Experimental. Crystal data. C 20 H 26 O 4 M r = Orthorhombic, P a = (1) Å b = (2) Å c = 13.

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Redetermination and absolute configuration of 6-hydroxysalvinolone Hoong-Kun Fun, a * Ching Kheng Quah a and Suchada Chantrapromma b } a X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, USM, Penang, Malaysia, and b Crystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand Correspondence hkfun@usm.my Received 8 December 2009; accepted 10 December 2009 Experimental Crystal data C 20 H 26 O 4 M r = Orthorhombic, P a = (1) Å b = (2) Å c = (2) Å V = (4) Å 3 Z =4 Cu K radiation = 0.70 mm 1 T = 100 K mm Key indicators: single-crystal X-ray study; T = 100 K; mean (C C) = Å; R factor = 0.033; wr factor = 0.089; data-to-parameter ratio = 8.3. The crystal structure of the title compound [systematic name: 5,6,10-trihydroxy-7-isopropyl-1,1,4a-trimethyl-2,3,4,4a-tetra hydrophenanthren-9(1h)-one], C 20 H 26 O 4, has been reported previously [Salae et al. (2009). Acta Cryst. E65, o2379 o2380], but the absolute configuration could not be determined as there was no significant anomalous dispersion using data collected with Mo radiation. The absolute configuration has now been determined by refinement of the Flack parameter with data collected using Cu radiation. The absolute configuration at position 4a of the diterpenoid is (R)-methyl; other features of the molecule and its crystal packing are similar to those previously described. Related literature For background to diterpenes, see: Fraga et al. (2005); Hueso- Rodríguez et al. (1983) and Topcu & Ulubelen (1996). For the previous determination, see: Salae et al. (2009). For bondlength data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For puckering parameters, see: Cremer & Pople (1975). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986). Thomson Reuters ResearcherID: A Thomson Reuters ResearcherID: A } Thomson Reuters ResearcherID: A Additional correspondence author, suchada.c@psu.ac.th Data collection Bruker APEX Duo CCD areadetector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009) T min = 0.790, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 317 parameters H atoms treated by a mixture of independent and constrained refinement Table 1 Hydrogen-bond geometry (Å, ) measured reflections 2622 independent reflections 2581 reflections with I > 2(I) R int = max = 0.22 e Å 3 min = 0.22 e Å 3 Absolute structure: Flack (1983), 1609 Friedel pairs Flack parameter: 0.06 (17) D HA D H HA DA D HA O1 H1O1O (2) 1.93 (2) (14) 128 (2) O3 H1O3O2 i 0.85 (3) 1.87 (3) (14) 167 (2) O4 H1O4O (3) 2.04 (3) (14) 123 (2) C14 H14AO3 ii (17) (17) (17) (14) C15 H15AO2 i (17) 132 C18 H18BO (18) (18) (19) (13) C19 H19AO (19) (19) (2) (14) C20 H20CO (2) (19) (18) (14) Symmetry codes: (i) x þ 1 2 ; y þ 1; z þ 1 2 ; (ii) x þ 1 2 ; y þ 1; z 1 2. Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009). The authors thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/ Mr Abdul Wahab Salae is acknowledged for supplying the sample of 6- hydroxysalvinolone. o146 Fun et al. doi: /s

2 organic compounds Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2711). References 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. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, Flack, H. D. (1983). Acta Cryst. A39, Fraga, B. M., Díaz, C. E., Guadaño, A. & González-Coloma, A. (2005). J. Agric. Food. Chem.. 53, Hueso-Rodríguez, J. A., Jimeno, M. L., Rodríguez, B., Savona, G. & Bruno, M. (1983). Phytochemistry, 22, Salae, A. W., Chantrapromma, S., Fun, H.-K. & Karalai, C. (2009). Acta Cryst. E65, o2379 o2380. Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, Topcu, G. & Ulubelen, A. (1996). J. Nat. Prod. 59, Fun et al. C 20 H 26 O 4 o147

