Acta Cryst. (2010). E66, o1441 [ doi:10.1107/S1600536810018374 ]
The title chromene, C14H16O4, was isolated from the stems of Polyalthia plagioneura Diels. The molecular structure is stabilized by an intramolecular O-H
O hydrogen bond, which generates an S(6) ring. In the crystal, the molecules are linked by C-HO interactions, generating [010] chains.
Air-dried stems of Polyalthia plagioneura (20 kg) were ground and percolated (4 × 3 h) with 75% EtOH at 60°C, which was suspended in 5 L water and then partitioned with chloroform, ethyl acetate and n-BuOH, successively, yielding a chloroform extract, an ethyl acetate extract and a n-BuOH extract, respectively. The chloroform extract was subjected to a silica gel CC column using petroleum ether as first eluent and then increasing the polarity with EtOAc, to afford 33 fractions. Fraction 5 was further separated by column chromatography with a gradient of chloroform–ether–EtOAc to give the title compound. The crude product was recrystallised from ethyl acetate to yield colourless blocks of (I).
H atoms bonded to C atoms were palced in geometrically calculated position and were refined using a riding model, with Uiso(H) = 1.2 Ueq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O—H distances fixed as initially found and with Uiso(H) values set at 1.5 Ueq(O).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hb5429fig1thm.gif)
| Fig. 1. View of the title compound with displacement ellipsoids drawn at the 30% probability level. |
| C14H16O4 | Z = 2 |
| Mr = 248.28 | F(000) = 264 |
| Triclinic, P1 | Dx = 1.297 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.3797 (9) Å | Cell parameters from 1208 reflections |
| b = 8.0066 (10) Å | θ = 2.6–24.1° |
| c = 11.2878 (14) Å | µ = 0.10 mm−1 |
| α = 77.948 (1)° | T = 298 K |
| β = 77.411 (1)° | Block, colourless |
| γ = 84.465 (2)° | 0.45 × 0.40 × 0.39 mm |
| V = 635.67 (14) Å3 |
| Bruker SMART CCD diffractometer | 2217 independent reflections |
| Radiation source: fine-focus sealed tube | 1361 reflections with I > 2σ(I) |
| graphite | Rint = 0.019 |
| ω scans | θmax = 25.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −8→8 |
| Tmin = 0.959, Tmax = 0.964 | k = −8→9 |
| 3335 measured reflections | l = −13→13 |
| 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.159 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0801P)2] where P = (Fo2 + 2Fc2)/3 |
| 2217 reflections | (Δ/σ)max < 0.001 |
| 167 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.23 e Å−3 |
| C14H16O4 | γ = 84.465 (2)° |
| Mr = 248.28 | V = 635.67 (14) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.3797 (9) Å | Mo Kα radiation |
| b = 8.0066 (10) Å | µ = 0.10 mm−1 |
| c = 11.2878 (14) Å | T = 298 K |
| α = 77.948 (1)° | 0.45 × 0.40 × 0.39 mm |
| β = 77.411 (1)° |
| Bruker SMART CCD diffractometer | 2217 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1361 reflections with I > 2σ(I) |
