Methyl eucomate

Li, L.; Zhou, G.-X.; Jiang, R.-W.

doi:10.1107/S1600536808018734

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1354

doi:10.1107/S1600536808018734

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Methyl eucomate

Linglin Li,^a Guang-Xiong Zhou ^b and Ren-Wang Jiang ^b ^*

^aNutrition and Metabolism Laboratory, Beth Israel Deaconess Medical Center, Boston, MA 02215, USA, and ^bInstitute of Traditional Chinese Medicine and Natural Products, College of Pharmacy, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: trwjiang@jnu.edu.cn

(Received 27 April 2008; accepted 20 June 2008; online 28 June 2008)

The crystal structure of the title compound [systematic name: methyl 3-carboxy-3-hydroxy-3-(4-hydroxybenzyl)propanoate], C₁₂H₁₄O₆, is stabilized by intermolecular O—H⋯O and C—H⋯O hydrogen bonds. The molecules are arranged in layers, parallel to (001), which are interconnected by the O—H⋯O hydrogen bonds.

Related literature

For related literature, see: Heller & Tamm (1974 ); Jiang et al. (2002 , 2006 ).

Experimental

Crystal data

C₁₂H₁₄O₆
M_r = 254.23
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.9109 (6) Å
b = 7.0348 (7) Å
c = 29.109 (3) Å
V = 1210.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.40 × 0.32 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
6709 measured reflections
1279 independent reflections
1047 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.066
S = 1.05
1278 reflections
168 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.82	1.96	2.775 (2)	172
O2—H2⋯O1ⁱⁱ	0.82	2.33	2.888 (2)	125
O4—H4⋯O2ⁱⁱⁱ	0.82	1.85	2.639 (2)	161
C12—H12B⋯O5^iv	0.96	2.42	3.268 (4)	148
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT and XPREP in SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1998 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018734/fb2096sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018734/fb2096Isup2.hkl

checkCIF report

Comment top

Methyl eucomate is the methyl ester of the eucomic acid. The title compound has been isolated from several edible plants, e. g. Opuntia dillenii (Jiang et al., 2006) or Opuntia vulgaris (Jiang et al., 2002). However, the stereochemistry of the ester has not been established yet. In the present paper, we report its crystal structure.

The molecule contains phenol, carboxyl, ester and hydroxyl functional groups (Fig. 1). The mean deviation of the benzene ring from planarity is 0.0004 Å and its dihedral angle with the plane of the carboxylic group at C8 is 50.3 (3)°, while it is roughly perpendicular to the ester group at C10 with a dihedral angle of 87.3 (3)°.

The intermolecular hydrogen bonds O1—H···O3, O2—H···O1 and O4—H···O2 (Tab. 1) link the molecules into layers that are parallel to (001) (Fig. 2).

There is no heavy atom with a significant anomalous dispersion contribution, so the absolute configuration from the diffraction pattern itself could not be determined. However, the absolute configuration of the eucomic acid has been established by synthesis (Heller & Tamm, 1974) though its crystal structure has not been determined. Therefore the title compound is expected to share the same R configuration at the chiral centre C8.

Related literature top

For related literature, see: Heller & Tamm (1974); Jiang et al. (2002, 2006).

Experimental top

The title compound was purified from the stems of Opuntia vulgaris according to the reported procedures (Jiang et al., 2002). Briefly, the stems of Opuntia vulgaris (1 kg) was extracted with 95% ethanol under room temperature. The extracted solution was concentrated with rotary evaporator to afford a crude extract, which was suspended in distilled water and partitioned with petroleum ether, ethyl acetate and n-butanol. Then the n-butanol fraction was subjected to silica gel column chromatography eluted with methanol-chloroform gradient solvent system to afford the title compound (16 mg). The transparent rectangular crystals of the title compound with average size of 0.50 × 0.40 × 0.30 mm were obtained by slow evaporation of the methanol solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART and SAINT (Bruker, 1998); data reduction: XPREP in SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title structure showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The packing diagram of the title structure viewed down the a axis.

