Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054384/hk2329sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054384/hk2329Isup2.hkl |
CCDC reference: 674078
Dimethyl sulfate (5.6 g, 45 mmol) and anhydrous potassium carbonate (6.1 g, 50 mmol) were added to a stirred solution of gallic acid (1.7 g, 10 mmol) in acetone (60 ml), and the mixture was refluxed under nitrogen for 6 h. The acetone was rotary evaporated, the residue was mixed with ice-water, and then extracted with ethyl acetate (3 x 50 ml). The extract was washed with NaHCO3 (5%), dried (MgSO4) and evaporated. The residue was recrystallized from aqueous methanol as needles (yield; 2.29 g, 92%, m.p. 355–356 K). The spectroscopic data was in agreement to that reported in literature (Aboul-Enein & Eid, 1979).
H atoms were positioned geometrically, with C—H = 0.95 and 0.98 Å for aromatic and methyl H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.2 for aromatic H and x = 1.5 for methyl H atoms.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C11H14O5 | F(000) = 480 |
Mr = 226.22 | Dx = 1.343 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7934 reflections |
a = 17.6930 (15) Å | θ = 3.5–25.6° |
b = 4.5050 (5) Å | µ = 0.11 mm−1 |
c = 14.6383 (12) Å | T = 173 K |
β = 106.545 (7)° | Block, colorless |
V = 1118.47 (18) Å3 | 0.42 × 0.37 × 0.21 mm |
Z = 4 |
STOE IPDS-II diffractometer | 1796 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.068 |
Graphite monochromator | θmax = 25.6°, θmin = 3.6° |
ω scans | h = −21→21 |
8229 measured reflections | k = −4→5 |
2094 independent reflections | l = −15→17 |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0714P)2 + 0.0891P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2094 reflections | Δρmax = 0.29 e Å−3 |
150 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.035 (5) |
C11H14O5 | V = 1118.47 (18) Å3 |
Mr = 226.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.6930 (15) Å | µ = 0.11 mm−1 |
b = 4.5050 (5) Å | T = 173 K |
c = 14.6383 (12) Å | 0.42 × 0.37 × 0.21 mm |
β = 106.545 (7)° |
STOE IPDS-II diffractometer | 1796 reflections with I > 2σ(I) |
8229 measured reflections | Rint = 0.068 |
2094 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.29 e Å−3 |
2094 reflections | Δρmin = −0.20 e Å−3 |
150 parameters |
Experimental. ; |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.69462 (7) | 0.3640 (3) | 0.37200 (9) | 0.0242 (3) | |
C2 | 0.69852 (7) | 0.5101 (3) | 0.28963 (9) | 0.0257 (3) | |
H2 | 0.6538 | 0.6118 | 0.2510 | 0.031* | |
C3 | 0.76894 (7) | 0.5054 (3) | 0.26446 (9) | 0.0253 (3) | |
C4 | 0.83503 (7) | 0.3570 (3) | 0.32254 (9) | 0.0231 (3) | |
C5 | 0.83048 (7) | 0.2175 (3) | 0.40627 (9) | 0.0233 (3) | |
C6 | 0.75980 (7) | 0.2157 (3) | 0.43092 (9) | 0.0246 (3) | |
H6 | 0.7561 | 0.1157 | 0.4866 | 0.030* | |
C11 | 0.62009 (7) | 0.3662 (3) | 0.40168 (9) | 0.0277 (3) | |
O11 | 0.61194 (5) | 0.2474 (3) | 0.47227 (7) | 0.0393 (3) | |
O12 | 0.56223 (5) | 0.5192 (3) | 0.34019 (7) | 0.0395 (3) | |
C12 | 0.48913 (8) | 0.5425 (5) | 0.36571 (12) | 0.0513 (5) | |
H12A | 0.4968 | 0.6739 | 0.4209 | 0.077* | |
H12B | 0.4732 | 0.3452 | 0.3816 | 0.077* | |
H12C | 0.4480 | 0.6241 | 0.3118 | 0.077* | |
O31 | 0.77982 (5) | 0.6370 (2) | 0.18506 (7) | 0.0333 (3) | |
