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3-Eth-oxy-carbonyl-2-hy-droxy-6-meth-oxy-4-methyl-benzoic acid.
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MedLine Citation:
PMID:  22590305     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
The title compound, C(12)H(14)O(6), a substituted isophthalic acid monoester which was isolated from the lichen Thamnolia vermicularis var. subuliformis, displays intra-molecular carbox-yl-meth-oxy O-H⋯O and hy-droxy-carboxyl O-H⋯O hydrogen-bonding inter-actions. The terminal methyl group of the ethyl ester is disordered over two sets of sites with occupancies of 0.599 (19) and 0.401 (19).
Authors:
Yun-Xia Deng; Tao Guo; Hui Xie; Sheng-Li Pan
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Publication Detail:
Type:  Journal Article     Date:  2012-04-18
Journal Detail:
Title:  Acta crystallographica. Section E, Structure reports online     Volume:  68     ISSN:  1600-5368     ISO Abbreviation:  Acta Crystallogr Sect E Struct Rep Online     Publication Date:  2012 May 
Date Detail:
Created Date:  2012-05-16     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101089178     Medline TA:  Acta Crystallogr Sect E Struct Rep Online     Country:  United States    
Other Details:
Languages:  eng     Pagination:  o1420     Citation Subset:  -    
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Journal Information
Journal ID (nlm-ta): Acta Crystallogr Sect E Struct Rep Online
Journal ID (iso-abbrev): Acta Crystallogr Sect E Struct Rep Online
Journal ID (publisher-id): Acta Cryst. E
ISSN: 1600-5368
Publisher: International Union of Crystallography
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A full version of this article is available from Crystallography Journals Online.© Deng et al. 2012
open-access:
Received Day: 23 Month: 3 Year: 2012
Accepted Day: 05 Month: 4 Year: 2012
collection publication date: Day: 01 Month: 5 Year: 2012
Electronic publication date: Day: 18 Month: 4 Year: 2012
pmc-release publication date: Day: 18 Month: 4 Year: 2012
Volume: 68 Issue: Pt 5
First Page: o1420 Last Page: o1420
ID: 3344543
PubMed Id: 22590305
Publisher Id: zs2195
DOI: 10.1107/S1600536812015012
Coden: ACSEBH
Publisher Item Identifier: S1600536812015012
3-Eth­oxy­carbonyl-2-hy­droxy-6-meth­oxy-4-methyl­benzoic acid Alternate Title:C12H14O6
Yun-Xia Denga
Tao Guob
Hui Xiea
Sheng-Li Pana*
aSchool of Pharmacy, Fudan University, Shanghai 201203, People’s Republic of China
bSchool of Life and Engineering, Lanzhou University of Technology, Lanzhou 730050, People’s Republic of China
Correspondence: Correspondence e-mail: slpan@shmu.edu.cn
Related literature  

For general background to the phenol compounds isolated from the lichen Thamnolia vermicularis var. subuliformis, see: Jiang et al. (2002 ▶); Milenkovic-Andjelkovic (2010 ▶). For applications of analogs of the title compound, see: Huneck (1999 ▶).[Chemical Structure ID: scheme1]

Experimental  
Crystal data  

  • C12H14O6
  • Mr = 254.23
  • Triclinic,
  • a = 6.8460 (14) Å
  • b = 8.0065 (16) Å
  • c = 11.469 (2) Å
  • α = 97.059 (4)°
  • β = 95.987 (4)°
  • γ = 98.072 (4)°
  • V = 612.9 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 293 K
  • 0.39 × 0.30 × 0.11 mm

Data collection  

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) Tmin = 0.245, Tmax = 1.000
  • 3352 measured reflections
  • 2359 independent reflections
  • 1379 reflections with I > 2σ(I)
  • Rint = 0.083

Refinement  

  • R[F2 > 2σ(F2)] = 0.057
  • wR(F2) = 0.174
  • S = 0.91
  • 2359 reflections
  • 186 parameters
  • 22 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015012/zs2195sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015012/zs2195Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812015012/zs2195Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Notes

fnu1Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2195).