methyl 3-carboxy-3-hydroxy-3-(4-hydroxybenzyl)propanoate top

Crystal data top

C₁₂H₁₄O₆	F(000) = 536
M_r = 254.23	D_x = 1.395 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6709 reflections
a = 5.9109 (6) Å	θ = 1.4–25.0°
b = 7.0348 (7) Å	µ = 0.11 mm⁻¹
c = 29.109 (3) Å	T = 293 K
V = 1210.4 (2) Å³	Rectangular, colourless
Z = 4	0.40 × 0.32 × 0.25 mm

Data collection top

Bruker SMART/CCD diffractometer	1047 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
Graphite monochromator	θ_max = 25.0°, θ_min = 1.4°
ω scans	h = −6→7
6709 measured reflections	k = −8→7
1279 independent reflections	l = −27→34

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0328P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1278 reflections	Δρ_max = 0.14 e Å⁻³
168 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
42 constraints	Extinction coefficient: 0.0070 (19)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₂H₁₄O₆	V = 1210.4 (2) Å³
M_r = 254.23	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.9109 (6) Å	µ = 0.11 mm⁻¹
b = 7.0348 (7) Å	T = 293 K
c = 29.109 (3) Å	0.40 × 0.32 × 0.25 mm

Data collection top

Bruker SMART/CCD diffractometer	1047 reflections with I > 2σ(I)
6709 measured reflections	R_int = 0.046
1279 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.05	Δρ_max = 0.14 e Å⁻³
1278 reflections	Δρ_min = −0.12 e Å⁻³
168 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	0.2505 (3)	0.2830 (2)	0.32392 (5)	0.0466 (5)
H1	0.1313	0.2346	0.3323	0.070*
O2	0.5510 (2)	0.5081 (2)	0.11441 (5)	0.0400 (4)
H2	0.5099	0.5865	0.1335	0.060*
O3	0.1405 (3)	0.6278 (2)	0.13901 (5)	0.0425 (4)
O4	−0.0301 (3)	0.3948 (3)	0.09911 (6)	0.0499 (5)
H4	−0.1460	0.4500	0.1070	0.075*
O5	0.2745 (4)	0.6569 (3)	0.03265 (6)	0.0640 (6)
O6	0.3709 (3)	0.4543 (2)	−0.02286 (5)	0.0543 (5)
C1	0.2722 (4)	0.2631 (3)	0.27718 (8)	0.0344 (6)
C2	0.4773 (4)	0.3133 (3)	0.25799 (8)	0.0367 (6)
H2B	0.5932	0.3598	0.2764	0.044*
C3	0.5089 (4)	0.2940 (3)	0.21133 (8)	0.0370 (6)
H3A	0.6475	0.3286	0.1987	0.044*
C4	0.3420 (4)	0.2253 (3)	0.18265 (8)	0.0346 (6)
