Eucomic acid methanol monosolvate

Li, G.-Q.; Li, Y.-L.; Wang, G.-C.; Liang, Z.-H.; Jiang, R.-W.

doi:10.1107/S1600536811030017

organic compounds

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Volume 67| Part 8| August 2011| Page o2192

doi:10.1107/S1600536811030017

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Eucomic acid methanol monosolvate

Guo-Qiang Li,^a Yao-Lan Li,^a Guo-Cai Wang,^a ^* Zhi-Hong Liang ^b and Ren-Wang Jiang ^a

^aGuangdong Province Key Laboratory of Pharmacodynamic Constituents of Traditional Chinese Medicine and New Drugs Research, Institute of Traditional Chinese Medicine and Natural Products, Jinan University, Guangzhou 510632, People's Republic of China, and ^bAnalysis and Testing Center, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: trwjiang@jnu.edu.cn

(Received 30 June 2011; accepted 25 July 2011; online 30 July 2011)

In the crystal structure of the title compound [systematic name: 2-hydroxy-2-(4-hydroxybenzyl)butanedioic acid methanol monosolvate], C₁₁H₁₂O₆·CH₃OH, the dihedral angles between the planes of the carboxyl groups and the benzene ring are 51.23 (9) and 87.97 (9)°. Intermolecular O—H⋯O hydrogen-bonding interactions involving the hydroxy and carboxylic acid groups and the methanol solvent molecule give a three-dimensional structure.

Related literature

For general background to natural existance and related structures, see: Jiang et al. (2006 ); Li et al. (2008 ). For the absolute configuration of eucomic acid, see: Heller & Tamm (1974 ).

Experimental

Crystal data

C₁₁H₁₂O₆·CH₄O
M_r = 272.25
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.8970 (2) Å
b = 7.2088 (3) Å
c = 31.3290 (4) Å
V = 1331.81 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.60 × 0.20 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer
7417 measured reflections
1408 independent reflections
1184 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.081
S = 1.05
1408 reflections
178 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 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	1.97	2.781 (3)	170
O2—H2⋯O1ⁱⁱ	0.82	2.33	2.861 (2)	123
O4—H4⋯O2ⁱⁱⁱ	0.82	1.85	2.639 (2)	162
O6—H6⋯O7	0.82	1.76	2.575 (4)	170
O7—H7⋯O5^iv	0.82	1.93	2.694 (4)	156
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030017/zs2127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030017/zs2127Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030017/zs2127Isup3.cml

checkCIF report

Comment top

The title compound C₁₁H₁₂O₆.CH₃OH (Fig. 1) is the monomethanol solvate of eucomic acid [systematic name: 2-hydroxy-2-(4-hydroxybenzyl)butanedioic acid], and was originally isolated from the stems of Opuntia dillenii (Jiang et al., 2006) and the absolute configuration was established by synthesis (Heller & Tamm, 1974). With the present compound,which was isolated from the stems of the related species Opuntia vulgaris, the dihedral angle between the plane of the benzene ring and that of the carboxylic group at C8 is 51.23 (9)°, and 87.97 (9)° with that at C9. These values are similar to those in the methyl eucomate structure (Li et al., 2008).

Intermolecular O—H···O hydrogen-bonding interactions involving the hydroxy and carboxylic acid groups and the methanol molecule (Table 1) give a three-dimensional structure. A short intramolecular interaction between the C8 hydroxy group and a carboxyl O acceptor is also present [O2—H2···O3 = 2.655 (2) Å; <O—H···O = 117°].

Related literature top

For general background, see: Jiang et al. (2006); Li et al. (2008). For the absolute configuration of eucomic acid, see: Heller & Tamm (1974).

Experimental top

The title compound was isolated from the stems of Opuntia vulgaris, 1 kg of which was extracted with 95% ethanol at room temperature, then concentrated by rotary evaporator. The crude extract was suspended in distilled water and partitioned with petroleum ether, ethyl acetate and n-butanol. The title compound (22 mg) was isolated from the n-butanol fraction using silica-gel column chromatography. Crystals of the title compound were obtained after slow evaporation of a methanolic 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: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme. The intermolecular hydrogen bond is shown as a dashed line.

