Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041530/hb2518sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041530/hb2518Isup2.hkl |
CCDC reference: 667275
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.039
- wR factor = 0.109
- Data-to-parameter ratio = 13.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 600 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared according to the method of Kazuaki & Katsuo (1979). 2,4-Dihydroxyacetophenone (10 g, 0.066 mo1) and anhydrous potassium carbonate (11 g, 0.080 mo1) was dissolved in 120 ml acetone and the mixture was stirred for 0.5 h at room temperature. Then 1-bromo-3-methyl-2-butene (13 g, 0.088 mo1) was added dropwise and the mixture was stirred for 3 h at 298–303 K. The solvent was removed in vacuuo and the residue was cooled to obtain solid 2-hydroxy-4-(3-methylbut-2-enyloxy)acetophenone.
2-hydroxy-4-(3-methylbut-2-enyloxy)acetophenone (10 g, 0.045 mo1) and potassium hydroxide (3.05 g, 0.055 mo1) were dissolved in 67 ml dried acetone. The mixture was stirred for 20 min. Then, ethyl bromoacetate (8 g, 0.048 mo1) was added dropwise. The mixture was stirred for 3 h. The solid was removed by filtration, and the solvent was evaporated in vacuo. The residue was cooled to obtain the title compound and colourless blocks of (I) (m.p. 336 K) were obtained by recrystallization from actone.
All the H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Sofalcone is an antiulcer agent which is effective for the treatment of gastric ulcer(Kazuaki & Katsuo, 1979). The structure of the title compound, (I), an intermediate in the synthesis of sofalcone, is reported here.
As shown in Fig. 1, atoms C13—C17 are almost coplanar, with an r.m.s. deviation from the mean plane of 0.017 (1) Å. This plane and the C1—C6 benzene ring plane form a dihedral angle of 61.86 (7) °. Another plane defined by atoms C9/C10/O2/O3 is almost coplanar with the C1—C6 plane with a dihedral angle of 5.22 (9)°. The packing is consolidated by a C—H···O interaction (Table 1) leading to centrosymmetric dimers (Fig. 2).
For related literature, see: Kazuaki & Katsuo (1979).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C17H22O5 | Z = 2 |
Mr = 306.35 | F(000) = 328 |
Triclinic, P1 | Dx = 1.284 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.271 (3) Å | Cell parameters from 2006 reflections |
b = 9.663 (3) Å | θ = 3.2–26.2° |
c = 10.514 (4) Å | µ = 0.09 mm−1 |
α = 108.837 (6)° | T = 294 K |
β = 90.689 (6)° | Block, colourless |
γ = 94.101 (6)° | 0.34 × 0.30 × 0.26 mm |
V = 792.7 (5) Å3 |