3 supporting information [doi: /s ] Redetermination and absolute configuration of 6-hydroxysalvinolone Hoong-Kun Fun, Ching Kheng Quah and Suchada Chantrapromma S1. Comment The title diterpenoid compound (I) known as 6-hydroxysalvinolone (Topcu & Ulubelen, 1996) or 14-deoxycoleon U (Fraga et al., 2005; Hueso-Rodríguez et al., 1983), was isolated from the roots of Premna obtusifolia, a Thai manglove plant which was collected from Satun province in the Southern part of Thailand. Its crystal structure has been reported (Salae et al., 2009) but the absolute configuration could not be determined due to no large anomalous dispersion using a data set collected with Mo radiation. Data on the same sample was recollected using Cu radiation with our newlyinstalled Bruker Apex-Duo CCD diffractometer and the absolute configuration at atom C10 (or the 4a position) was determined as (R)-methyl making use of the large anomalous scattering of Cu Kα X-radiation with the Flack parameter being refined to 0.06 (17). We report herein the crystal structure of (I) determined from the Cu data. Fig. 1 shows the molecular structure of (I); the ring conformations, bond lengths and angles are almost identical to those previously described (Salae et al., 2009). Fig. 2 shows the crystal packing of (I), intermolecular O H O hydrogen bonds and weak C H O interactions (Table 1) linked the molecules into infinite one dimensional screw chains along the [0 0 1] direction. This feature and also the O H O hydrogen bonds and weak C H O interactions are also similar to those in the previous report by Salae et al. (2009). S2. Experimental The compound was isolated and the crystal grown as reported by Salae et al. (2009). S3. Refinement The H atom attached to C15 was placed in a calculated position with d(c H) = 0.96 Å and the U iso values was constrained to be 1.2U eq of the carrier atom. The remaining H atoms were located from the difference map and isotropically refined. The highest residual electron density peak is located at 0.73 Å from C13 and the deepest hole is located at 0.50 Å from O Friedel pairs were used to determine the absolute configuration. sup-1

4 Figure 1 The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. Intramolecular hydrogen bonds are shown as dashed lines. sup-2

5 Figure 2 The crystal packing of (I) viewed along the a axis, showing screw chains along the [0 0 1] direction. Hydrogen bonds are shown as dashed lines. 5,6,10-trihydroxy-7-isopropyl-1,1,4a-trimethyl-2,3,4,4a-tetrahydrophenanthren- 9(1H)-one Crystal data C 20 H 26 O 4 M r = Orthorhombic, P Hall symbol: P 2ac 2ab a = (1) Å b = (2) Å c = (2) Å V = (4) Å 3 Z = 4 F(000) = 712 D x = Mg m 3 Cu Kα radiation, λ = Å Cell parameters from 2622 reflections θ = µ = 0.70 mm 1 T = 100 K Block, colorless mm sup-3

6 Data collection Bruker APEX Duo CCD area-detector diffractometer Radiation source: sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2009) T min = 0.790, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 317 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map 6410 measured reflections 2622 independent reflections 2581 reflections with I > 2σ(I) R int = θ max = 62.5, θ min = 5.7 h = k = l = Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.062P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.22 e Å 3 Δρ min = 0.22 e Å 3 Absolute structure: Flack (1983), 1609 Friedel pairs Absolute structure parameter: 0.06 (17) Special details Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at (1) K. 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq O (14) (8) (8) (3) H1O (3) (19) (17) (6)* O (15) (7) (7) (3) O (12) (8) (7) (2) H1O (3) (2) (17) (6)* O (13) (7) (8) (3) H1O (3) (19) (19) (7)* C (17) (11) (11) (3) H1A (2) (15) (15) (5)* H1B (2) (15) (15) (5)* C (16) (11) (11) (3) H2A (2) (17) (16) (5)* H2B (2) (13) (14) (4)* sup-4