2-hydroxy-2-(4-hydroxybenzyl)butanedioic acid methanol monosolvate top

Crystal data top

C₁₁H₁₂O₆·CH₄O	D_x = 1.358 Mg m⁻³
M_r = 272.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 2341 reflections
a = 5.8970 (2) Å	θ = 1.3–25.0°
b = 7.2088 (3) Å	µ = 0.11 mm⁻¹
c = 31.3290 (4) Å	T = 293 K
V = 1331.81 (7) Å³	Prism, colourless
Z = 4	0.60 × 0.20 × 0.10 mm
F(000) = 576

Data collection top

Bruker SMART 1000 CCD diffractometer	1184 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.0°, θ_min = 1.3°
ω scans	h = −7→6
7417 measured reflections	k = −8→6
1408 independent reflections	l = −36→37

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0459P)² + 0.0811P] where P = (F_o² + 2F_c²)/3
1408 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₁H₁₂O₆·CH₄O	V = 1331.81 (7) Å³
M_r = 272.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.8970 (2) Å	µ = 0.11 mm⁻¹
b = 7.2088 (3) Å	T = 293 K
c = 31.3290 (4) Å	0.60 × 0.20 × 0.10 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1184 reflections with I > 2σ(I)
7417 measured reflections	R_int = 0.036
1408 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
1408 reflections	Δρ_min = −0.19 e Å⁻³
178 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
O4	0.5195 (3)	0.2588 (3)	0.38870 (6)	0.0496 (5)
H4	0.6358	0.3081	0.3799	0.074*
O2	−0.0623 (2)	0.3712 (2)	0.37354 (5)	0.0399 (4)
H2	−0.0175	0.4478	0.3561	0.060*
O1	0.2583 (3)	0.1398 (3)	0.18267 (5)	0.0503 (5)
H1	0.3811	0.0962	0.1756	0.075*
O3	0.3496 (3)	0.4842 (3)	0.35125 (5)	0.0465 (5)
C5	−0.0136 (4)	0.1541 (3)	0.28608 (7)	0.0390 (6)
H5	−0.1536	0.1885	0.2972	0.047*
C4	0.1514 (4)	0.0859 (3)	0.31338 (7)	0.0346 (5)
C1	0.2305 (4)	0.1201 (3)	0.22599 (7)	0.0373 (5)
C8	0.1204 (4)	0.2530 (3)	0.38545 (7)	0.0337 (5)
C3	0.3574 (4)	0.0333 (3)	0.29570 (7)	0.0401 (6)
H3	0.4705	−0.0139	0.3133	0.048*
O6	−0.0015 (5)	0.3883 (3)	0.49413 (6)	0.0750 (6)
H6	0.0124	0.4873	0.5068	0.112*
C6	0.0240 (4)	0.1722 (3)	0.24286 (7)	0.0380 (6)
H6A	−0.0889	0.2193	0.2252	0.046*
O5	0.2358 (4)	0.5185 (3)	0.44936 (6)	0.0769 (7)
C11	0.3419 (4)	0.3486 (4)	0.37382 (7)	0.0361 (5)