| Tmin = 0.959, Tmax = 0.964 | Rint = 0.019 |
| 3335 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
| wR(F2) = 0.159 | Δρmax = 0.26 e Å−3 |
| S = 1.08 | Δρmin = −0.23 e Å−3 |
| 2217 reflections | Absolute structure: ? |
| 167 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 > 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 | 0.1836 (2) | 0.20248 (18) | 0.25325 (13) | 0.0529 (5) | |
| O2 | 0.2390 (2) | 0.76852 (19) | 0.29434 (15) | 0.0659 (5) | |
| H2 | 0.2508 | 0.8241 | 0.3453 | 0.099* | |
| O3 | 0.2742 (3) | 0.8220 (2) | 0.49648 (17) | 0.0720 (6) | |
| O4 | 0.2615 (2) | 0.30717 (19) | 0.63521 (13) | 0.0604 (5) | |
| C1 | 0.2377 (3) | 0.2453 (3) | 0.11859 (19) | 0.0534 (7) | |
| C2 | 0.2004 (4) | 0.4317 (3) | 0.0732 (2) | 0.0584 (7) | |
| H2A | 0.1813 | 0.4684 | −0.0072 | 0.070* | |
| C3 | 0.1938 (3) | 0.5467 (3) | 0.1434 (2) | 0.0546 (7) | |
| H3 | 0.1751 | 0.6624 | 0.1116 | 0.066* | |
| C4 | 0.2160 (3) | 0.4900 (3) | 0.27044 (19) | 0.0431 (6) | |
| C5 | 0.2349 (3) | 0.6020 (3) | 0.3466 (2) | 0.0451 (6) | |
| C6 | 0.2498 (3) | 0.5431 (3) | 0.47159 (19) | 0.0419 (5) | |
| C7 | 0.2432 (3) | 0.3632 (3) | 0.51639 (19) | 0.0429 (6) | |
| C8 | 0.2232 (3) | 0.2528 (3) | 0.44272 (19) | 0.0433 (5) | |
| H8 | 0.2184 | 0.1360 | 0.4741 | 0.052* | |
| C9 | 0.2101 (3) | 0.3175 (3) | 0.32112 (19) | 0.0411 (5) | |
| C10 | 0.1212 (4) | 0.1353 (3) | 0.0740 (2) | 0.0695 (8) | |
| H10A | 0.1443 | 0.0172 | 0.1090 | 0.104* | |
| H10B | 0.1534 | 0.1517 | −0.0146 | 0.104* | |
| H10C | −0.0081 | 0.1672 | 0.0992 | 0.104* | |
| C11 | 0.4434 (4) | 0.1947 (4) | 0.0849 (2) | 0.0791 (8) | |
| H11A | 0.5131 | 0.2610 | 0.1191 | 0.119* | |
| H11B | 0.4831 | 0.2157 | −0.0035 | 0.119* | |
| H11C | 0.4640 | 0.0754 | 0.1176 | 0.119* | |
| C12 | 0.2686 (3) | 0.6685 (3) | 0.5448 (2) | 0.0501 (6) | |
| C13 | 0.2816 (3) | 0.6241 (3) | 0.6777 (2) | 0.0598 (7) | |
| H13A | 0.2903 | 0.7267 | 0.7070 | 0.090* | |
| H13B | 0.3900 | 0.5500 | 0.6867 | 0.090* | |
| H13C | 0.1727 | 0.5670 | 0.7251 | 0.090* | |
| C14 | 0.2647 (4) | 0.1275 (3) | 0.6819 (2) | 0.0717 (8) | |
| H14A | 0.1481 | 0.0845 | 0.6811 | 0.108* | |
| H14B | 0.2846 | 0.1051 | 0.7652 | 0.108* | |
| H14C | 0.3635 | 0.0720 | 0.6310 | 0.108* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0793 (12) | 0.0426 (10) | 0.0413 (9) | −0.0099 (8) | −0.0147 (8) | −0.0124 (7) |
| O2 | 0.0982 (14) | 0.0346 (10) | 0.0677 (11) | −0.0076 (8) | −0.0267 (10) | −0.0039 (8) |
| O3 | 0.1000 (15) | 0.0432 (11) | 0.0818 (13) | −0.0087 (9) | −0.0265 (10) | −0.0213 (9) |
| O4 | 0.0955 (14) | 0.0452 (10) | 0.0444 (9) | −0.0021 (8) | −0.0218 (8) | −0.0104 (8) |
| C1 | 0.0680 (18) | 0.0559 (16) | 0.0383 (12) | −0.0089 (12) | −0.0100 (11) | −0.0119 (11) |
| C2 | 0.0750 (18) | 0.0597 (17) | 0.0403 (13) | −0.0108 (13) | −0.0151 (12) | −0.0023 (12) |
| C3 | 0.0694 (17) | 0.0430 (14) | 0.0500 (14) | −0.0079 (11) | −0.0164 (12) | 0.0010 (11) |
