Acta Cryst. (2008). E64, o1020 [ doi:10.1107/S1600536808012956 ]
In the title molecule, C19H18O2, the cyclohexene ring adopts an envelope conformation, with all substituents equatorial. The dihedral angle between the benzene and phenyl rings is 83.75 (16)°. No classical hydrogen bonds are found in the crystal structure.
The title compound was prepared according to the general procedure reported by Pandiarajan et al. (2005). A mixture of 2,4-bis(ethoxycarbonyl)-5-hydroxy-5-methyl-3,3'-phenoxy phenylcyclohexanone (4.40 g, 0.01 mol) in glacial acetic acid (25 ml) and concentrated hydrochloric acid (50 ml) was refluxed for 12 h. After completion of the reaction, the reaction mixture was neutralized with aqueous ammonia and separated by using chloroform. The product was purified by column chromatography (benzene-EtOAc, 9.5:0.5 v/v). The yield of the isolated product was 2.08 g (75%).
H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–1.00 Å and Uiso(H) = xUeq(carrier atom), where x = 1.5 for methyl and 1.2 for all other C atoms. The maximum residual electron density peak is located 1.08 Å from C5.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).
![[Figure 1]](./wn2258fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 40% probability level. Hydrogen atoms are represented by spheres of arbitrary radius. |
| C19H18O2 | Dx = 1.270 Mg m−3 |
| Mr = 278.33 | Melting point: 478 K |
| Orthorhombic, Pbca | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 2911 reflections |
| a = 9.6002 (3) Å | θ = 2.0–25.0º |
| b = 17.1594 (7) Å | µ = 0.08 mm−1 |
| c = 17.6730 (5) Å | T = 160 (1) K |
| V = 2911.34 (17) Å3 | Tablet, colourless |
| Z = 8 | 0.20 × 0.15 × 0.08 mm |
| F000 = 1184 |
| Nonius KappaCCD area-detector diffractometer | 2566 independent reflections |
| Radiation source: Nonius FR590 sealed tube generator | 1708 reflections with I > 2σ(I) |
| Monochromator: horizontally mounted graphite crystal | Rint = 0.115 |
| Detector resolution: 9 pixels mm-1 | θmax = 25.1º |
| T = 160(1) K | θmin = 2.4º |
| ω scans with κ offsets | h = −11→11 |
| Absorption correction: none | k = −20→20 |
| 32821 measured reflections | l = −21→21 |
| 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)] = 0.070 | H-atom parameters constrained |
| wR(F2) = 0.198 | w = 1/[σ2(Fo2) + (0.0847P)2 + 2.668P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 2566 reflections | Δρmax = 1.04 e Å−3 |
| 191 parameters | Δρmin = −0.38 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C19H18O2 | V = 2911.34 (17) Å3 |
| Mr = 278.33 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα |
| a = 9.6002 (3) Å | µ = 0.08 mm−1 |
| b = 17.1594 (7) Å | T = 160 (1) K |
| c = 17.6730 (5) Å | 0.20 × 0.15 × 0.08 mm |
| Nonius KappaCCD area-detector diffractometer | 2566 independent reflections |
| Absorption correction: none | 1708 reflections with I > 2σ(I) |