supplementary crystallographic information
Comment

The title compound, C12H14O6, a substituted isophthalic acid monoester, is one of the phenol compounds isolated from the lichen Thamnolia vermicularis var.subuliformis (Jiang et al., 2002; Milenkovic-Andjelkovic, 2010). The X-ray structural analysis of this compound reported here confirms the assignment of its structure determined from experimental spectroscopic data. In the molecule (Fig. 1), intramolecular carboxylic acid O—H···Omethoxy and hydroxy O—H···Ocarboxyl hydrogen -bonding interactions (Table 1) result in the formation of two six-membered rings. In the crystal (Fig. 2), no significant hydrogen-bonding interactions are found. The terminal methyl group of the ethyl ester is disordered over two sites with occupancies 0.599:0.401.

Experimental

Extraction of the title compound. The air-dried and powdered plant materials (5 kg) were extracted by 95% EtOH (3 times, 20L) at room temperature and concentrated under vacuum. The residue was partitioned with petroleum ether (PE) and EtOAc,successively. The EtOAc extract (47 g) was chromatographed on a silica gel column eluted successively with PE-EtOAc/ EtOAc–MeOH to afford six major fractions. Fraction 3 eluted with PE-EtOAc (1:3) was further purified by silica gel chromatography [CHCl3-MeOH (15:1)] and then Sephadex LH-20 using MeOH (100%) to yield the title compound (200 mg). The solvent was removed in vacuo to give colorless crystals (m.p. 435–437 K). 1H-NMR (CDCl3, 400 MHz): 12.6 (1H, s, OH), 11.2 (1H, s, COOH), 6.34 (1H, s), 4.4 (2H, q, CH2), 4.08 (3H, s, CH3), 2.37 (3H, s, CH3), 1.39 (3H, t, CH3). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution.

Refinement

Hydroxy and carboxylic acid H-atoms were located in a difference-Fourier analysis and both positional and isotropic displacement parameters were refined. Other H-atoms were positioned geometrically with C—H = 0.93 Å (for aromatic H) or 0.96 or 0.97 Å (for methyl or methylene H-atoms respectively) and constrained to ride on their parent atoms, with Uiso(H) = 1.2 or 1.5 Ueq(C). Disorder in the terminal methyl group (C12) of the ethyl ester resulted in the refinement at two sites with occupancies of 0.599 (19) (C12) and 0.401 (19) (C12').

Figures
Crystal data
Data collection
Refinement
Special details
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Atomic displacement parameters (Å2)
Geometric parameters (Å, º)
Hydrogen-bond geometry (Å, º)
References
Bruker (2003). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
Huneck, S. (1999). Naturwissenschaften, 86, 559–570.
Jiang, B., Zhao, Q., Peng, L., Lin, Z. & Sun, H. (2002). Yunnan Zhiwu Yanjiu, 24, 525–530.
Milenkovic-Andjelkovic, A. (2010). Planta Med.76, 1304–1304.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Figures

[Figure ID: Fap1] 		Fig. 1. 

The molecular structure of the title compound, showing 30% probability displacement ellipsoids. The disorder in the ethyl ester group is not shown. Intramolecular hydrogen bonds are shown as dashed lines.

[Figure ID: Fap2] 		Fig. 2. 

The crystal packing of the title compound viewed down the a axis.
Tables
[TableWrap ID: d1e166]
C12H14O6 Z = 2
Mr = 254.23 F(000) = 268
Triclinic, P1 Dx = 1.378 Mg m−3
Hall symbol: -P 1 Melting point = 435–437 K
a = 6.8460 (14) Å Mo Kα radiation, λ = 0.71073 Å
b = 8.0065 (16) Å Cell parameters from 969 reflections
c = 11.469 (2) Å θ = 5.2–52.9°
α = 97.059 (4)° µ = 0.11 mm−1
β = 95.987 (4)° T = 293 K
γ = 98.072 (4)° Prismatic, colorless
V = 612.9 (2) Å3 0.39 × 0.30 × 0.11 mm

[TableWrap ID: d1e300]
Bruker SMART CCD area-detector diffractometer 2359 independent reflections
Radiation source: fine-focus sealed tube 1379 reflections with I > 2σ(I)
Graphite monochromator Rint = 0.083
φ and ω scans θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003) h = −8→8
Tmin = 0.245, Tmax = 1.000 k = −9→7
3352 measured reflections l = −14→13

