Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101786X/tk6041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101786X/tk6041Isup2.hkl |
CCDC reference: 176038
The hexane extract of the fresh fruit of Melicope ellyrana, after concentration (Smith, Wang et al., 2001) gave a precipitate of crystals of the title compound suitable for single-crystal structural analysis.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON for Windows (Spek, 1999); software used to prepare material for publication: TEXSAN for Windows.
Fig. 1. The molecular configuration and atom-naming scheme for the title compound. Atoms are shown as the 30% probability ellipsoids (Spek, 1999). |
C15H18O4 | Dx = 1.238 Mg m−3 |
Mr = 262.29 | Melting point: 380 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 7.2233 (19) Å | Cell parameters from 25 reflections |
b = 10.354 (3) Å | θ = 12–18° |
c = 18.825 (2) Å | µ = 0.09 mm−1 |
β = 91.334 (19)° | T = 293 K |
V = 1407.5 (6) Å3 | Plate, colourless |
Z = 4 | 0.40 × 0.35 × 0.15 mm |
F(000) = 560 |
Rigaku AFC-7R diffractometer | Rint = 0.050 |
Radiation source: Rigaku rotating anode | θmax = 25.0°, θmin = 2.8° |
Graphite monochromator | h = 0→8 |
ω–2θ scans | k = 0→12 |
2698 measured reflections | l = −22→22 |
2486 independent reflections | 3 standard reflections every 150 reflections |
1106 reflections with I > 2σ(I) | intensity decay: 2.2% |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.224 | H-atom parameters not refined |
S = 1.39 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
2486 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C15H18O4 | V = 1407.5 (6) Å3 |
Mr = 262.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2233 (19) Å | µ = 0.09 mm−1 |
b = 10.354 (3) Å | T = 293 K |
c = 18.825 (2) Å | 0.40 × 0.35 × 0.15 mm |
β = 91.334 (19)° |
Rigaku AFC-7R diffractometer | Rint = 0.050 |
2698 measured reflections | 3 standard reflections every 150 reflections |
2486 independent reflections | intensity decay: 2.2% |
1106 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.224 | H-atom parameters not refined |
S = 1.39 | Δρmax = 0.32 e Å−3 |
2486 reflections | Δρmin = −0.31 e Å−3 |
173 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 | 0.1504 (4) | 0.3078 (3) | 0.39021 (14) | 0.0636 (9) | |
O5 | 0.7121 (4) | 0.0752 (3) | 0.37529 (16) | 0.0788 (11) | |
O7 | 0.5009 (4) | 0.2447 (3) | 0.59881 (15) | 0.0738 (10) | |
O81 | 0.0737 (5) | 0.3082 (4) | 0.5677 (2) | 0.1121 (15) | |
C2 | 0.1561 (6) | 0.3408 (5) | 0.3142 (2) | 0.0680 (13) | |
C3 | 0.2608 (7) | 0.2384 (6) | 0.2749 (2) | 0.0817 (15) | |
C4A | 0.4368 (6) | 0.1890 (4) | 0.3815 (2) | 0.0594 (12) | |
C4 | 0.3927 (7) | 0.1706 (5) | 0.3064 (2) | 0.0773 (15) | |
C5 | 0.5929 (6) | 0.1393 (4) | 0.4174 (2) | 0.0558 (11) | |
C6 | 0.6197 (5) | 0.1544 (4) | 0.4893 (2) | 0.0580 (12) | |