| 32821 measured reflections | Rint = 0.115 |
| R[F2 > 2σ(F2)] = 0.070 | 191 parameters |
| wR(F2) = 0.198 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 1.04 e Å−3 |
| 2566 reflections | Δρmin = −0.38 e Å−3 |
Experimental. Solvent used: ? Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.560 (2) Frames collected: 270 Seconds exposure per frame: 114 Degrees rotation per frame: 1.2 Crystal-Detector distance (mm): 30.0 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | −0.0247 (3) | −0.18365 (15) | 0.28956 (14) | 0.0629 (9) | |
| O13 | 0.5599 (2) | 0.05049 (13) | 0.11517 (15) | 0.0591 (9) | |
| C1 | −0.0118 (3) | −0.14143 (19) | 0.2341 (2) | 0.0455 (11) | |
| C2 | −0.1041 (3) | −0.14696 (19) | 0.16869 (19) | 0.0451 (11) | |
| C3 | −0.0947 (3) | −0.09996 (18) | 0.10876 (19) | 0.0413 (10) | |
| C4 | 0.0161 (3) | −0.03832 (18) | 0.10374 (17) | 0.0395 (10) | |
| C5 | 0.0737 (4) | −0.0131 (2) | 0.1805 (2) | 0.0567 (12) | |
| C6 | 0.1045 (4) | −0.0818 (2) | 0.2293 (2) | 0.0550 (12) | |
| C11 | 0.1921 (3) | 0.0452 (2) | 0.17330 (17) | 0.0493 (13) | |
| C12 | 0.3246 (4) | 0.0212 (2) | 0.14640 (18) | 0.0514 (11) | |
| C13 | 0.4298 (3) | 0.07684 (19) | 0.13841 (17) | 0.0412 (10) | |
| C14 | 0.4052 (3) | 0.15345 (18) | 0.15702 (17) | 0.0399 (10) | |
| C15 | 0.2749 (3) | 0.1745 (2) | 0.18305 (18) | 0.0478 (11) | |
| C16 | 0.1706 (4) | 0.1217 (2) | 0.19066 (18) | 0.0523 (14) | |
| C21 | 0.6445 (3) | 0.10391 (19) | 0.07643 (19) | 0.0450 (11) | |
| C22 | 0.6069 (3) | 0.1299 (2) | 0.0053 (2) | 0.0490 (11) | |
| C23 | 0.6939 (4) | 0.1795 (2) | −0.0331 (2) | 0.0512 (11) | |
| C24 | 0.8177 (4) | 0.20337 (19) | −0.0009 (2) | 0.0485 (11) | |
| C25 | 0.8541 (4) | 0.1771 (2) | 0.0703 (2) | 0.0517 (11) | |
| C26 | 0.7668 (3) | 0.1271 (2) | 0.10933 (19) | 0.0472 (11) | |
| C31 | −0.1933 (3) | −0.1052 (2) | 0.0437 (2) | 0.0547 (12) | |
| H2 | −0.17441 | −0.18594 | 0.16881 | 0.0541* | |
| H4A | 0.09381 | −0.05832 | 0.07242 | 0.0474* | |
| H4B | −0.02296 | 0.00786 | 0.07774 | 0.0474* | |
| H5 | −0.00388 | 0.01545 | 0.20614 | 0.0677* | |
| H6A | 0.18905 | −0.10791 | 0.20966 | 0.0662* | |
| H6B | 0.12561 | −0.06310 | 0.28098 | 0.0662* | |
| H12 | 0.34146 | −0.03181 | 0.13401 | 0.0619* | |
| H14 | 0.47676 | 0.19132 | 0.15203 | 0.0479* | |
| H15 | 0.25785 | 0.22737 | 0.19600 | 0.0576* | |
| H16 | 0.08181 | 0.13819 | 0.20821 | 0.0627* | |
| H22 | 0.52162 | 0.11346 | −0.01684 | 0.0588* | |
| H23 | 0.66872 | 0.19757 | −0.08207 | 0.0616* | |
| H24 | 0.87765 | 0.23777 | −0.02755 | 0.0582* | |
| H25 | 0.93940 | 0.19332 | 0.09252 | 0.0622* | |
| H26 | 0.79133 | 0.10911 | 0.15838 | 0.0566* | |
| H31A | −0.26101 | −0.14680 | 0.05316 | 0.0820* | |
| H31B | −0.24236 | −0.05547 | 0.03789 | 0.0820* | |
| H31C | −0.14127 | −0.11674 | −0.00267 | 0.0820* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0680 (17) | 0.0558 (16) | 0.0649 (16) | −0.0136 (13) | 0.0041 (13) | 0.0168 (14) |
