Acta Cryst. (2009). E65, o434 [ doi:10.1107/S1600536809003080 ]
The title compound, C13H18O4, is an intermediate product in the synthesis of quinazoline derivatives. Crystal structure analysis shows that the benzene-butoxy Car-O-C-C torsion angle is 175.3 (2)° and that the benzene-methoxycarbonyl Car-C-O-C torsion angle is 175.2 (2)°. Torsion angles close to 180° indicate that the molecule is almost planar.
For the preparation of the title compound, methyl 3-methoxy-4-hydroxybenzoate (55 mmol), 1-bromobutane (110 mmol) and potassium carbonate (165 mmol) were mixed with DMF (60 ml), and then the mixture was heated to reflux for 2 h. Reaction progress was monitored by TLC. After cooling and filtration, the title compound was obtained (yield 92%, m.p. 317 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution.
H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: PLATON (Spek, 2003).
| C13H18O4 | Z = 2 |
| Mr = 238.27 | F(000) = 256 |
| Triclinic, P1 | Dx = 1.252 Mg m−3 |
| Hall symbol: -P 1 | Melting point: 317 K |
| a = 7.9660 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 9.1630 (18) Å | Cell parameters from 25 reflections |
| c = 10.143 (2) Å | θ = 9–12° |
| α = 64.80 (2)° | µ = 0.09 mm−1 |
| β = 70.96 (3)° | T = 293 K |
| γ = 79.26 (3)° | Block, colourless |
| V = 632.3 (2) Å3 | 0.30 × 0.20 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | 1567 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.067 |
| graphite | θmax = 25.3°, θmin = 2.3° |
| ω/2θ scans | h = 0→9 |
| Absorption correction: ψ scan (North et al., 1968) | k = −10→11 |
| Tmin = 0.973, Tmax = 0.991 | l = −11→12 |
| 2474 measured reflections | 3 standard reflections every 200 reflections |
| 2294 independent reflections | intensity decay: 1% |
| 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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.168 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.07P)2 + 0.43P] where P = (Fo2 + 2Fc2)/3 |
| 2294 reflections | (Δ/σ)max < 0.001 |
| 154 parameters | Δρmax = 0.18 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
| C13H18O4 | γ = 79.26 (3)° |
| Mr = 238.27 | V = 632.3 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.9660 (16) Å | Mo Kα radiation |
| b = 9.1630 (18) Å | µ = 0.09 mm−1 |
| c = 10.143 (2) Å | T = 293 K |
| α = 64.80 (2)° | 0.30 × 0.20 × 0.10 mm |
| β = 70.96 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 1567 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.067 |
| Tmin = 0.973, Tmax = 0.991 | θmax = 25.3° |
| 2474 measured reflections | 3 standard reflections every 200 reflections |
| 2294 independent reflections | intensity decay: 1% |
| R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
| wR(F2) = 0.168 | Δρmax = 0.18 e Å−3 |
| S = 1.00 | Δρmin = −0.21 e Å−3 |
| 2294 reflections | Absolute structure: ? |
| 154 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
| O1 | 0.3147 (2) | 0.6241 (2) | 0.05115 (19) | 0.0488 (5) | |
| O2 | 0.0656 (2) | 0.4271 (2) | 0.15700 (19) | 0.0516 (5) | |
| O3 | 0.0117 (3) | 0.1304 (3) | 0.7289 (2) | 0.0733 (7) | |
| O4 | 0.1887 (2) | 0.2708 (2) | 0.75552 (19) | 0.0570 (5) | |
| C1 | 0.6296 (5) | 1.0667 (4) | −0.4050 (3) | 0.0749 (10) | |
| H1A | 0.7158 | 1.1438 | −0.4358 | 0.112* | |