C31 | 0.71604 (8) | 0.8117 (3) | 0.12770 (10) | 0.0335 (3) | |
H31A | 0.7012 | 0.9633 | 0.1674 | 0.050* | |
H31B | 0.6707 | 0.6830 | 0.0999 | 0.050* | |
H31C | 0.7326 | 0.9081 | 0.0766 | 0.050* | |
O41 | 0.90383 (5) | 0.34196 (19) | 0.29594 (7) | 0.0259 (3) | |
C41 | 0.95168 (8) | 0.6036 (3) | 0.32068 (12) | 0.0336 (3) | |
H41A | 0.9677 | 0.6291 | 0.3900 | 0.050* | |
H41B | 0.9213 | 0.7772 | 0.2905 | 0.050* | |
H41C | 0.9987 | 0.5830 | 0.2984 | 0.050* | |
O51 | 0.89959 (5) | 0.0934 (2) | 0.46006 (7) | 0.0287 (3) | |
C51 | 0.89795 (7) | −0.0633 (3) | 0.54457 (10) | 0.0322 (3) | |
H51A | 0.8620 | −0.2330 | 0.5273 | 0.048* | |
H51B | 0.8796 | 0.0701 | 0.5867 | 0.048* | |
H51C | 0.9511 | −0.1342 | 0.5775 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0216 (6) | 0.0282 (7) | 0.0245 (7) | −0.0041 (5) | 0.0092 (5) | −0.0066 (5) |
C2 | 0.0232 (6) | 0.0300 (7) | 0.0244 (7) | 0.0002 (5) | 0.0075 (5) | −0.0024 (5) |
C3 | 0.0288 (6) | 0.0256 (7) | 0.0246 (7) | −0.0014 (5) | 0.0125 (5) | −0.0023 (5) |
C4 | 0.0244 (6) | 0.0211 (6) | 0.0278 (7) | −0.0008 (4) | 0.0137 (5) | −0.0047 (5) |
C5 | 0.0245 (6) | 0.0211 (6) | 0.0257 (7) | −0.0008 (5) | 0.0096 (5) | −0.0044 (5) |
C6 | 0.0271 (6) | 0.0260 (7) | 0.0231 (6) | −0.0035 (5) | 0.0109 (5) | −0.0027 (5) |
C11 | 0.0229 (6) | 0.0367 (8) | 0.0241 (7) | −0.0028 (5) | 0.0076 (5) | −0.0039 (5) |
O11 | 0.0280 (5) | 0.0589 (7) | 0.0355 (6) | 0.0020 (4) | 0.0162 (4) | 0.0110 (5) |
O12 | 0.0223 (5) | 0.0683 (8) | 0.0305 (5) | 0.0077 (4) | 0.0119 (4) | 0.0096 (5) |
C12 | 0.0246 (6) | 0.0905 (14) | 0.0431 (9) | 0.0153 (7) | 0.0166 (6) | 0.0177 (9) |
O31 | 0.0325 (5) | 0.0423 (6) | 0.0304 (5) | 0.0080 (4) | 0.0173 (4) | 0.0112 (4) |
C31 | 0.0355 (7) | 0.0372 (8) | 0.0299 (7) | 0.0059 (6) | 0.0127 (6) | 0.0062 (6) |
O41 | 0.0261 (4) | 0.0219 (5) | 0.0362 (5) | 0.0001 (3) | 0.0191 (4) | −0.0029 (4) |
C41 | 0.0311 (6) | 0.0245 (7) | 0.0531 (9) | −0.0036 (5) | 0.0245 (6) | −0.0031 (6) |
O51 | 0.0239 (4) | 0.0346 (5) | 0.0301 (5) | 0.0054 (4) | 0.0118 (4) | 0.0057 (4) |
C51 | 0.0300 (6) | 0.0367 (8) | 0.0311 (7) | 0.0013 (5) | 0.0105 (5) | 0.0070 (6) |
C1—C2 | 1.3925 (19) | C12—H12A | 0.9800 |
C1—C6 | 1.3978 (18) | C12—H12B | 0.9800 |
C1—C11 | 1.5013 (15) | C12—H12C | 0.9800 |
C2—C3 | 1.3964 (17) | O31—C31 | 1.4345 (16) |
C2—H2 | 0.9500 | C31—H31A | 0.9800 |
C3—O31 | 1.3663 (16) | C31—H31B | 0.9800 |
C3—C4 | 1.4039 (18) | C31—H31C | 0.9800 |
C4—O41 | 1.3813 (13) | O41—C41 | 1.4362 (16) |
C4—C5 | 1.4001 (19) | C41—H41A | 0.9800 |
C5—O51 | 1.3710 (15) | C41—H41B | 0.9800 |
C5—C6 | 1.3967 (15) | C41—H41C | 0.9800 |
C6—H6 | 0.9500 | O51—C51 | 1.4317 (16) |
C11—O11 | 1.2082 (17) | C51—H51A | 0.9800 |
C11—O12 | 1.3448 (16) | C51—H51B | 0.9800 |
O12—C12 | 1.4485 (15) | C51—H51C | 0.9800 |
C2—C1—C6 | 121.64 (11) | O12—C12—H12C | 109.5 |
C2—C1—C11 | 120.77 (11) | H12A—C12—H12C | 109.5 |
C6—C1—C11 | 117.58 (11) | H12B—C12—H12C | 109.5 |
C1—C2—C3 | 119.30 (12) | C3—O31—C31 | 117.27 (9) |
C1—C2—H2 | 120.3 | O31—C31—H31A | 109.5 |
C3—C2—H2 | 120.3 | O31—C31—H31B | 109.5 |
O31—C3—C2 | 124.78 (11) | H31A—C31—H31B | 109.5 |
O31—C3—C4 | 115.28 (10) | O31—C31—H31C | 109.5 |
C2—C3—C4 | 119.94 (12) | H31A—C31—H31C | 109.5 |
O41—C4—C5 | 119.98 (11) | H31B—C31—H31C | 109.5 |