| O13 | 0.0528 (15) | 0.0379 (14) | 0.0866 (18) | 0.0057 (12) | 0.0163 (13) | 0.0127 (12) |
| C1 | 0.0423 (18) | 0.0383 (18) | 0.056 (2) | 0.0021 (15) | 0.0055 (15) | 0.0018 (17) |
| C2 | 0.0354 (17) | 0.0379 (19) | 0.062 (2) | −0.0055 (14) | 0.0070 (15) | −0.0097 (16) |
| C3 | 0.0336 (16) | 0.0369 (18) | 0.0533 (19) | 0.0012 (14) | 0.0011 (14) | −0.0100 (15) |
| C4 | 0.0351 (16) | 0.0394 (18) | 0.0440 (17) | −0.0002 (14) | −0.0006 (13) | −0.0026 (14) |
| C5 | 0.054 (2) | 0.063 (2) | 0.053 (2) | −0.0137 (19) | −0.0044 (17) | 0.0033 (18) |
| C6 | 0.060 (2) | 0.044 (2) | 0.061 (2) | −0.0104 (17) | −0.0137 (18) | 0.0118 (17) |
| C11 | 0.0363 (18) | 0.077 (3) | 0.0347 (17) | −0.0184 (17) | −0.0048 (14) | 0.0115 (17) |
| C12 | 0.072 (2) | 0.0363 (19) | 0.0459 (19) | −0.0121 (18) | −0.0090 (17) | 0.0034 (15) |
| C13 | 0.0388 (17) | 0.0402 (19) | 0.0446 (18) | −0.0023 (15) | 0.0004 (14) | 0.0055 (14) |
| C14 | 0.0372 (17) | 0.0372 (19) | 0.0452 (18) | −0.0040 (14) | −0.0012 (14) | 0.0045 (14) |
| C15 | 0.047 (2) | 0.055 (2) | 0.0415 (18) | 0.0008 (17) | 0.0018 (15) | 0.0035 (16) |
| C16 | 0.048 (2) | 0.067 (3) | 0.0420 (19) | 0.0032 (19) | 0.0000 (15) | 0.0037 (17) |
| C21 | 0.0392 (17) | 0.0357 (18) | 0.060 (2) | 0.0048 (15) | 0.0081 (16) | 0.0010 (16) |
| C22 | 0.0410 (18) | 0.047 (2) | 0.059 (2) | 0.0015 (16) | −0.0023 (16) | −0.0042 (17) |
| C23 | 0.056 (2) | 0.050 (2) | 0.0476 (19) | 0.0128 (18) | 0.0041 (17) | −0.0002 (16) |
| C24 | 0.050 (2) | 0.0376 (19) | 0.058 (2) | 0.0036 (15) | 0.0159 (17) | 0.0008 (16) |
| C25 | 0.0421 (19) | 0.053 (2) | 0.060 (2) | 0.0040 (17) | −0.0005 (17) | −0.0115 (18) |
| C26 | 0.0466 (19) | 0.049 (2) | 0.0461 (19) | 0.0116 (16) | 0.0019 (16) | 0.0005 (16) |
| C31 | 0.050 (2) | 0.048 (2) | 0.066 (2) | −0.0049 (17) | −0.0103 (17) | −0.0078 (18) |
| O1—C1 | 1.225 (4) | C24—C25 | 1.382 (5) |
| O13—C13 | 1.390 (4) | C25—C26 | 1.384 (5) |
| O13—C21 | 1.403 (4) | C2—H2 | 0.9500 |
| C1—C2 | 1.460 (5) | C4—H4A | 0.9900 |
| C1—C6 | 1.517 (5) | C4—H4B | 0.9900 |
| C2—C3 | 1.334 (5) | C5—H5 | 1.0000 |
| C3—C4 | 1.503 (4) | C6—H6A | 0.9900 |
| C3—C31 | 1.492 (5) | C6—H6B | 0.9900 |
| C4—C5 | 1.528 (5) | C12—H12 | 0.9500 |
| C5—C6 | 1.490 (5) | C14—H14 | 0.9500 |
| C5—C11 | 1.520 (5) | C15—H15 | 0.9500 |
| C11—C12 | 1.419 (5) | C16—H16 | 0.9500 |
| C11—C16 | 1.364 (5) | C22—H22 | 0.9500 |
| C12—C13 | 1.397 (5) | C23—H23 | 0.9500 |
| C13—C14 | 1.376 (4) | C24—H24 | 0.9500 |
| C14—C15 | 1.381 (4) | C25—H25 | 0.9500 |
| C15—C16 | 1.357 (5) | C26—H26 | 0.9500 |
| C21—C22 | 1.382 (5) | C31—H31A | 0.9800 |
| C21—C26 | 1.369 (4) | C31—H31B | 0.9800 |
| C22—C23 | 1.372 (5) | C31—H31C | 0.9800 |
| C23—C24 | 1.380 (5) | ||
| O1···H23i | 2.6700 | H4A···C23x | 2.9900 |
| O1···H15ii | 2.7200 | H4A···C24x | 2.9200 |