[TableWrap ID: d1e417]
Refinement on F2 Secondary atom site location: difference Fourier map
Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057 H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.174 w = 1/[σ2(Fo2) + (0.0955P)2] where P = (Fo2 + 2Fc2)/3
S = 0.91 (Δ/σ)max < 0.001
2359 reflections Δρmax = 0.32 e Å−3
186 parameters Δρmin = −0.21 e Å−3
22 restraints Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods Extinction coefficient: 0.036 (12)

[TableWrap ID: d1e595]
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.

[TableWrap ID: d1e694]
x y z Uiso*/Ueq Occ. (<1)
O1 0.1285 (4) 0.1888 (3) 0.3537 (2) 0.0692 (7)
O2 0.3292 (3) 0.6477 (3) 0.66405 (18) 0.0640 (7)
O3 0.1945 (4) 0.1389 (3) 0.5664 (2) 0.0771 (8)
O4 0.2762 (4) 0.3453 (3) 0.7124 (2) 0.0773 (8)
O5 −0.0464 (4) 0.3799 (4) 0.1320 (2) 0.0992 (10)
O6 0.2714 (5) 0.3547 (4) 0.1310 (2) 0.0992 (10)
C1 0.1806 (4) 0.3544 (3) 0.3938 (3) 0.0501 (8)
C2 0.2325 (4) 0.4167 (3) 0.5141 (2) 0.0472 (7)
C3 0.2804 (4) 0.5934 (4) 0.5465 (2) 0.0485 (7)
C4 0.2788 (4) 0.7035 (3) 0.4632 (3) 0.0518 (8)
H4A 0.3110 0.8204 0.4867 0.062*
C5 0.2289 (4) 0.6395 (4) 0.3439 (3) 0.0526 (8)
C6 0.1793 (4) 0.4666 (4) 0.3092 (2) 0.0519 (8)
C7 0.2327 (4) 0.2914 (4) 0.5983 (3) 0.0575 (8)
C8 0.3758 (6) 0.8247 (4) 0.7062 (3) 0.0777 (11)
H8A 0.4967 0.8708 0.6783 0.117*
H8B 0.3928 0.8415 0.7912 0.117*
H8C 0.2696 0.8814 0.6777 0.117*
C9 0.2292 (6) 0.7624 (4) 0.2541 (3) 0.0742 (10)
H9A 0.3583 0.8302 0.2612 0.111*
H9B 0.1317 0.8355 0.2682 0.111*
H9C 0.1977 0.6999 0.1759 0.111*
C10 0.1172 (6) 0.3942 (4) 0.1827 (3) 0.0668 (9)
C11 0.2310 (10) 0.2902 (7) 0.0054 (4) 0.136 (2)
H11A 0.1002 0.2215 −0.0116 0.164* 0.599 (19)
H11B 0.2327 0.3847 −0.0402 0.164* 0.599 (19)
H11C 0.3379 0.3382 −0.0339 0.164* 0.401 (19)
H11D 0.1099 0.3252 −0.0259 0.164* 0.401 (19)
C12 0.376 (2) 0.1907 (18) −0.0273 (7) 0.128 (5) 0.599 (19)
H12A 0.3768 0.0993 0.0196 0.192* 0.599 (19)
H12B 0.5047 0.2605 −0.0141 0.192* 0.599 (19)
H12C 0.3461 0.1445 −0.1096 0.192* 0.599 (19)
C12' 0.213 (4) 0.107 (2) −0.0170 (14) 0.137 (7) 0.401 (19)
H12D 0.2147 0.0720 −0.0999 0.205* 0.401 (19)
H12E 0.0899 0.0571 0.0065 0.205* 0.401 (19)
H12F 0.3219 0.0709 0.0276 0.205* 0.401 (19)
H1 0.144 (7) 0.131 (5) 0.410 (3) 0.113 (16)*
H4 0.301 (6) 0.457 (3) 0.728 (4) 0.110 (16)*