Bruker SMART 1000 CCD diffractometer | 2779 independent reflections |
Radiation source: fine-focus sealed tube | 2119 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.954, Tmax = 0.976 | k = −11→10 |
4147 measured reflections | l = −12→12 |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.1875P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2779 reflections | Δρmax = 0.17 e Å−3 |
204 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.034 (5) |
C17H22O5 | γ = 94.101 (6)° |
Mr = 306.35 | V = 792.7 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.271 (3) Å | Mo Kα radiation |
b = 9.663 (3) Å | µ = 0.09 mm−1 |
c = 10.514 (4) Å | T = 294 K |
α = 108.837 (6)° | 0.34 × 0.30 × 0.26 mm |
β = 90.689 (6)° |
Bruker SMART 1000 CCD diffractometer | 2779 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2119 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.976 | Rint = 0.026 |
4147 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
2779 reflections | Δρmin = −0.16 e Å−3 |
204 parameters |
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 | ||
O1 | 0.34331 (13) | 0.16237 (13) | 0.45657 (12) | 0.0523 (3) | |
O2 | 0.01594 (14) | −0.08029 (15) | 0.29291 (13) | 0.0662 (4) | |
O3 | 0.28162 (13) | −0.08099 (13) | 0.27446 (12) | 0.0517 (3) | |
O4 | 0.82619 (14) | 0.29474 (17) | 0.52084 (15) | 0.0751 (4) | |
O5 | 0.23306 (13) | 0.61679 (13) | 0.78407 (12) | 0.0554 (4) | |
C1 | 0.39009 (18) | 0.29473 (17) | 0.54707 (15) | 0.0401 (4) | |
C2 | 0.27944 (18) | 0.38430 (17) | 0.62136 (15) | 0.0427 (4) | |
H2 | 0.1696 | 0.3534 | 0.6117 | 0.051* | |
C3 | 0.33193 (19) | 0.51963 (18) | 0.70987 (15) | 0.0436 (4) | |
C4 | 0.4951 (2) | 0.56354 (19) | 0.72555 (17) | 0.0490 (4) | |
H4 | 0.5314 | 0.6547 | 0.7858 | 0.059* | |
C5 | 0.60211 (19) | 0.47321 (19) | 0.65274 (17) | 0.0475 (4) | |
H5 | 0.7119 | 0.5044 | 0.6646 | 0.057* | |
C6 | 0.55584 (18) | 0.33658 (18) | 0.56134 (15) | 0.0413 (4) | |
C7 | 0.6866 (2) | 0.2509 (2) | 0.48763 (17) | 0.0487 (4) | |
C8 | 0.6515 (2) | 0.1141 (2) | 0.3735 (2) | 0.0629 (5) | |
H8A | 0.7514 | 0.0783 | 0.3356 | 0.094* | |
H8B | 0.5856 | 0.1333 | 0.3063 | 0.094* | |
H8C | 0.5946 | 0.0417 | 0.4047 | 0.094* | |
C9 | 0.17736 (18) | 0.11706 (19) | 0.43778 (17) | 0.0489 (4) | |
H9A | 0.1194 | 0.1908 | 0.4161 | 0.059* | |
H9B | 0.1357 | 0.1068 | 0.5204 | 0.059* | |
C10 | 0.14942 (19) | −0.02523 (19) | 0.32741 (16) | 0.0463 (4) | |
C11 | 0.2603 (2) | −0.21987 (19) | 0.16799 (18) | 0.0552 (5) | |
H11A | 0.1845 | −0.2142 | 0.0991 | 0.066* | |
H11B | 0.2181 | −0.2961 | 0.2030 | 0.066* | |