| O13···H6Biii | 2.7500 | H4B···C26viii | 2.9300 |
| C2···C6iv | 3.511 (5) | H4B···H31B | 2.4700 |
| C6···C2iii | 3.511 (5) | H5···C2 | 3.0200 |
| C14···C22 | 3.332 (4) | H5···H16 | 2.2600 |
| C22···C14 | 3.332 (4) | H5···C12iv | 3.0800 |
| C24···C31v | 3.583 (5) | H5···C13iv | 3.0100 |
| C31···C24vi | 3.583 (5) | H6A···C12 | 2.8000 |
| C1···H6Aiv | 3.0900 | H6A···H12 | 2.3700 |
| C2···H6Aiv | 3.0000 | H6A···C1iii | 3.0900 |
| C2···H6Biv | 3.1000 | H6A···C2iii | 3.0000 |
| C2···H5 | 3.0200 | H6B···O13iv | 2.7500 |
| C2···H14vi | 3.0500 | H6B···C2iii | 3.1000 |
| C6···H12 | 2.9600 | H12···C6 | 2.9600 |
| C12···H5iii | 3.0800 | H12···H6A | 2.3700 |
| C12···H4A | 2.9100 | H12···C22x | 3.0200 |
| C12···H6A | 2.8000 | H14···C21 | 2.5700 |
| C13···H22 | 2.9500 | H14···C22 | 3.0700 |
| C13···H5iii | 3.0100 | H14···C26 | 3.0900 |
| C14···H24vii | 2.9600 | H14···C2v | 3.0500 |
| C14···H16iii | 2.9400 | H15···H23vii | 2.5400 |
| C15···H23vii | 3.0100 | H15···O1xi | 2.7200 |
| C15···H26iv | 3.0200 | H16···H5 | 2.2600 |
| C16···H25viii | 3.0700 | H16···C14iv | 2.9400 |
| C16···H26iv | 2.9200 | H22···C13 | 2.9500 |
| C21···H31Bix | 3.0200 | H23···O1xii | 2.6700 |
| C21···H14 | 2.5700 | H23···C15xiii | 3.0100 |
| C22···H14 | 3.0700 | H23···H15xiii | 2.5400 |
| C22···H12x | 3.0200 | H24···C14xiii | 2.9600 |
| C23···H4Ax | 2.9900 | H25···C16ix | 3.0700 |
| C24···H4Ax | 2.9200 | H26···C15iii | 3.0200 |
| C24···H31Av | 2.8000 | H26···C16iii | 2.9200 |
| C26···H4Bix | 2.9300 | H31A···H2 | 2.3100 |
| C26···H14 | 3.0900 | H31A···C24vi | 2.8000 |
| H2···H31A | 2.3100 | H31B···C21viii | 3.0200 |
| H4A···C12 | 2.9100 | H31B···H4B | 2.4700 |
| C13—O13—C21 | 116.9 (2) | C5—C4—H4A | 109.00 |
| O1—C1—C2 | 122.3 (3) | C5—C4—H4B | 109.00 |
| O1—C1—C6 | 121.2 (3) | H4A—C4—H4B | 108.00 |
| C2—C1—C6 | 116.5 (3) | C4—C5—H5 | 106.00 |
| C1—C2—C3 | 123.3 (3) | C6—C5—H5 | 106.00 |
| C2—C3—C4 | 121.3 (3) | C11—C5—H5 | 106.00 |
| C2—C3—C31 | 122.2 (3) | C1—C6—H6A | 109.00 |
| C4—C3—C31 | 116.5 (3) | C1—C6—H6B | 109.00 |
| C3—C4—C5 | 113.8 (3) | C5—C6—H6A | 109.00 |
| C4—C5—C6 | 111.2 (3) | C5—C6—H6B | 109.00 |
| C4—C5—C11 | 112.5 (3) | H6A—C6—H6B | 108.00 |
| C6—C5—C11 | 114.9 (3) | C11—C12—H12 | 121.00 |
| C1—C6—C5 | 114.8 (3) | C13—C12—H12 | 121.00 |
| C5—C11—C12 | 120.5 (3) | C13—C14—H14 | 120.00 |
| C5—C11—C16 | 120.1 (3) | C15—C14—H14 | 120.00 |
| C12—C11—C16 | 119.4 (3) | C14—C15—H15 | 119.00 |
| C11—C12—C13 | 118.9 (3) | C16—C15—H15 | 119.00 |
| O13—C13—C12 | 117.2 (3) | C11—C16—H16 | 120.00 |
| O13—C13—C14 | 122.4 (3) | C15—C16—H16 | 120.00 |
| C12—C13—C14 | 120.3 (3) | C21—C22—H22 | 120.00 |
| C13—C14—C15 | 119.0 (3) | C23—C22—H22 | 120.00 |
| C14—C15—C16 | 121.8 (3) | C22—C23—H23 | 120.00 |
| C11—C16—C15 | 120.6 (3) | C24—C23—H23 | 120.00 |
| O13—C21—C22 | 120.2 (3) | C23—C24—H24 | 120.00 |