| H1B | 0.5201 | 1.1226 | −0.4245 | 0.112* | |
| H1C | 0.6732 | 0.9990 | −0.4612 | 0.112* | |
| C2 | 0.5977 (4) | 0.9645 (4) | −0.2387 (3) | 0.0606 (8) | |
| H2A | 0.5569 | 1.0348 | −0.1838 | 0.073* | |
| H2B | 0.7101 | 0.9117 | −0.2204 | 0.073* | |
| C3 | 0.4645 (3) | 0.8369 (3) | −0.1746 (3) | 0.0473 (6) | |
| H3A | 0.3493 | 0.8884 | −0.1865 | 0.057* | |
| H3B | 0.5016 | 0.7675 | −0.2305 | 0.057* | |
| C4 | 0.4487 (4) | 0.7377 (3) | −0.0111 (3) | 0.0493 (7) | |
| H4A | 0.5619 | 0.6806 | 0.0002 | 0.059* | |
| H4B | 0.4189 | 0.8078 | 0.0438 | 0.059* | |
| C5 | 0.2767 (3) | 0.5331 (3) | 0.2032 (3) | 0.0410 (6) | |
| C6 | 0.3595 (3) | 0.5399 (3) | 0.3000 (3) | 0.0495 (7) | |
| H6A | 0.4504 | 0.6098 | 0.2622 | 0.059* | |
| C7 | 0.3085 (3) | 0.4438 (3) | 0.4524 (3) | 0.0477 (6) | |
| H7A | 0.3639 | 0.4505 | 0.5172 | 0.057* | |
| C8 | 0.1752 (3) | 0.3373 (3) | 0.5099 (3) | 0.0443 (6) | |
| C9 | 0.0934 (3) | 0.3285 (3) | 0.4133 (3) | 0.0438 (6) | |
| H9A | 0.0051 | 0.2559 | 0.4516 | 0.053* | |
| C10 | 0.1400 (3) | 0.4256 (3) | 0.2606 (3) | 0.0401 (6) | |
| C11 | −0.0929 (4) | 0.3439 (4) | 0.2120 (3) | 0.0564 (8) | |
| H11A | −0.1314 | 0.3542 | 0.1278 | 0.085* | |
| H11B | −0.1841 | 0.3895 | 0.2749 | 0.085* | |
| H11C | −0.0703 | 0.2317 | 0.2702 | 0.085* | |
| C12 | 0.1161 (3) | 0.2332 (3) | 0.6753 (3) | 0.0468 (6) | |
| C13 | 0.1295 (4) | 0.1866 (4) | 0.9164 (3) | 0.0661 (8) | |
| H13A | 0.1890 | 0.2239 | 0.9638 | 0.099* | |
| H13B | 0.1562 | 0.0729 | 0.9425 | 0.099* | |
| H13C | 0.0034 | 0.2066 | 0.9511 | 0.099* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0478 (10) | 0.0490 (11) | 0.0479 (10) | −0.0110 (8) | −0.0085 (8) | −0.0176 (8) |
| O2 | 0.0480 (10) | 0.0598 (12) | 0.0497 (10) | −0.0140 (9) | −0.0114 (8) | −0.0211 (9) |
| O3 | 0.0858 (16) | 0.0749 (15) | 0.0559 (12) | −0.0289 (13) | −0.0188 (11) | −0.0135 (11) |
| O4 | 0.0592 (12) | 0.0667 (13) | 0.0460 (10) | −0.0054 (10) | −0.0141 (9) | −0.0226 (9) |
| C1 | 0.076 (2) | 0.065 (2) | 0.066 (2) | −0.0173 (18) | −0.0084 (16) | −0.0119 (16) |
| C2 | 0.0603 (18) | 0.0566 (18) | 0.0607 (17) | −0.0145 (15) | −0.0097 (14) | −0.0198 (14) |
| C3 | 0.0466 (15) | 0.0402 (15) | 0.0547 (15) | 0.0003 (12) | −0.0074 (11) | −0.0241 (12) |
| C4 | 0.0486 (15) | 0.0425 (15) | 0.0589 (16) | −0.0092 (12) | −0.0099 (12) | −0.0228 (12) |
| C5 | 0.0390 (13) | 0.0368 (13) | 0.0485 (13) | 0.0017 (11) | −0.0093 (10) | −0.0215 (11) |
| C6 | 0.0443 (15) | 0.0510 (16) | 0.0575 (16) | −0.0088 (12) | −0.0119 (12) | −0.0245 (13) |
| C7 | 0.0444 (15) | 0.0497 (16) | 0.0563 (15) | 0.0033 (12) | −0.0201 (12) | −0.0254 (12) |
| C8 | 0.0394 (13) | 0.0425 (14) | 0.0528 (15) | 0.0072 (11) | −0.0137 (11) | −0.0236 (12) |
| C9 | 0.0403 (14) | 0.0397 (14) | 0.0536 (15) | 0.0013 (11) | −0.0115 (11) | −0.0228 (11) |
| C10 | 0.0361 (13) | 0.0417 (14) | 0.0498 (14) | 0.0055 (11) | −0.0125 (10) | −0.0274 (11) |
| C11 | 0.0539 (17) | 0.0673 (19) | 0.0517 (15) | −0.0164 (15) | −0.0143 (12) | −0.0217 (14) |
| C12 | 0.0418 (14) | 0.0487 (16) | 0.0534 (15) | 0.0075 (12) | −0.0184 (12) | −0.0235 (12) |
| C13 | 0.0680 (19) | 0.079 (2) | 0.0490 (16) | −0.0016 (17) | −0.0149 (14) | −0.0253 (15) |
| O1—C5 | 1.364 (3) | C4—H4B | 0.9700 |
| O1—C4 | 1.427 (3) | C5—C6 | 1.375 (3) |
| O2—C10 | 1.359 (3) | C5—C10 | 1.411 (3) |