| C4 | 0.0455 (14) | 0.0384 (13) | 0.0461 (13) | −0.0026 (10) | −0.0111 (10) | −0.0077 (10) |
| C5 | 0.0464 (14) | 0.0335 (12) | 0.0547 (14) | −0.0029 (9) | −0.0110 (10) | −0.0059 (10) |
| C6 | 0.0422 (13) | 0.0392 (13) | 0.0467 (13) | −0.0003 (10) | −0.0109 (10) | −0.0126 (10) |
| C7 | 0.0487 (14) | 0.0425 (13) | 0.0374 (12) | −0.0004 (10) | −0.0089 (10) | −0.0087 (10) |
| C8 | 0.0545 (15) | 0.0321 (12) | 0.0432 (12) | −0.0029 (10) | −0.0097 (10) | −0.0069 (10) |
| C9 | 0.0452 (14) | 0.0394 (13) | 0.0410 (12) | −0.0041 (10) | −0.0089 (10) | −0.0114 (10) |
| C10 | 0.097 (2) | 0.0722 (19) | 0.0490 (14) | −0.0204 (15) | −0.0228 (14) | −0.0173 (13) |
| C11 | 0.076 (2) | 0.092 (2) | 0.0690 (18) | −0.0014 (15) | −0.0054 (15) | −0.0255 (16) |
| C12 | 0.0460 (14) | 0.0452 (15) | 0.0628 (15) | −0.0024 (11) | −0.0109 (11) | −0.0191 (12) |
| C13 | 0.0643 (17) | 0.0611 (17) | 0.0636 (16) | −0.0029 (12) | −0.0148 (12) | −0.0322 (13) |
| C14 | 0.113 (2) | 0.0547 (17) | 0.0450 (14) | −0.0050 (15) | −0.0215 (14) | 0.0016 (12) |
| O1—C9 | 1.367 (2) | C6—C12 | 1.460 (3) |
| O1—C1 | 1.460 (2) | C7—C8 | 1.371 (3) |
| O2—C5 | 1.341 (2) | C8—C9 | 1.383 (3) |
| O2—H2 | 0.8200 | C8—H8 | 0.9300 |
| O3—C12 | 1.237 (3) | C10—H10A | 0.9600 |
| O4—C7 | 1.354 (2) | C10—H10B | 0.9600 |
| O4—C14 | 1.424 (3) | C10—H10C | 0.9600 |
| C1—C2 | 1.493 (3) | C11—H11A | 0.9600 |
| C1—C10 | 1.513 (3) | C11—H11B | 0.9600 |
| C1—C11 | 1.519 (3) | C11—H11C | 0.9600 |
| C2—C3 | 1.326 (3) | C12—C13 | 1.490 (3) |
| C2—H2A | 0.9300 | C13—H13A | 0.9600 |
| C3—C4 | 1.451 (3) | C13—H13B | 0.9600 |
| C3—H3 | 0.9300 | C13—H13C | 0.9600 |
| C4—C9 | 1.381 (3) | C14—H14A | 0.9600 |
| C4—C5 | 1.401 (3) | C14—H14B | 0.9600 |
| C5—C6 | 1.415 (3) | C14—H14C | 0.9600 |
| C6—C7 | 1.426 (3) | ||
| C9—O1—C1 | 118.89 (16) | O1—C9—C4 | 120.78 (18) |
| C5—O2—H2 | 109.5 | O1—C9—C8 | 116.67 (18) |
| C7—O4—C14 | 118.00 (17) | C4—C9—C8 | 122.51 (19) |
| O1—C1—C2 | 110.59 (18) | C1—C10—H10A | 109.5 |
| O1—C1—C10 | 104.22 (17) | C1—C10—H10B | 109.5 |
| C2—C1—C10 | 112.3 (2) | H10A—C10—H10B | 109.5 |
| O1—C1—C11 | 106.92 (19) | C1—C10—H10C | 109.5 |
| C2—C1—C11 | 111.2 (2) | H10A—C10—H10C | 109.5 |
| C10—C1—C11 | 111.3 (2) | H10B—C10—H10C | 109.5 |
| C3—C2—C1 | 122.2 (2) | C1—C11—H11A | 109.5 |
| C3—C2—H2A | 118.9 | C1—C11—H11B | 109.5 |
| C1—C2—H2A | 118.9 | H11A—C11—H11B | 109.5 |
| C2—C3—C4 | 119.3 (2) | C1—C11—H11C | 109.5 |
| C2—C3—H3 | 120.3 | H11A—C11—H11C | 109.5 |
| C4—C3—H3 | 120.3 | H11B—C11—H11C | 109.5 |
| C9—C4—C5 | 117.9 (2) | O3—C12—C6 | 119.8 (2) |
| C9—C4—C3 | 118.6 (2) | O3—C12—C13 | 116.2 (2) |
| C5—C4—C3 | 123.4 (2) | C6—C12—C13 | 124.0 (2) |
| O2—C5—C4 | 116.2 (2) | C12—C13—H13A | 109.5 |
| O2—C5—C6 | 121.7 (2) | C12—C13—H13B | 109.5 |
| C4—C5—C6 | 122.1 (2) | H13A—C13—H13B | 109.5 |
| C5—C6—C7 | 116.38 (19) | C12—C13—H13C | 109.5 |
| C5—C6—C12 | 118.6 (2) | H13A—C13—H13C | 109.5 |
| C7—C6—C12 | 125.0 (2) | H13B—C13—H13C | 109.5 |