| O13—C21—C26 | 118.6 (3) | C25—C24—H24 | 120.00 |
| C22—C21—C26 | 121.1 (3) | C24—C25—H25 | 120.00 |
| C21—C22—C23 | 119.4 (3) | C26—C25—H25 | 120.00 |
| C22—C23—C24 | 120.3 (3) | C21—C26—H26 | 120.00 |
| C23—C24—C25 | 119.8 (3) | C25—C26—H26 | 120.00 |
| C24—C25—C26 | 120.2 (3) | C3—C31—H31A | 109.00 |
| C21—C26—C25 | 119.2 (3) | C3—C31—H31B | 109.00 |
| C1—C2—H2 | 118.00 | C3—C31—H31C | 109.00 |
| C3—C2—H2 | 118.00 | H31A—C31—H31B | 109.00 |
| C3—C4—H4A | 109.00 | H31A—C31—H31C | 109.00 |
| C3—C4—H4B | 109.00 | H31B—C31—H31C | 109.00 |
| C21—O13—C13—C12 | 153.1 (3) | C6—C5—C11—C16 | −125.0 (3) |
| C21—O13—C13—C14 | −30.3 (4) | C5—C11—C12—C13 | 178.1 (3) |
| C13—O13—C21—C22 | −67.2 (4) | C16—C11—C12—C13 | 0.0 (5) |
| C13—O13—C21—C26 | 115.2 (3) | C5—C11—C16—C15 | −178.7 (3) |
| O1—C1—C2—C3 | 177.8 (3) | C12—C11—C16—C15 | −0.6 (5) |
| C6—C1—C2—C3 | −3.8 (5) | C11—C12—C13—O13 | 177.2 (3) |
| O1—C1—C6—C5 | −153.3 (3) | C11—C12—C13—C14 | 0.6 (5) |
| C2—C1—C6—C5 | 28.3 (4) | O13—C13—C14—C15 | −177.0 (3) |
| C1—C2—C3—C4 | 1.6 (5) | C12—C13—C14—C15 | −0.5 (5) |
| C1—C2—C3—C31 | −178.0 (3) | C13—C14—C15—C16 | −0.1 (5) |
| C2—C3—C4—C5 | −23.1 (4) | C14—C15—C16—C11 | 0.7 (5) |
| C31—C3—C4—C5 | 156.5 (3) | O13—C21—C22—C23 | −177.2 (3) |
| C3—C4—C5—C6 | 45.7 (4) | C26—C21—C22—C23 | 0.3 (5) |
| C3—C4—C5—C11 | 176.2 (3) | O13—C21—C26—C25 | 177.2 (3) |
| C4—C5—C6—C1 | −48.6 (4) | C22—C21—C26—C25 | −0.3 (5) |
| C11—C5—C6—C1 | −177.8 (3) | C21—C22—C23—C24 | −0.2 (5) |
| C4—C5—C11—C12 | −71.7 (4) | C22—C23—C24—C25 | 0.1 (5) |
| C4—C5—C11—C16 | 106.4 (3) | C23—C24—C25—C26 | −0.1 (5) |
| C6—C5—C11—C12 | 56.9 (4) | C24—C25—C26—C21 | 0.2 (5) |
| Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x+1/2, y, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) −x+1/2, y+1/2, z; (vi) −x+1/2, y−1/2, z; (vii) x−1/2, −y+1/2, −z; (viii) x−1, y, z; (ix) x+1, y, z; (x) −x+1, −y, −z; (xi) −x, y+1/2, −z+1/2; (xii) −x+1/2, −y, z−1/2; (xiii) x+1/2, −y+1/2, −z. |
AT thanks the UGC, India, for the award of a Minor Research Project [file No. MRP-2355/06 (UGC-SERO), link No. 2355, 10/01/2007].
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Pandiarajan, K., Sabapathy Mohan, R. T., Gomathi, R. & Muthukumaran, G. (2005). Magn. Reson. Chem. 43, 430–434.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
The present X-ray diffraction study was undertaken to determine how the conformation of the system is affected by the substitution of a methyl group at position 3 and a phenoxyphenyl group at position 5 of the cyclohexenone ring. The molecular structure of the title compound, with atomic numbering scheme, is shown in Fig. 1. The cyclohexene ring adopts an envelope conformation, with all substituents equatorial. The dihedral angle between the benzene and phenyl rings is 83.75 (16)°. No classical hydrogen bonds are found in the crystal structure.