C5	0.1367 (4)	0.1752 (3)	0.20275 (8)	0.0389 (6)
H5A	0.0209	0.1285	0.1843	0.047*
C6	0.1010 (4)	0.1933 (3)	0.24947 (9)	0.0387 (6)
H6A	−0.0373	0.1588	0.2622	0.046*
C7	0.3804 (4)	0.2011 (3)	0.13179 (8)	0.0400 (6)
H7A	0.2693	0.1119	0.1201	0.048*
H7B	0.5286	0.1451	0.1272	0.048*
C8	0.3660 (4)	0.3855 (3)	0.10324 (7)	0.0336 (5)
C9	0.3831 (4)	0.3384 (3)	0.05217 (8)	0.0403 (6)
H9A	0.5339	0.2904	0.0459	0.048*
H9B	0.2767	0.2375	0.0452	0.048*
C10	0.3374 (4)	0.5023 (4)	0.02090 (8)	0.0424 (6)
C11	0.1476 (4)	0.4865 (4)	0.11534 (7)	0.0347 (5)
C12	0.3196 (5)	0.5985 (4)	−0.05667 (9)	0.0681 (9)
H12A	0.3552	0.5515	−0.0868	0.102*
H12B	0.4079	0.7102	−0.0505	0.102*
H12C	0.1617	0.6297	−0.0552	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0418 (10)	0.0604 (11)	0.0377 (10)	−0.0079 (10)	0.0050 (8)	0.0063 (9)
O2	0.0255 (9)	0.0527 (11)	0.0418 (11)	−0.0021 (8)	0.0013 (7)	−0.0105 (9)
O3	0.0368 (9)	0.0474 (10)	0.0432 (10)	0.0061 (9)	0.0051 (8)	−0.0103 (8)
O4	0.0229 (9)	0.0617 (12)	0.0651 (12)	0.0047 (9)	−0.0011 (9)	−0.0157 (11)
O5	0.0819 (15)	0.0646 (12)	0.0454 (11)	0.0208 (12)	0.0057 (11)	−0.0017 (10)
O6	0.0678 (12)	0.0652 (11)	0.0298 (9)	−0.0045 (11)	0.0042 (10)	−0.0054 (9)
C1	0.0334 (13)	0.0335 (13)	0.0363 (14)	0.0024 (11)	0.0021 (11)	0.0060 (11)
C2	0.0315 (12)	0.0395 (14)	0.0391 (15)	−0.0086 (12)	−0.0029 (11)	0.0020 (12)
C3	0.0277 (12)	0.0404 (13)	0.0429 (15)	−0.0040 (12)	0.0035 (11)	0.0041 (12)
C4	0.0294 (12)	0.0326 (12)	0.0417 (14)	0.0046 (11)	−0.0010 (11)	0.0021 (11)
C5	0.0293 (12)	0.0412 (13)	0.0463 (15)	−0.0009 (12)	−0.0045 (12)	0.0000 (12)
C6	0.0263 (12)	0.0430 (13)	0.0470 (15)	−0.0029 (11)	0.0030 (11)	0.0068 (13)
C7	0.0336 (12)	0.0431 (13)	0.0431 (14)	0.0062 (12)	−0.0021 (12)	−0.0074 (12)
C8	0.0223 (11)	0.0441 (14)	0.0344 (13)	0.0009 (12)	−0.0012 (11)	−0.0054 (12)
C9	0.0334 (13)	0.0521 (14)	0.0356 (14)	0.0060 (12)	0.0028 (11)	−0.0071 (12)
C10	0.0315 (13)	0.0572 (16)	0.0385 (14)	−0.0011 (15)	0.0029 (12)	−0.0075 (14)
C11	0.0277 (12)	0.0460 (14)	0.0303 (12)	0.0012 (13)	−0.0001 (11)	0.0007 (12)
C12	0.085 (2)	0.080 (2)	0.0393 (15)	−0.023 (2)	−0.0078 (16)	0.0111 (16)