C12 | 0.4202 (3) | −0.2529 (2) | 0.1116 (2) | 0.0712 (6) | |
H12A | 0.4613 | −0.1761 | 0.0784 | 0.107* | |
H12B | 0.4103 | −0.3445 | 0.0392 | 0.107* | |
H12C | 0.4936 | −0.2598 | 0.1804 | 0.107* | |
C13 | 0.06248 (19) | 0.58754 (19) | 0.75686 (18) | 0.0510 (4) | |
H13A | 0.0214 | 0.5093 | 0.7897 | 0.061* | |
H13B | 0.0388 | 0.5575 | 0.6608 | 0.061* | |
C14 | −0.0144 (2) | 0.72352 (19) | 0.82578 (17) | 0.0478 (4) | |
H14 | 0.0133 | 0.8030 | 0.7966 | 0.057* | |
C15 | −0.11704 (19) | 0.74632 (17) | 0.92300 (16) | 0.0437 (4) | |
C16 | −0.1704 (2) | 0.6375 (2) | 0.98913 (19) | 0.0587 (5) | |
H16A | −0.1138 | 0.5507 | 0.9531 | 0.088* | |
H16B | −0.2850 | 0.6129 | 0.9730 | 0.088* | |
H16C | −0.1470 | 0.6784 | 1.0842 | 0.088* | |
C17 | −0.1906 (2) | 0.8888 (2) | 0.9761 (2) | 0.0615 (5) | |
H17A | −0.1407 | 0.9572 | 0.9367 | 0.092* | |
H17B | −0.1737 | 0.9265 | 1.0721 | 0.092* | |
H17C | −0.3048 | 0.8746 | 0.9539 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0314 (6) | 0.0518 (7) | 0.0579 (7) | 0.0009 (5) | 0.0063 (5) | −0.0039 (6) |
O2 | 0.0364 (7) | 0.0719 (9) | 0.0689 (9) | −0.0024 (6) | −0.0001 (6) | −0.0051 (7) |
O3 | 0.0376 (6) | 0.0504 (7) | 0.0534 (7) | 0.0022 (5) | 0.0063 (5) | −0.0021 (5) |
O4 | 0.0318 (7) | 0.0928 (11) | 0.0856 (10) | 0.0073 (7) | 0.0039 (6) | 0.0078 (8) |
O5 | 0.0402 (6) | 0.0567 (7) | 0.0521 (7) | 0.0063 (5) | −0.0015 (5) | −0.0064 (6) |
C1 | 0.0356 (8) | 0.0455 (9) | 0.0364 (8) | 0.0019 (7) | 0.0019 (6) | 0.0096 (7) |
C2 | 0.0301 (8) | 0.0513 (10) | 0.0415 (9) | 0.0020 (7) | 0.0028 (7) | 0.0080 (7) |
C3 | 0.0400 (9) | 0.0489 (9) | 0.0375 (9) | 0.0071 (7) | 0.0017 (7) | 0.0070 (7) |
C4 | 0.0414 (9) | 0.0497 (10) | 0.0479 (10) | −0.0004 (8) | −0.0056 (8) | 0.0060 (8) |
C5 | 0.0316 (8) | 0.0582 (10) | 0.0500 (10) | −0.0016 (8) | −0.0039 (7) | 0.0151 (8) |
C6 | 0.0320 (8) | 0.0514 (10) | 0.0410 (9) | 0.0042 (7) | 0.0013 (7) | 0.0154 (7) |
C7 | 0.0345 (9) | 0.0623 (11) | 0.0522 (10) | 0.0080 (8) | 0.0066 (7) | 0.0214 (9) |
C8 | 0.0434 (10) | 0.0638 (12) | 0.0734 (13) | 0.0123 (9) | 0.0167 (9) | 0.0086 (10) |
C9 | 0.0323 (8) | 0.0542 (10) | 0.0499 (10) | 0.0029 (7) | 0.0029 (7) | 0.0030 (8) |
C10 | 0.0351 (9) | 0.0534 (10) | 0.0457 (9) | 0.0035 (8) | 0.0034 (7) | 0.0094 (8) |
C11 | 0.0524 (10) | 0.0487 (10) | 0.0510 (10) | 0.0029 (8) | 0.0034 (8) | −0.0024 (8) |
C12 | 0.0651 (13) | 0.0719 (13) | 0.0625 (13) | 0.0082 (10) | 0.0206 (10) | 0.0013 (10) |
C13 | 0.0373 (9) | 0.0543 (10) | 0.0504 (10) | 0.0044 (8) | 0.0034 (7) | 0.0017 (8) |
C14 | 0.0431 (9) | 0.0459 (9) | 0.0500 (10) | 0.0028 (7) | 0.0020 (8) | 0.0093 (8) |