O41—C4—C3 | 120.10 (11) | C4—O41—C41 | 113.09 (9) |
C5—C4—C3 | 119.89 (11) | O41—C41—H41A | 109.5 |
O51—C5—C6 | 124.54 (11) | O41—C41—H41B | 109.5 |
O51—C5—C4 | 114.94 (10) | H41A—C41—H41B | 109.5 |
C6—C5—C4 | 120.51 (11) | O41—C41—H41C | 109.5 |
C5—C6—C1 | 118.68 (12) | H41A—C41—H41C | 109.5 |
C5—C6—H6 | 120.7 | H41B—C41—H41C | 109.5 |
C1—C6—H6 | 120.7 | C5—O51—C51 | 117.59 (9) |
O11—C11—O12 | 123.08 (11) | O51—C51—H51A | 109.5 |
O11—C11—C1 | 124.97 (12) | O51—C51—H51B | 109.5 |
O12—C11—C1 | 111.95 (11) | H51A—C51—H51B | 109.5 |
C11—O12—C12 | 115.46 (11) | O51—C51—H51C | 109.5 |
O12—C12—H12A | 109.5 | H51A—C51—H51C | 109.5 |
O12—C12—H12B | 109.5 | H51B—C51—H51C | 109.5 |
H12A—C12—H12B | 109.5 | ||
C6—C1—C2—C3 | 0.84 (19) | C2—C1—C6—C5 | 0.49 (19) |
C11—C1—C2—C3 | 179.53 (11) | C11—C1—C6—C5 | −178.24 (11) |
C1—C2—C3—O31 | 179.20 (12) | C2—C1—C11—O11 | −179.39 (13) |
C1—C2—C3—C4 | −0.63 (19) | C6—C1—C11—O11 | −0.6 (2) |
O31—C3—C4—O41 | −2.40 (17) | C2—C1—C11—O12 | 0.29 (17) |
C2—C3—C4—O41 | 177.45 (11) | C6—C1—C11—O12 | 179.03 (12) |
O31—C3—C4—C5 | 179.26 (11) | O11—C11—O12—C12 | 2.1 (2) |
C2—C3—C4—C5 | −0.89 (19) | C1—C11—O12—C12 | −177.58 (13) |
O41—C4—C5—O51 | 5.05 (17) | C2—C3—O31—C31 | 5.12 (19) |
C3—C4—C5—O51 | −176.61 (11) | C4—C3—O31—C31 | −175.04 (11) |
O41—C4—C5—C6 | −176.09 (10) | C5—C4—O41—C41 | −99.28 (14) |
C3—C4—C5—C6 | 2.25 (18) | C3—C4—O41—C41 | 82.39 (14) |
O51—C5—C6—C1 | 176.71 (11) | C6—C5—O51—C51 | 3.72 (18) |
C4—C5—C6—C1 | −2.03 (18) | C4—C5—O51—C51 | −177.48 (11) |
Experimental details
Crystal data | |
Chemical formula | C11H14O5 |
Mr | 226.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 17.6930 (15), 4.5050 (5), 14.6383 (12) |
β (°) | 106.545 (7) |
V (Å3) | 1118.47 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.42 × 0.37 × 0.21 |
Data collection | |
Diffractometer | STOE IPDS-II diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8229, 2094, 1796 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.114, 1.06 |
No. of reflections | 2094 |
No. of parameters | 150 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.20 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
The title ester is a constituent of the volatile oils of the genus eucalyptus (Hellyer et al., 1966) and an important intermediate in the synthesis of a variety of natural products. These include lomandrone, the principal pigment of Lomandra hastilis (Cooke & Rainbow 1974), the aglycon of Actinoflavoside (Suzuki et al., 2004), the cactus alkaloid, mescaline well known on account of its interesting effects on the psychic states of human subjects (Aboul-Enein & Eid 1979) and Cercidinin A, an ellagitannin isolated from the bark of Cercidiphyllum japonicum (Tanaka et al., 2001). In addition a number of isocoumarins like kigelin (Saeed & Ehesan, 2005a), reticulol (Saeed & Ehesan, 2005b) and cAMP phosphodiesterase inhibitor 8-hydroxy-6,7-dimethoxy -3-hydroxymethylisocoumarin (Saeed, 2007). We report herein the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The methyl acetate and the two O—Me residues in meta position to the ester residue are almost coplanar, while the O—Me residue in para-position is almost perpendicular with respect to the aromatic ring.