Geometric parameters (Å, º) top

O1—C1	1.374 (3)	C4—C5	1.392 (3)
O1—H1	0.8200	C4—C7	1.507 (3)
O2—C8	1.430 (3)	C5—C6	1.382 (3)
O2—H2	0.8200	C5—H5A	0.9300
O3—C11	1.210 (3)	C6—H6A	0.9300
O4—C11	1.320 (3)	C7—C8	1.543 (3)
O4—H4	0.8200	C7—H7A	0.9700
O5—C10	1.200 (3)	C7—H7B	0.9700
O6—C10	1.333 (3)	C8—C11	1.515 (3)
O6—C12	1.446 (3)	C8—C9	1.526 (3)
C1—C2	1.380 (3)	C9—C10	1.494 (3)
C1—C6	1.384 (3)	C9—H9A	0.9700
C2—C3	1.378 (3)	C9—H9B	0.9700
C2—H2B	0.9300	C12—H12A	0.9600
C3—C4	1.380 (3)	C12—H12B	0.9600
C3—H3A	0.9300	C12—H12C	0.9600

C1—O1—H1	109.5	C8—C7—H7B	108.5
C8—O2—H2	109.5	H7A—C7—H7B	107.5
C11—O4—H4	109.5	O2—C8—C11	108.40 (17)
C10—O6—C12	116.2 (2)	O2—C8—C9	107.55 (19)
O1—C1—C2	117.2 (2)	C11—C8—C9	112.63 (19)
O1—C1—C6	123.0 (2)	O2—C8—C7	110.03 (18)
C2—C1—C6	119.8 (2)	C11—C8—C7	108.44 (18)
C3—C2—C1	119.5 (2)	C9—C8—C7	109.77 (19)
C3—C2—H2B	120.2	C10—C9—C8	114.4 (2)
C1—C2—H2B	120.2	C10—C9—H9A	108.6
C2—C3—C4	122.3 (2)	C8—C9—H9A	108.6
C2—C3—H3A	118.9	C10—C9—H9B	108.6
C4—C3—H3A	118.9	C8—C9—H9B	108.6
C3—C4—C5	117.2 (2)	H9A—C9—H9B	107.6
C3—C4—C7	121.8 (2)	O5—C10—O6	123.3 (2)
C5—C4—C7	121.0 (2)	O5—C10—C9	125.6 (2)
C6—C5—C4	121.5 (2)	O6—C10—C9	111.1 (2)
C6—C5—H5A	119.2	O3—C11—O4	125.3 (2)
C4—C5—H5A	119.2	O3—C11—C8	123.2 (2)
C5—C6—C1	119.6 (2)	O4—C11—C8	111.43 (19)
C5—C6—H6A	120.2	O6—C12—H12A	109.5
C1—C6—H6A	120.2	O6—C12—H12B	109.5
C4—C7—C8	115.19 (19)	H12A—C12—H12B	109.5
C4—C7—H7A	108.5	O6—C12—H12C	109.5
C8—C7—H7A	108.5	H12A—C12—H12C	109.5
C4—C7—H7B	108.5	H12B—C12—H12C	109.5

O1—C1—C2—C3	179.3 (2)	C4—C7—C8—C9	−174.1 (2)
C6—C1—C2—C3	0.3 (4)	O2—C8—C9—C10	−68.8 (2)
C1—C2—C3—C4	−0.2 (4)	C11—C8—C9—C10	50.5 (3)
C2—C3—C4—C5	0.1 (3)	C7—C8—C9—C10	171.5 (2)
C2—C3—C4—C7	−178.7 (2)	C12—O6—C10—O5	−2.1 (4)
C3—C4—C5—C6	0.0 (3)	C12—O6—C10—C9	176.6 (2)
C7—C4—C5—C6	178.7 (2)	C8—C9—C10—O5	−5.7 (4)
C4—C5—C6—C1	0.1 (4)	C8—C9—C10—O6	175.6 (2)
O1—C1—C6—C5	−179.2 (2)	O2—C8—C11—O3	−13.9 (3)
C2—C1—C6—C5	−0.2 (4)	C9—C8—C11—O3	−132.8 (2)
C3—C4—C7—C8	−78.5 (3)	C7—C8—C11—O3	105.5 (2)
C5—C4—C7—C8	102.8 (3)	O2—C8—C11—O4	169.74 (19)
C4—C7—C8—O2	67.7 (3)	C9—C8—C11—O4	50.9 (3)
C4—C7—C8—C11	−50.7 (3)	C7—C8—C11—O4	−70.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.96	2.775 (2)	172
O2—H2···O1ⁱⁱ	0.82	2.34	2.888 (2)	125
O4—H4···O2ⁱⁱⁱ	0.82	1.85	2.639 (2)	161
C12—H12B···O5^iv	0.96	2.42	3.268 (4)	148

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, y, z; (iv) x+1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₆
M_r	254.23
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.9109 (6), 7.0348 (7), 29.109 (3)
V (Å³)	1210.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.32 × 0.25

Data collection
Diffractometer	Bruker SMART/CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6709, 1279, 1047
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.066, 1.05
No. of reflections	1278
No. of parameters	168
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.12

Computer programs: SMART (Bruker, 1998), SMART and SAINT (Bruker, 1998), XPREP in SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.820	1.960	2.775 (2)	172.1
O2—H2···O1ⁱⁱ	0.820	2.335	2.888 (2)	125.3
O4—H4···O2ⁱⁱⁱ	0.820	1.850	2.639 (2)	161.1
C12—H12B···O5^iv	0.960	2.420	3.268 (4)	147.6

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, y, z; (iv) x+1/2, −y+3/2, −z.

Acknowledgements

This work was supported by the Starting Fund for Excellent Talents of Jinan University.

References

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