[TableWrap ID: d1e1222]
U11 U22 U33 U12 U13 U23
O1 0.0993 (18) 0.0384 (13) 0.0710 (16) 0.0188 (11) 0.0075 (13) 0.0049 (10)
O2 0.0797 (15) 0.0543 (14) 0.0555 (14) 0.0149 (10) −0.0031 (10) 0.0023 (9)
O3 0.1013 (19) 0.0482 (15) 0.0865 (18) 0.0195 (12) 0.0037 (13) 0.0254 (12)
O4 0.106 (2) 0.0709 (18) 0.0605 (16) 0.0252 (15) 0.0042 (13) 0.0245 (13)
O5 0.091 (2) 0.126 (3) 0.0735 (18) 0.0161 (17) −0.0105 (15) 0.0056 (15)
O6 0.124 (2) 0.132 (3) 0.0519 (15) 0.069 (2) 0.0086 (14) −0.0027 (13)
C1 0.0554 (17) 0.0362 (16) 0.0614 (19) 0.0177 (13) 0.0087 (13) 0.0047 (12)
C2 0.0432 (16) 0.0471 (17) 0.0572 (18) 0.0180 (12) 0.0096 (13) 0.0148 (13)
C3 0.0434 (16) 0.0484 (17) 0.0553 (18) 0.0148 (12) 0.0039 (12) 0.0065 (13)
C4 0.0540 (18) 0.0389 (16) 0.0638 (19) 0.0112 (12) 0.0069 (14) 0.0073 (13)
C5 0.0536 (18) 0.0469 (17) 0.063 (2) 0.0151 (13) 0.0113 (14) 0.0168 (14)
C6 0.0583 (18) 0.0502 (18) 0.0519 (18) 0.0197 (14) 0.0114 (14) 0.0091 (13)
C7 0.0561 (18) 0.055 (2) 0.069 (2) 0.0188 (14) 0.0095 (15) 0.0221 (15)
C8 0.096 (3) 0.056 (2) 0.072 (2) 0.0133 (18) −0.0136 (19) −0.0104 (16)
C9 0.093 (3) 0.061 (2) 0.072 (2) 0.0127 (18) 0.0080 (18) 0.0270 (17)
C10 0.086 (3) 0.058 (2) 0.060 (2) 0.0230 (18) 0.0068 (19) 0.0108 (15)
C11 0.199 (5) 0.168 (5) 0.055 (3) 0.097 (5) 0.006 (3) −0.006 (3)
C12 0.173 (10) 0.159 (9) 0.068 (5) 0.083 (8) 0.021 (5) 0.005 (5)
C12' 0.163 (13) 0.131 (11) 0.107 (9) 0.037 (9) −0.003 (8) −0.020 (7)