C7 | 0.4873 (6) | 0.2219 (4) | 0.5274 (2) | 0.0559 (11) | |
C8A | 0.3105 (5) | 0.2589 (4) | 0.4215 (2) | 0.0553 (11) | |
C8 | 0.3310 (5) | 0.2750 (4) | 0.4941 (2) | 0.0522 (11) | |
C21 | −0.0468 (7) | 0.3462 (6) | 0.2913 (3) | 0.0949 (19) | |
C22 | 0.2447 (8) | 0.4714 (6) | 0.3081 (3) | 0.0927 (18) | |
C51 | 0.8796 (7) | 0.0234 (6) | 0.4082 (3) | 0.0902 (17) | |
C71 | 0.6490 (6) | 0.1866 (5) | 0.6387 (2) | 0.0718 (14) | |
C81 | 0.1994 (6) | 0.3563 (5) | 0.5358 (2) | 0.0635 (12) | |
C82 | 0.2338 (7) | 0.4995 (6) | 0.5330 (3) | 0.0903 (17) | |
H3 | 0.2302 | 0.2219 | 0.2263 | 0.098* | |
H4 | 0.4604 | 0.1095 | 0.2798 | 0.093* | |
H6 | 0.7262 | 0.1195 | 0.5128 | 0.070* | |
H51 | 0.9797 | 0.0345 | 0.3777 | 0.108* | |
H52 | 0.8623 | −0.0666 | 0.4175 | 0.108* | |
H53 | 0.9036 | 0.0667 | 0.4520 | 0.108* | |
H71 | 0.6254 | 0.1940 | 0.6881 | 0.088* | |
H72 | 0.6579 | 0.0979 | 0.6264 | 0.088* | |
H73 | 0.7617 | 0.2290 | 0.6286 | 0.088* | |
H82 | 0.2434 | 0.5319 | 0.5803 | 0.108* | |
H83 | 0.3451 | 0.5154 | 0.5092 | 0.108* | |
H84 | 0.1332 | 0.5399 | 0.5087 | 0.108* | |
H211 | −0.0779 | 0.2713 | 0.2644 | 0.114* | |
H212 | −0.0687 | 0.4209 | 0.2631 | 0.114* | |
H213 | −0.1214 | 0.3496 | 0.3323 | 0.114* | |
H221 | 0.2703 | 0.5050 | 0.3544 | 0.111* | |
H222 | 0.1636 | 0.5282 | 0.2830 | 0.111* | |
H223 | 0.3576 | 0.4639 | 0.2833 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0519 (18) | 0.081 (2) | 0.0582 (19) | −0.0017 (16) | 0.0017 (13) | 0.0119 (15) |
O5 | 0.075 (2) | 0.094 (3) | 0.067 (2) | 0.0218 (19) | 0.0099 (17) | −0.0093 (18) |
O7 | 0.0664 (19) | 0.104 (3) | 0.0509 (19) | 0.0198 (18) | −0.0007 (14) | −0.0036 (17) |
O81 | 0.087 (3) | 0.108 (3) | 0.144 (4) | 0.020 (2) | 0.063 (2) | 0.041 (3) |
C2 | 0.068 (3) | 0.080 (4) | 0.056 (3) | −0.004 (3) | 0.000 (2) | 0.017 (2) |
C3 | 0.082 (3) | 0.108 (4) | 0.055 (3) | 0.001 (3) | −0.003 (3) | 0.001 (3) |
C4A | 0.057 (3) | 0.060 (3) | 0.061 (3) | 0.004 (2) | 0.011 (2) | 0.005 (2) |
C4 | 0.086 (3) | 0.095 (4) | 0.052 (3) | 0.012 (3) | 0.007 (2) | −0.007 (3) |
C5 | 0.054 (3) | 0.051 (3) | 0.062 (3) | 0.005 (2) | 0.014 (2) | −0.002 (2) |
C6 | 0.049 (2) | 0.058 (3) | 0.067 (3) | 0.008 (2) | 0.003 (2) | 0.007 (2) |
C7 | 0.052 (2) | 0.064 (3) | 0.052 (3) | 0.000 (2) | 0.006 (2) | 0.004 (2) |
C8A | 0.046 (2) | 0.059 (3) | 0.061 (3) | −0.003 (2) | 0.004 (2) | 0.010 (2) |
C8 | 0.046 (2) | 0.059 (3) | 0.053 (3) | 0.002 (2) | 0.0070 (19) | 0.0067 (19) |
C21 | 0.081 (4) | 0.132 (5) | 0.071 (3) | −0.004 (4) | −0.017 (3) | 0.019 (3) |
C22 | 0.103 (4) | 0.088 (4) | 0.087 (4) | −0.020 (3) | −0.003 (3) | 0.028 (3) |
C51 | 0.071 (3) | 0.107 (5) | 0.092 (4) | 0.033 (3) | 0.012 (3) | −0.009 (3) |
C71 | 0.066 (3) | 0.093 (4) | 0.056 (3) | 0.010 (3) | −0.008 (2) | 0.004 (3) |
C81 | 0.051 (3) | 0.078 (4) | 0.062 (3) | 0.011 (2) | 0.006 (2) | 0.009 (2) |
C82 | 0.067 (3) | 0.089 (4) | 0.115 (4) | 0.003 (3) | 0.015 (3) | −0.025 (3) |