C15 | 0.0350 (8) | 0.0425 (9) | 0.0459 (9) | 0.0017 (7) | −0.0030 (7) | 0.0042 (7) |
C16 | 0.0515 (11) | 0.0604 (12) | 0.0627 (12) | 0.0071 (9) | 0.0078 (9) | 0.0173 (9) |
C17 | 0.0509 (11) | 0.0504 (11) | 0.0746 (13) | 0.0097 (9) | 0.0103 (9) | 0.0069 (9) |
O1—C1 | 1.3510 (19) | C9—C10 | 1.486 (2) |
O1—C9 | 1.4023 (19) | C9—H9A | 0.9700 |
O2—C10 | 1.1896 (19) | C9—H9B | 0.9700 |
O3—C10 | 1.304 (2) | C11—C12 | 1.470 (3) |
O3—C11 | 1.441 (2) | C11—H11A | 0.9700 |
O4—C7 | 1.208 (2) | C11—H11B | 0.9700 |
O5—C3 | 1.3457 (19) | C12—H12A | 0.9600 |
O5—C13 | 1.4260 (19) | C12—H12B | 0.9600 |
C1—C2 | 1.375 (2) | C12—H12C | 0.9600 |
C1—C6 | 1.394 (2) | C13—C14 | 1.474 (2) |
C2—C3 | 1.374 (2) | C13—H13A | 0.9700 |
C2—H2 | 0.9300 | C13—H13B | 0.9700 |
C3—C4 | 1.377 (2) | C14—C15 | 1.310 (2) |
C4—C5 | 1.351 (2) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—C16 | 1.482 (2) |
C5—C6 | 1.383 (2) | C15—C17 | 1.486 (2) |
C5—H5 | 0.9300 | C16—H16A | 0.9600 |
C6—C7 | 1.480 (2) | C16—H16B | 0.9600 |
C7—C8 | 1.478 (3) | C16—H16C | 0.9600 |
C8—H8A | 0.9600 | C17—H17A | 0.9600 |
C8—H8B | 0.9600 | C17—H17B | 0.9600 |
C8—H8C | 0.9600 | C17—H17C | 0.9600 |
C1—O1—C9 | 118.66 (13) | O3—C10—C9 | 114.29 (13) |
C10—O3—C11 | 116.17 (13) | O3—C11—C12 | 107.18 (14) |
C3—O5—C13 | 118.37 (12) | O3—C11—H11A | 110.3 |
O1—C1—C2 | 121.63 (14) | C12—C11—H11A | 110.3 |
O1—C1—C6 | 116.88 (14) | O3—C11—H11B | 110.3 |
C2—C1—C6 | 121.49 (15) | C12—C11—H11B | 110.3 |
C3—C2—C1 | 119.71 (14) | H11A—C11—H11B | 108.5 |
C3—C2—H2 | 120.1 | C11—C12—H12A | 109.5 |
C1—C2—H2 | 120.1 | C11—C12—H12B | 109.5 |
O5—C3—C2 | 124.21 (14) | H12A—C12—H12B | 109.5 |
O5—C3—C4 | 115.94 (14) | C11—C12—H12C | 109.5 |
C2—C3—C4 | 119.85 (15) | H12A—C12—H12C | 109.5 |
C5—C4—C3 | 119.53 (16) | H12B—C12—H12C | 109.5 |
C5—C4—H4 | 120.2 | O5—C13—C14 | 107.62 (13) |
C3—C4—H4 | 120.2 | O5—C13—H13A | 110.2 |
C4—C5—C6 | 123.02 (15) | C14—C13—H13A | 110.2 |
C4—C5—H5 | 118.5 | O5—C13—H13B | 110.2 |
C6—C5—H5 | 118.5 | C14—C13—H13B | 110.2 |
C5—C6—C1 | 116.38 (15) | H13A—C13—H13B | 108.5 |
C5—C6—C7 | 116.88 (14) | C15—C14—C13 | 128.05 (17) |
C1—C6—C7 | 126.73 (15) | C15—C14—H14 | 116.0 |
O4—C7—C8 | 119.01 (17) | C13—C14—H14 | 116.0 |
O4—C7—C6 | 119.05 (17) | C14—C15—C16 | 124.75 (16) |
C8—C7—C6 | 121.94 (15) | C14—C15—C17 | 121.01 (17) |
C7—C8—H8A | 109.5 | C16—C15—C17 | 114.24 (16) |
C7—C8—H8B | 109.5 | C15—C16—H16A | 109.5 |
H8A—C8—H8B | 109.5 | C15—C16—H16B | 109.5 |
C7—C8—H8C | 109.5 | H16A—C16—H16B | 109.5 |
H8A—C8—H8C | 109.5 | C15—C16—H16C | 109.5 |
H8B—C8—H8C | 109.5 | H16A—C16—H16C | 109.5 |