| O4—C7—C8 | 121.91 (19) | O4—C14—H14A | 109.5 |
| O4—C7—C6 | 116.15 (18) | O4—C14—H14B | 109.5 |
| C8—C7—C6 | 121.93 (19) | H14A—C14—H14B | 109.5 |
| C7—C8—C9 | 119.2 (2) | O4—C14—H14C | 109.5 |
| C7—C8—H8 | 120.4 | H14A—C14—H14C | 109.5 |
| C9—C8—H8 | 120.4 | H14B—C14—H14C | 109.5 |
| C9—O1—C1—C2 | −36.1 (3) | C5—C6—C7—O4 | 178.63 (19) |
| C9—O1—C1—C10 | −157.02 (19) | C12—C6—C7—O4 | −2.0 (3) |
| C9—O1—C1—C11 | 85.1 (2) | C5—C6—C7—C8 | −0.1 (3) |
| O1—C1—C2—C3 | 25.1 (3) | C12—C6—C7—C8 | 179.2 (2) |
| C10—C1—C2—C3 | 141.0 (2) | O4—C7—C8—C9 | −178.26 (18) |
| C11—C1—C2—C3 | −93.6 (3) | C6—C7—C8—C9 | 0.4 (3) |
| C1—C2—C3—C4 | −2.5 (4) | C1—O1—C9—C4 | 25.4 (3) |
| C2—C3—C4—C9 | −11.4 (3) | C1—O1—C9—C8 | −157.02 (19) |
| C2—C3—C4—C5 | 171.5 (2) | C5—C4—C9—O1 | 177.07 (19) |
| C9—C4—C5—O2 | −179.63 (18) | C3—C4—C9—O1 | −0.1 (3) |
| C3—C4—C5—O2 | −2.6 (3) | C5—C4—C9—C8 | −0.4 (3) |
| C9—C4—C5—C6 | 0.7 (3) | C3—C4—C9—C8 | −177.6 (2) |
| C3—C4—C5—C6 | 177.72 (19) | C7—C8—C9—O1 | −177.73 (18) |
| O2—C5—C6—C7 | 179.90 (18) | C7—C8—C9—C4 | −0.2 (3) |
| C4—C5—C6—C7 | −0.4 (3) | C5—C6—C12—O3 | −1.2 (3) |
| O2—C5—C6—C12 | 0.5 (3) | C7—C6—C12—O3 | 179.5 (2) |
| C4—C5—C6—C12 | −179.84 (19) | C5—C6—C12—C13 | 178.7 (2) |
| C14—O4—C7—C8 | 1.7 (3) | C7—C6—C12—C13 | −0.6 (4) |
| C14—O4—C7—C6 | −177.06 (19) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O3 | 0.82 | 1.75 | 2.479 (2) | 147 |
| C8—H8···O3i | 0.93 | 2.48 | 3.374 (3) | 162 |
| Symmetry codes: (i) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O3 | 0.82 | 1.75 | 2.479 (2) | 147 |
| C8—H8···O3i | 0.93 | 2.48 | 3.374 (3) | 162 |
| Symmetry codes: (i) x, y−1, z. |
This work was supported by the National Natural Science Foundation of China (20862005), the Program for New Century Excellent Talents in Universities (NCET-08-0656) and the University Graduate Student Innovation Science Research Project of Hainan Province (No. Hxwsy2009-10).
Allan, R. D., Correll, R. L. & Wells, R. J. (1969). Tetrahedron Lett. 53, 4669–4672.
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Li, G. L., Zeng, J. F., Song, C. Q. & Zhu, D. Y. (1997). Phytochemistry, 44, 1175–1178.
Manandhar, M. D., Hussaini, F. A., Kapil, R. S. & Shoeb, A. (1985). Phytochemistry, 24, 199–200.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
The title chromene was isolated from plants such as Remirea maritima (Allan et al., 1969), Euodia lunu-ankenda (Manandhar et al., 1985) and Evodia lepta (Li et al., 1997). In our ongoing studies of natural products with biological activity we isolated the chromene from the 75% EtOH extract of the stems of Polyalthia plagioneura, a plant used as a flok medicine which were collected from Bawangling, Hainan Province, P. R. China. We have undertaken the X-ray crystal structure analysis of the title compound in order to establish its molecular structure and relative stereochemistry.
The hydrogen bonds and angles are listed in Table 1.