| O2—C11 | 1.423 (3) | C6—C7 | 1.376 (4) |
| O3—C12 | 1.198 (3) | C6—H6A | 0.9300 |
| O4—C12 | 1.317 (3) | C7—C8 | 1.385 (3) |
| O4—C13 | 1.429 (3) | C7—H7A | 0.9300 |
| C1—C2 | 1.501 (4) | C8—C9 | 1.376 (3) |
| C1—H1A | 0.9600 | C8—C12 | 1.495 (4) |
| C1—H1B | 0.9600 | C9—C10 | 1.379 (3) |
| C1—H1C | 0.9600 | C9—H9A | 0.9300 |
| C2—C3 | 1.510 (4) | C11—H11A | 0.9600 |
| C2—H2A | 0.9700 | C11—H11B | 0.9600 |
| C2—H2B | 0.9700 | C11—H11C | 0.9600 |
| C3—C4 | 1.488 (4) | C13—H13A | 0.9600 |
| C3—H3A | 0.9700 | C13—H13B | 0.9600 |
| C3—H3B | 0.9700 | C13—H13C | 0.9600 |
| C4—H4A | 0.9700 | ||
| C5—O1—C4 | 116.99 (19) | C5—C6—C7 | 120.4 (2) |
| C10—O2—C11 | 117.84 (19) | C5—C6—H6A | 119.8 |
| C12—O4—C13 | 116.2 (2) | C7—C6—H6A | 119.8 |
| C2—C1—H1A | 109.5 | C6—C7—C8 | 120.5 (2) |
| C2—C1—H1B | 109.5 | C6—C7—H7A | 119.8 |
| H1A—C1—H1B | 109.5 | C8—C7—H7A | 119.8 |
| C2—C1—H1C | 109.5 | C9—C8—C7 | 119.4 (2) |
| H1A—C1—H1C | 109.5 | C9—C8—C12 | 119.2 (2) |
| H1B—C1—H1C | 109.5 | C7—C8—C12 | 121.4 (2) |
| C1—C2—C3 | 115.2 (3) | C8—C9—C10 | 121.2 (2) |
| C1—C2—H2A | 108.5 | C8—C9—H9A | 119.4 |
| C3—C2—H2A | 108.5 | C10—C9—H9A | 119.4 |
| C1—C2—H2B | 108.5 | O2—C10—C9 | 125.5 (2) |
| C3—C2—H2B | 108.5 | O2—C10—C5 | 115.7 (2) |
| H2A—C2—H2B | 107.5 | C9—C10—C5 | 118.9 (2) |
| C4—C3—C2 | 111.0 (2) | O2—C11—H11A | 109.5 |
| C4—C3—H3A | 109.4 | O2—C11—H11B | 109.5 |
| C2—C3—H3A | 109.4 | H11A—C11—H11B | 109.5 |
| C4—C3—H3B | 109.4 | O2—C11—H11C | 109.5 |
| C2—C3—H3B | 109.4 | H11A—C11—H11C | 109.5 |
| H3A—C3—H3B | 108.0 | H11B—C11—H11C | 109.5 |
| O1—C4—C3 | 110.7 (2) | O3—C12—O4 | 124.0 (2) |
| O1—C4—H4A | 109.5 | O3—C12—C8 | 123.9 (2) |
| C3—C4—H4A | 109.5 | O4—C12—C8 | 112.0 (2) |
| O1—C4—H4B | 109.5 | O4—C13—H13A | 109.5 |
| C3—C4—H4B | 109.5 | O4—C13—H13B | 109.5 |
| H4A—C4—H4B | 108.1 | H13A—C13—H13B | 109.5 |
| O1—C5—C6 | 125.3 (2) | O4—C13—H13C | 109.5 |
| O1—C5—C10 | 115.1 (2) | H13A—C13—H13C | 109.5 |
| C6—C5—C10 | 119.7 (2) | H13B—C13—H13C | 109.5 |
| C1—C2—C3—C4 | 177.4 (3) | C11—O2—C10—C5 | −168.8 (2) |
| C5—O1—C4—C3 | −175.3 (2) | C8—C9—C10—O2 | −179.1 (2) |
| C2—C3—C4—O1 | 176.4 (2) | C8—C9—C10—C5 | 1.3 (4) |
| C4—O1—C5—C6 | −1.4 (4) | O1—C5—C10—O2 | 0.2 (3) |
| C4—O1—C5—C10 | 178.3 (2) | C6—C5—C10—O2 | 179.9 (2) |
| O1—C5—C6—C7 | 179.0 (2) | O1—C5—C10—C9 | 179.8 (2) |
| C10—C5—C6—C7 | −0.7 (4) | C6—C5—C10—C9 | −0.4 (4) |
| C5—C6—C7—C8 | 1.0 (4) | C13—O4—C12—O3 | −3.1 (4) |
| C6—C7—C8—C9 | −0.2 (4) | C13—O4—C12—C8 | 175.2 (2) |
| C6—C7—C8—C12 | −179.3 (2) | C9—C8—C12—O3 | 7.1 (4) |
| C7—C8—C9—C10 | −0.9 (4) | C7—C8—C12—O3 | −173.9 (3) |
| C12—C8—C9—C10 | 178.1 (2) | C9—C8—C12—O4 | −171.2 (2) |
| C11—O2—C10—C9 | 11.6 (4) | C7—C8—C12—O4 | 7.8 (4) |
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. [Please check amended reference]
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. [Reference not cited - may it be removed?]
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
Knesl, P., Roeseling, D. & Jordis, U. (2006). Molecules, 11, 286–297.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
![[Figure 1]](./wk2098fig1thm.gif)
As part of our ongoing studies on quinazoline derivatives (Knesl et al., 2006), we report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C4–C9) is, of course, planar.