C2	0.3976 (4)	0.0497 (4)	0.25230 (7)	0.0420 (6)
H2A	0.5365	0.0136	0.2409	0.050*
C7	0.1074 (4)	0.0688 (3)	0.36073 (7)	0.0397 (6)
H7A	0.2170	−0.0167	0.3728	0.048*
H7B	−0.0421	0.0156	0.3649	0.048*
C10	0.1187 (4)	0.3916 (4)	0.45945 (7)	0.0449 (6)
C9	0.0974 (4)	0.2185 (4)	0.43323 (7)	0.0412 (6)
H9A	−0.0491	0.1622	0.4388	0.049*
H9B	0.2134	0.1311	0.4421	0.049*
O7	0.0058 (6)	0.6834 (4)	0.54040 (10)	0.1137 (10)
H7	−0.0761	0.7730	0.5357	0.171*
C12	0.1744 (7)	0.7337 (6)	0.56770 (13)	0.1048 (14)
H12A	0.3167	0.6874	0.5573	0.157*
H12B	0.1446	0.6828	0.5954	0.157*
H12C	0.1808	0.8666	0.5696	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0228 (8)	0.0617 (12)	0.0644 (12)	−0.0021 (9)	−0.0012 (8)	0.0092 (9)
O2	0.0262 (8)	0.0491 (10)	0.0446 (9)	−0.0002 (8)	0.0008 (7)	0.0065 (8)
O1	0.0462 (10)	0.0669 (13)	0.0378 (9)	0.0088 (10)	0.0061 (8)	−0.0085 (9)
O3	0.0389 (10)	0.0530 (11)	0.0474 (10)	−0.0084 (9)	0.0064 (8)	0.0099 (9)
C5	0.0297 (12)	0.0451 (14)	0.0421 (13)	0.0043 (12)	0.0037 (10)	−0.0067 (11)
C4	0.0293 (11)	0.0371 (12)	0.0374 (12)	−0.0031 (11)	−0.0008 (10)	−0.0057 (10)
C1	0.0362 (12)	0.0398 (13)	0.0360 (12)	−0.0020 (11)	0.0037 (10)	−0.0075 (11)
C8	0.0232 (11)	0.0434 (13)	0.0345 (12)	0.0004 (11)	−0.0002 (9)	0.0034 (10)
C3	0.0312 (13)	0.0442 (14)	0.0449 (13)	0.0002 (12)	−0.0058 (11)	−0.0028 (11)
O6	0.0911 (16)	0.0758 (14)	0.0580 (12)	−0.0167 (15)	0.0377 (12)	−0.0163 (10)
C6	0.0336 (13)	0.0430 (13)	0.0375 (13)	0.0072 (12)	−0.0018 (10)	−0.0022 (10)
O5	0.0892 (16)	0.0762 (15)	0.0653 (12)	−0.0429 (13)	0.0272 (12)	−0.0222 (11)
C11	0.0272 (12)	0.0485 (15)	0.0325 (12)	−0.0041 (12)	0.0018 (10)	−0.0049 (12)
C2	0.0287 (12)	0.0488 (14)	0.0485 (14)	0.0006 (12)	0.0033 (11)	−0.0114 (12)
C7	0.0344 (13)	0.0416 (13)	0.0430 (13)	−0.0068 (12)	0.0000 (10)	0.0015 (11)
C10	0.0399 (14)	0.0588 (16)	0.0361 (13)	−0.0049 (14)	0.0047 (11)	0.0011 (12)
C9	0.0361 (13)	0.0501 (14)	0.0373 (13)	−0.0072 (12)	0.0027 (10)	0.0033 (11)
O7	0.134 (2)	0.0946 (19)	0.112 (2)	0.0550 (19)	−0.042 (2)	−0.0518 (17)
C12	0.101 (3)	0.096 (3)	0.118 (3)	0.032 (3)	−0.028 (3)	−0.024 (3)