O1—C8A | 1.382 (5) | C7—C8 | 1.392 (6) |
O1—C2 | 1.472 (5) | C8A—C8 | 1.381 (6) |
O5—C5 | 1.357 (5) | C8—C81 | 1.504 (6) |
O5—C51 | 1.450 (6) | C21—H211 | 0.95 |
O7—C7 | 1.365 (5) | C21—H212 | 0.95 |
O7—C71 | 1.426 (5) | C21—H213 | 0.95 |
O81—C81 | 1.207 (5) | C22—H221 | 0.95 |
C2—C22 | 1.501 (7) | C22—H222 | 0.95 |
C2—C3 | 1.507 (7) | C22—H223 | 0.95 |
C2—C21 | 1.519 (7) | C51—H51 | 0.94 |
C3—C4 | 1.314 (7) | C51—H52 | 0.96 |
C3—H3 | 0.95 | C51—H53 | 0.95 |
C4A—C8A | 1.399 (6) | C71—H71 | 0.95 |
C4A—C5 | 1.400 (6) | C71—H72 | 0.95 |
C4A—C4 | 1.454 (6) | C71—H73 | 0.95 |
C4—H4 | 0.95 | C81—C82 | 1.504 (7) |
C5—C6 | 1.372 (6) | C82—H82 | 0.95 |
C6—C7 | 1.396 (6) | C82—H83 | 0.94 |
C6—H6 | 0.95 | C82—H84 | 0.95 |
C8A—O1—C2 | 117.2 (3) | C2—C21—H211 | 110 |
C5—O5—C51 | 117.8 (4) | C2—C21—H212 | 110 |
C7—O7—C71 | 118.8 (3) | H211—C21—H212 | 110 |
O1—C2—C22 | 107.8 (4) | C2—C21—H213 | 109 |
O1—C2—C3 | 109.9 (4) | H211—C21—H213 | 109 |
C22—C2—C3 | 112.1 (4) | H212—C21—H213 | 109 |
O1—C2—C21 | 103.6 (4) | C2—C22—H221 | 109 |
C22—C2—C21 | 110.8 (5) | C2—C22—H222 | 110 |
C3—C2—C21 | 112.2 (5) | H221—C22—H222 | 109 |
C4—C3—C2 | 121.4 (4) | C2—C22—H223 | 110 |
C4—C3—H3 | 119 | H221—C22—H223 | 109 |
C2—C3—H3 | 119 | H222—C22—H223 | 110 |
C8A—C4A—C5 | 117.2 (4) | O5—C51—H51 | 110 |
C8A—C4A—C4 | 117.5 (4) | O5—C51—H52 | 109 |
C5—C4A—C4 | 125.3 (4) | H51—C51—H52 | 110 |
C3—C4—C4A | 120.5 (4) | O5—C51—H53 | 109 |
C3—C4—H4 | 120 | H51—C51—H53 | 110 |
C4A—C4—H4 | 120 | H52—C51—H53 | 109 |
O5—C5—C6 | 123.7 (4) | O7—C71—H71 | 109 |
O5—C5—C4A | 114.3 (4) | O7—C71—H72 | 110 |
C6—C5—C4A | 121.9 (4) | H71—C71—H72 | 109 |
C5—C6—C7 | 118.8 (4) | O7—C71—H73 | 110 |
C5—C6—H6 | 121 | H71—C71—H73 | 110 |
C7—C6—H6 | 121 | H72—C71—H73 | 110 |
O7—C7—C8 | 114.5 (4) | O81—C81—C8 | 121.3 (5) |
O7—C7—C6 | 123.9 (4) | O81—C81—C82 | 123.4 (5) |
C8—C7—C6 | 121.6 (4) | C8—C81—C82 | 115.2 (4) |
C8—C8A—O1 | 116.6 (4) | C81—C82—H82 | 109 |
C8—C8A—C4A | 122.7 (4) | C81—C82—H83 | 109 |
O1—C8A—C4A | 120.6 (4) | H82—C82—H83 | 110 |
C8A—C8—C7 | 117.7 (4) | C81—C82—H84 | 109 |
C8A—C8—C81 | 121.9 (4) | H82—C82—H84 | 110 |
C7—C8—C81 | 120.1 (4) | H83—C82—H84 | 110 |
C8A—O1—C2—C22 | −81.1 (5) | C5—C6—C7—C8 | −0.8 (7) |
C8A—O1—C2—C3 | 41.3 (5) | C2—O1—C8A—C8 | 155.5 (4) |
C8A—O1—C2—C21 | 161.4 (4) | C2—O1—C8A—C4A | −28.8 (6) |
O1—C2—C3—C4 | −28.8 (7) | C5—C4A—C8A—C8 | −2.8 (6) |
C22—C2—C3—C4 | 91.1 (6) | C4—C4A—C8A—C8 | 175.4 (4) |
C21—C2—C3—C4 | −143.5 (5) | C5—C4A—C8A—O1 | −178.1 (4) |
C2—C3—C4—C4A | 2.4 (8) | C4—C4A—C8A—O1 | 0.1 (6) |
C8A—C4A—C4—C3 | 13.5 (7) | O1—C8A—C8—C7 | 177.4 (4) |
C5—C4A—C4—C3 | −168.5 (5) | C4A—C8A—C8—C7 | 1.9 (6) |
C51—O5—C5—C6 | −1.8 (6) | O1—C8A—C8—C81 | −7.8 (6) |
C51—O5—C5—C4A | 178.6 (4) | C4A—C8A—C8—C81 | 176.7 (4) |
C8A—C4A—C5—O5 | −178.5 (4) | O7—C7—C8—C8A | 178.2 (4) |