O1—C9—C10 | 110.65 (13) | H16B—C16—H16C | 109.5 |
O1—C9—H9A | 109.5 | C15—C17—H17A | 109.5 |
C10—C9—H9A | 109.5 | C15—C17—H17B | 109.5 |
O1—C9—H9B | 109.5 | H17A—C17—H17B | 109.5 |
C10—C9—H9B | 109.5 | C15—C17—H17C | 109.5 |
H9A—C9—H9B | 108.1 | H17A—C17—H17C | 109.5 |
O2—C10—O3 | 124.59 (16) | H17B—C17—H17C | 109.5 |
O2—C10—C9 | 121.11 (15) | ||
C9—O1—C1—C2 | 0.7 (2) | C2—C1—C6—C7 | −179.87 (15) |
C9—O1—C1—C6 | −179.11 (15) | C5—C6—C7—O4 | 8.6 (2) |
O1—C1—C2—C3 | −178.37 (15) | C1—C6—C7—O4 | −172.29 (17) |
C6—C1—C2—C3 | 1.4 (2) | C5—C6—C7—C8 | −170.68 (16) |
C13—O5—C3—C2 | −9.0 (2) | C1—C6—C7—C8 | 8.4 (3) |
C13—O5—C3—C4 | 170.27 (15) | C1—O1—C9—C10 | 175.61 (14) |
C1—C2—C3—O5 | 177.99 (15) | C11—O3—C10—O2 | −0.7 (3) |
C1—C2—C3—C4 | −1.3 (2) | C11—O3—C10—C9 | 179.33 (15) |
O5—C3—C4—C5 | −178.82 (15) | O1—C9—C10—O2 | −177.66 (16) |
C2—C3—C4—C5 | 0.5 (3) | O1—C9—C10—O3 | 2.3 (2) |
C3—C4—C5—C6 | 0.2 (3) | C10—O3—C11—C12 | 172.84 (16) |
C4—C5—C6—C1 | 0.0 (3) | C3—O5—C13—C14 | −166.29 (15) |
C4—C5—C6—C7 | 179.18 (16) | O5—C13—C14—C15 | −116.58 (19) |
O1—C1—C6—C5 | 179.03 (14) | C13—C14—C15—C16 | 3.5 (3) |
C2—C1—C6—C5 | −0.8 (2) | C13—C14—C15—C17 | −176.47 (16) |
O1—C1—C6—C7 | −0.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O2i | 0.97 | 2.41 | 3.373 (2) | 170 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C17H22O5 |
Mr | 306.35 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 8.271 (3), 9.663 (3), 10.514 (4) |
α, β, γ (°) | 108.837 (6), 90.689 (6), 94.101 (6) |
V (Å3) | 792.7 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.34 × 0.30 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.954, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4147, 2779, 2119 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.109, 1.03 |
No. of reflections | 2779 |
No. of parameters | 204 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O2i | 0.97 | 2.41 | 3.373 (2) | 170 |
Symmetry code: (i) −x, −y, −z+1. |
Sofalcone is an antiulcer agent which is effective for the treatment of gastric ulcer(Kazuaki & Katsuo, 1979). The structure of the title compound, (I), an intermediate in the synthesis of sofalcone, is reported here.
As shown in Fig. 1, atoms C13—C17 are almost coplanar, with an r.m.s. deviation from the mean plane of 0.017 (1) Å. This plane and the C1—C6 benzene ring plane form a dihedral angle of 61.86 (7) °. Another plane defined by atoms C9/C10/O2/O3 is almost coplanar with the C1—C6 plane with a dihedral angle of 5.22 (9)°. The packing is consolidated by a C—H···O interaction (Table 1) leading to centrosymmetric dimers (Fig. 2).