[TableWrap ID: d1e1569]
O1—C1 1.334 (3) C6—C10 1.488 (4)
O1—H1 0.84 (2) C8—H8A 0.9600
O2—C3 1.357 (3) C8—H8B 0.9600
O2—C8 1.420 (4) C8—H8C 0.9600
O3—C7 1.214 (4) C9—H9A 0.9600
O4—C7 1.316 (4) C9—H9B 0.9600
O4—H4 0.88 (2) C9—H9C 0.9600
O5—C10 1.190 (4) C11—C12 1.411 (10)
O6—C10 1.321 (4) C11—C12' 1.441 (15)
O6—C11 1.453 (4) C11—H11A 0.9700
C1—C2 1.399 (4) C11—H11B 0.9700
C1—C6 1.401 (4) C11—H11C 0.9580
C2—C3 1.401 (4) C11—H11D 0.9607
C2—C7 1.475 (4) C12—H12A 0.9600
C3—C4 1.377 (4) C12—H12B 0.9600
C4—C5 1.390 (4) C12—H12C 0.9600
C4—H4A 0.9300 C12'—H12D 0.9600
C5—C6 1.376 (4) C12'—H12E 0.9600
C5—C9 1.509 (4) C12'—H12F 0.9600
C1—O1—H1 110 (3) C5—C9—H9A 109.5
C3—O2—C8 120.1 (2) C5—C9—H9B 109.5
C7—O4—H4 113 (3) H9A—C9—H9B 109.5
C10—O6—C11 115.9 (3) C5—C9—H9C 109.5
O1—C1—C2 122.7 (2) H9A—C9—H9C 109.5
O1—C1—C6 116.8 (3) H9B—C9—H9C 109.5
C2—C1—C6 120.5 (3) O5—C10—O6 123.6 (3)
C1—C2—C3 117.9 (2) O5—C10—C6 125.6 (3)
C1—C2—C7 117.7 (3) O6—C10—C6 110.8 (3)
C3—C2—C7 124.5 (3) C12—C11—O6 109.7 (5)
O2—C3—C4 122.7 (3) C12'—C11—O6 112.2 (7)
O2—C3—C2 115.7 (2) C12—C11—H11A 109.7
C4—C3—C2 121.6 (3) O6—C11—H11A 109.7
C3—C4—C5 119.8 (3) C12—C11—H11B 109.7
C3—C4—H4A 120.1 O6—C11—H11B 109.7
C5—C4—H4A 120.1 H11A—C11—H11B 108.2
C6—C5—C4 120.1 (2) C12'—C11—H11C 108.5
C6—C5—C9 121.0 (3) O6—C11—H11C 108.9
C4—C5—C9 118.9 (3) C12'—C11—H11D 109.6
C5—C6—C1 120.2 (3) O6—C11—H11D 108.5
C5—C6—C10 121.5 (3) H11C—C11—H11D 109.1
C1—C6—C10 118.3 (3) C11—C12—H12A 109.5
O3—C7—O4 118.1 (3) C11—C12—H12B 109.5
O3—C7—C2 122.5 (3) C11—C12—H12C 109.5
O4—C7—C2 119.4 (3) C11—C12'—H12D 109.5
O2—C8—H8A 109.5 C11—C12'—H12E 109.5
O2—C8—H8B 109.5 H12D—C12'—H12E 109.5
H8A—C8—H8B 109.5 C11—C12'—H12F 109.5
O2—C8—H8C 109.5 H12D—C12'—H12F 109.5
H8A—C8—H8C 109.5 H12E—C12'—H12F 109.5
H8B—C8—H8C 109.5
O1—C1—C2—C3 −178.6 (2) C9—C5—C6—C10 −2.2 (5)
C6—C1—C2—C3 0.6 (4) O1—C1—C6—C5 179.2 (3)
O1—C1—C2—C7 1.4 (4) C2—C1—C6—C5 −0.1 (4)
C6—C1—C2—C7 −179.4 (2) O1—C1—C6—C10 1.1 (4)
C8—O2—C3—C4 1.8 (4) C2—C1—C6—C10 −178.2 (3)
C8—O2—C3—C2 −178.6 (3) C1—C2—C7—O3 1.7 (4)
C1—C2—C3—O2 179.8 (2) C3—C2—C7—O3 −178.3 (3)
C7—C2—C3—O2 −0.2 (4) C1—C2—C7—O4 −178.4 (3)
C1—C2—C3—C4 −0.5 (4) C3—C2—C7—O4 1.5 (4)
C7—C2—C3—C4 179.5 (2) C11—O6—C10—O5 −0.3 (6)
O2—C3—C4—C5 179.5 (2) C11—O6—C10—C6 −177.2 (3)
C2—C3—C4—C5 −0.1 (4) C5—C6—C10—O5 −83.8 (4)
C3—C4—C5—C6 0.6 (4) C1—C6—C10—O5 94.2 (4)
C3—C4—C5—C9 −179.7 (3) C5—C6—C10—O6 93.0 (4)
C4—C5—C6—C1 −0.5 (4) C1—C6—C10—O6 −88.9 (4)
C9—C5—C6—C1 179.8 (3) C10—O6—C11—C12 −156.0 (9)
C4—C5—C6—C10 177.5 (3) C10—O6—C11—C12' −100.3 (13)

[TableWrap ID: d1e2240]
D—H···A D—H H···A D···A D—H···A
O4—H4···O2 0.88 (2) 1.77 (3) 2.535 (3) 144 (4)
O1—H1···O3 0.84 (2) 1.78 (3) 2.524 (3) 146 (4)

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