Geometric parameters (Å, º) top

O4—H4	0.8200	C3—H3	0.9300
O4—C11	1.317 (3)	C3—C2	1.385 (3)
O2—H2	0.8200	O6—H6	0.8200
O2—C8	1.424 (3)	O6—C10	1.298 (3)
O1—H1	0.8200	C6—H6A	0.9300
O1—C1	1.374 (3)	O5—C10	1.189 (3)
O3—C11	1.207 (3)	C2—H2A	0.9300
C5—H5	0.9300	C7—H7A	0.9700
C5—C4	1.386 (3)	C7—H7B	0.9700
C5—C6	1.378 (3)	C10—C9	1.499 (4)
C4—C3	1.388 (3)	C9—H9A	0.9700
C4—C7	1.511 (3)	C9—H9B	0.9700
C1—C6	1.380 (3)	O7—H7	0.8200
C1—C2	1.381 (3)	O7—C12	1.361 (4)
C8—C11	1.521 (3)	C12—H12A	0.9600
C8—C7	1.539 (3)	C12—H12B	0.9600
C8—C9	1.523 (3)	C12—H12C	0.9600

C11—O4—H4	109.5	O3—C11—C8	122.6 (2)
C8—O2—H2	109.5	C1—C2—C3	119.7 (2)
C1—O1—H1	109.5	C1—C2—H2A	120.2
C4—C5—H5	119.1	C3—C2—H2A	120.2
C6—C5—H5	119.1	C4—C7—C8	114.53 (19)
C6—C5—C4	121.8 (2)	C4—C7—H7A	108.6
C5—C4—C3	117.7 (2)	C4—C7—H7B	108.6
C5—C4—C7	120.9 (2)	C8—C7—H7A	108.6
C3—C4—C7	121.3 (2)	C8—C7—H7B	108.6
O1—C1—C6	117.1 (2)	H7A—C7—H7B	107.6
O1—C1—C2	122.8 (2)	O6—C10—C9	113.4 (2)
C6—C1—C2	120.1 (2)	O5—C10—O6	123.6 (2)
O2—C8—C11	108.42 (17)	O5—C10—C9	122.9 (2)
O2—C8—C7	110.29 (18)	C8—C9—H9A	108.9
O2—C8—C9	106.74 (18)	C8—C9—H9B	108.9
C11—C8—C7	108.24 (18)	C10—C9—C8	113.2 (2)
C11—C8—C9	112.71 (18)	C10—C9—H9A	108.9
C9—C8—C7	110.41 (19)	C10—C9—H9B	108.9
C4—C3—H3	119.4	H9A—C9—H9B	107.7
C2—C3—C4	121.2 (2)	C12—O7—H7	109.5
C2—C3—H3	119.4	O7—C12—H12A	109.5
C10—O6—H6	109.5	O7—C12—H12B	109.5
C5—C6—C1	119.5 (2)	O7—C12—H12C	109.5
C5—C6—H6A	120.2	H12A—C12—H12B	109.5
C1—C6—H6A	120.2	H12A—C12—H12C	109.5
O4—C11—C8	112.08 (19)	H12B—C12—H12C	109.5
O3—C11—O4	125.1 (2)

O2—C8—C11—O4	171.94 (19)	C6—C5—C4—C7	179.4 (2)
O2—C8—C11—O3	−12.4 (3)	C6—C1—C2—C3	−0.5 (4)
O2—C8—C7—C4	68.0 (2)	O5—C10—C9—C8	−32.1 (4)
O2—C8—C9—C10	−62.6 (2)	C11—C8—C7—C4	−50.5 (3)
O1—C1—C6—C5	179.5 (2)	C11—C8—C9—C10	56.3 (3)
O1—C1—C2—C3	−179.8 (2)	C2—C1—C6—C5	0.2 (4)
C5—C4—C3—C2	0.6 (3)	C7—C4—C3—C2	−179.7 (2)
C5—C4—C7—C8	−77.1 (3)	C7—C8—C11—O4	−68.4 (2)
C4—C5—C6—C1	0.5 (4)	C7—C8—C11—O3	107.2 (2)
C4—C3—C2—C1	0.1 (4)	C7—C8—C9—C10	177.5 (2)
C3—C4—C7—C8	103.2 (3)	C9—C8—C11—O4	54.0 (3)
O6—C10—C9—C8	148.3 (2)	C9—C8—C11—O3	−130.3 (2)
C6—C5—C4—C3	−0.9 (3)	C9—C8—C7—C4	−174.29 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.97	2.781 (3)	170
O2—H2···O3	0.82	2.19	2.655 (2)	116
O2—H2···O1ⁱⁱ	0.82	2.33	2.861 (2)	123
O4—H4···O2ⁱⁱⁱ	0.82	1.85	2.639 (2)	162
O6—H6···O7	0.82	1.76	2.575 (4)	170
O7—H7···O5^iv	0.82	1.93	2.694 (4)	156

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂O₆·CH₄O
M_r	272.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.8970 (2), 7.2088 (3), 31.3290 (4)
V (Å³)	1331.81 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.60 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7417, 1408, 1184
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.081, 1.05
No. of reflections	1408
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: SMART (Bruker, 1998), SMART and SAINT (Bruker, 1998), XPREP in SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.97	2.781 (3)	170
O2—H2···O1ⁱⁱ	0.82	2.33	2.861 (2)	123
O4—H4···O2ⁱⁱⁱ	0.82	1.85	2.639 (2)	162
O6—H6···O7	0.82	1.76	2.575 (4)	170
O7—H7···O5^iv	0.82	1.93	2.694 (4)	156

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

Acknowledgements

This work was supported by a grant from the Natural Science Fund of Guangdong Province (grant No. 07005971) and by the Guangdong High Level Talent Scheme (to RWJ).

References

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