5 (2)	C(16)—C(17)—C(18)	111.7 (1)
C(1)—C(6)—H(6)	119.7	C(16)—C(17)—H(17a)	108.9
C(5)—C(6)—H(6)	119.9	C(16)—C(17)—H(17b)	108.8
C(4)—C(7)—C(8)	126.1 (2)	C(18)—C(17)—H(17a)	108.8
C(4)—C(7)—H(7)	116.8	C(18)—C(17)—H(17b)	108.8
C(8)—C(7)—H(7)	117.1	H(17a)—C(17)—H(17b)	109.9
C(7)—C(8)—C(9)	125.4 (2)	C(17)—C(18)—C(19)	126.7 (2)
C(7)—C(8)—H(8)	117.4	C(17)—C(18)—H(18)	116.5
C(9)—C(8)—H(8)	117.1	C(19)—C(18)—H(18)	116.8
O(3)—C(9)—O(4)	122.5 (2)	C(18)—C(19)—C(20)	121.9 (2)
O(3)—C(9)—C(8)	124.2 (2)	C(18)—C(19)—C(22)	123.4 (2)
O(4)—C(9)—C(8)	113.2 (1)	C(20)—C(19)—C(22)	114.7 (2)
O(4)—C(10)—C(11)	106.0 (1)	C(19)—C(20)—H(20a)	109.5
O(4)—C(10)—H(10a)	110.3	C(19)—C(20)—H(20b)	109.4
O(4)—C(10)—H(10b)	110.7	C(19)—C(20)—H(20c)	109.5
C(11)—C(10)—H(10a)	109.9	H(20a)—C(20)—H(20b)	109.7
C(11)—C(10)—H(10b)	110.2	H(20a)—C(20)—H(20c)	109.4
H(10a)—C(10)—H(10b)	109.7	H(20b)—C(20)—H(20c)	109.4
C(10)—C(11)—H(11a)	109.6	C(15)—C(21)—H(21a)	109.5
C(10)—C(11)—H(11b)	109.6	C(15)—C(21)—H(21b)	109.4
C(10)—C(11)—H(11c)	109.7	C(15)—C(21)—H(21c)	109.6
H(11a)—C(11)—H(11b)	109.4	H(21a)—C(21)—H(21b)	109.4
H(11a)—C(11)—H(11c)	109.3	H(21a)—C(21)—H(21c)	109.5
H(11b)—C(11)—H(11c)	109.2	H(21b)—C(21)—H(21c)	109.5
O(2)—C(12)—H(12a)	109.8	C(19)—C(22)—H(22a)	109.5
O(2)—C(12)—H(12b)	109.2	C(19)—C(22)—H(22b)	109.1
O(2)—C(12)—H(12c)	109.2	C(19)—C(22)—H(22c)	109.0
H(12a)—C(12)—H(12b)	109.8	H(22a)—C(22)—H(22b)	110.0
H(12a)—C(12)—H(12c)	109.8	H(22a)—C(22)—H(22c)	109.6
H(12b)—C(12)—H(12c)	109.0	H(22b)—C(22)—H(22c)	109.6
O(1)—C(1)—C(2)—O(2)	0.7 (2)	C(3)—C(2)—C(1)—C(6)	0.7 (2)
O(1)—C(1)—C(2)—C(3)	−178.2 (1)	C(3)—C(4)—C(5)—C(6)	0.7 (3)
O(1)—C(1)—C(6)—C(5)	179.2 (1)	C(3)—C(4)—C(7)—C(8)	174.6 (2)
O(1)—C(13)—C(14)—C(15)	180.0 (1)	C(4)—C(7)—C(8)—C(9)	178.4 (2)
O(2)—C(2)—C(1)—C(6)	179.6 (1)	C(5)—C(4)—C(7)—C(8)	−5.9 (3)
O(2)—C(2)—C(3)—C(4)	−179.9 (2)	C(6)—C(1)—O(1)—C(13)	0.6 (2)
O(3)—C(9)—O(4)—C(10)	−1.1 (3)	C(6)—C(5)—C(4)—C(7)	−178.9 (1)
O(3)—C(9)—C(8)—C(7)	−176.8 (2)	C(8)—C(9)—O(4)—C(10)	178.9 (1)
O(4)—C(9)—C(8)—C(7)	3.2 (3)	C(9)—O(4)—C(10)—C(11)	−177.5 (2)
C(1)—O(1)—C(13)—C(14)	−178.2 (1)	C(13)—C(14)—C(15)—C(16)	178.3 (1)
C(1)—C(2)—O(2)—C(12)	177.6 (2)	C(13)—C(14)—C(15)—C(21)	−0.1 (3)
C(1)—C(2)—C(3)—C(4)	−1.2 (3)	C(14)—C(15)—C(16)—C(17)	−2.3 (2)
C(1)—C(6)—C(5)—C(4)	−1.2 (3)	C(15)—C(16)—C(17)—C(18)	−177.1 (1)
C(2)—C(1)—O(1)—C(13)	179.4 (1)	C(16)—C(17)—C(18)—C(19)	170.5 (2)
C(2)—C(1)—C(6)—C(5)	0.5 (3)	C(17)—C(16)—C(15)—C(21)	176.1 (1)
C(2)—C(3)—C(4)—C(5)	0.5 (3)	C(17)—C(18)—C(19)—C(20)	179.6 (2)
C(2)—C(3)—C(4)—C(7)	−179.9 (1)	C(17)—C(18)—C(19)—C(22)	0.8 (3)
C(3)—C(2)—O(2)—C(12)	−3.6 (3)

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z; (iii) −x+2, −y, −z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+2.