C4—C4A—C5—O5 | 3.5 (7) | C6—C7—C8—C8A | 0.0 (6) |
C8A—C4A—C5—C6 | 1.9 (6) | O7—C7—C8—C81 | 3.3 (6) |
C4—C4A—C5—C6 | −176.1 (4) | C6—C7—C8—C81 | −174.9 (4) |
O5—C5—C6—C7 | −179.8 (4) | C8A—C8—C81—O81 | 98.2 (6) |
C4A—C5—C6—C7 | −0.2 (6) | C7—C8—C81—O81 | −87.2 (6) |
C71—O7—C7—C8 | 175.6 (4) | C8A—C8—C81—C82 | −80.5 (5) |
C71—O7—C7—C6 | −6.2 (6) | C7—C8—C81—C82 | 94.2 (5) |
C5—C6—C7—O7 | −178.9 (4) |
Experimental details
Crystal data | |
Chemical formula | C15H18O4 |
Mr | 262.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.2233 (19), 10.354 (3), 18.825 (2) |
β (°) | 91.334 (19) |
V (Å3) | 1407.5 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.35 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2698, 2486, 1106 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.224, 1.39 |
No. of reflections | 2486 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.31 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999a), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1999b), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON for Windows (Spek, 1999), TEXSAN for Windows.
The hexane-extracted components of the fruit of the indiginous Australian tree Melicope ellyrana (Hartley, 1981) resulted in the isolation of a number of flavonoids, and the crystal structures of two of these, i.e. pachypodol [4',5-dihydroxy-3,3',7-trimethoxyflavone; Smith, Wang et al., 2001] and 4',5-dihydroxy-3,3',8-trimethoxy-7-(3-methylbut-2-enyloxy)flavone (Smith, Bartley et al., 2001), have been reported. In addition to these, several substituted α-chromenes have been isolated, including the title compound, 1-(5,7-dimethoxy-2,2-dimethyl-2H-1-benzopyran-8-yl)ethanone, (I) (alloevodionol methyl ether: CA Registry No. 31367–55-2). This compound was first isolated from Evodia elleryana (Jones & Wright, 1946) and from Medicosma cunninghamii, its trivial name being given, along with the parent alloevodionol by Sutherland (1949). It was also isolated from Melicope simplex (Briggs & Locker, 1950), while more recently, a total of 18 variants of 2,2-dimethyl-substituted α-chromenes, including (I), were identified in the leaves of M. ptelefolia Kamperdick et al. (1997). Interest in the chromenes, such as (I) and its variants, has also resulted in a number of patent applications for synthetic procedures, e.g. Nakayama et al. (1979).
The crystal structure of (I) (Fig. 1) shows the 2,2-dimethyl-2H-1-benzopyran moiety with the methoxy substituents at C5 and C7 being close to coplanarity with the aromatic ring [torsion angles C6—C5—O5—C51 - 1.8 (6)° and C6—C7—O7—C71 - 6.2 (6)°]. In contrast, the acetyl group is almost perpendicular to the ring [torsion angle C7—C8—C81—C82 94.2 (5)°]. As might be expected for this type of compound, there are no significant intermolecular associations involved in the packing in the unit cell.