7 C (16) (11) (11) (3) H3A (18) (14) (12) (4)* H3B (2) (15) (15) (5)* C (18) (10) (10) (3) C (16) (10) (11) (3) C (17) (11) (10) (3) C (17) (11) (10) (3) C (16) (10) (10) (3) C (14) (10) (10) (3) C (15) (10) (10) (3) C (15) (11) (10) (3) C (15) (11) (9) (3) C (15) (10) (10) (3) C (16) (10) (10) (3) H14A (2) (13) (12) (4)* C (17) (10) (10) (3) H15A * C (2) (12) (14) (4) H16A (2) (18) (18) (7)* H16B (19) (16) (15) (5)* H16C (2) (16) (16) (5)* C (16) (11) (13) (4) H17A (2) (15) (16) (5)* H17B (2) (16) (16) (5)* H17C (18) (14) (13) (4)* C (17) (11) (12) (3) H18A (2) (14) (14) (4)* H18B (19) (14) (13) (4)* H18C (19) (16) (14) (5)* C (17) (12) (12) (4) H19A (2) (14) (14) (5)* H19B (2) (14) (15) (5)* H19C (18) (14) (13) (4)* C (15) (11) (11) (3) H20A (2) (14) (15) (5)* H20B (18) (15) (13) (4)* H20C (2) (14) (15) (5)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (7) (5) (5) (5) (5) (4) O (7) (5) (5) (5) (5) (4) O (6) (5) (5) (5) (4) (4) O (6) (5) (5) (5) (5) (4) C (8) (7) (8) (6) (6) (6) C (8) (7) (7) (6) (6) (6) C (7) (7) (8) (5) (6) (6) sup-5

8 C (7) (7) (7) (6) (6) (5) C (7) (7) (7) (6) (6) (5) C (8) (7) (7) (6) (6) (5) C (8) (7) (7) (7) (6) (5) C (7) (7) (7) (6) (6) (5) C (7) (7) (7) (5) (6) (5) C (7) (7) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (5) C (7) (7) (7) (6) (6) (5) C (6) (7) (7) (6) (6) (5) C (7) (6) (7) (6) (6) (6) C (8) (7) (7) (6) (6) (5) C (12) (8) (9) (8) (9) (7) C (8) (7) (9) (7) (7) (7) C (8) (7) (8) (6) (7) (6) C (9) (8) (8) (7) (7) (6) C (7) (7) (7) (6) (6) (6) Geometric parameters (Å, º) O1 C (17) C9 C (2) O1 H1O (3) C9 C (18) O2 C (18) C10 C (2) O3 C (16) C11 C (2) O3 H1O (3) C12 C (19) O4 C (16) C13 C (2) O4 H1O (3) C13 C (17) C1 C (2) C14 H14A (18) C1 C (2) C15 C (2) C1 H1A 1.02 (2) C15 C (2) C1 H1B 0.94 (2) C15 H15A C2 C (2) C16 H16A 1.04 (2) C2 H2A 1.00 (2) C16 H16B 0.99 (2) C2 H2B 0.99 (2) C16 H16C 0.96 (2) C3 C (2) C17 H17A 1.02 (2) C3 H3A (19) C17 H17B 0.98 (2) C3 H3B 0.96 (2) C17 H17C (18) C4 C (2) C18 H18A 0.98 (2) C4 C (18) C18 H18B (19) C4 C (2) C18 H18C 0.97 (2) C5 C (2) C19 H19A (19) C5 C (19) C19 H19B 1.00 (2) C6 C (19) C19 H19C (18) C7 C (2) C20 H20A 0.97 (2) C8 C (19) C20 H20B (19) C8 C (19) C20 H20C 1.00 (2) C6 O1 H1O (15) O4 C11 C (12) sup-6

9 C12 O3 H1O (16) O4 C11 C (12) C11 O4 H1O (17) C9 C11 C (12) C2 C1 C (12) O3 C12 C (12) C2 C1 H1A (11) O3 C12 C (12) C10 C1 H1A (11) C13 C12 C (12) C2 C1 H1B (12) C14 C13 C (13) C10 C1 H1B (12) C14 C13 C (13) H1A C1 H1B (17) C12 C13 C (12) C3 C2 C (12) C13 C14 C (13) C3 C2 H2A (12) C13 C14 H14A (10) C1 C2 H2A (12) C8 C14 H14A (10) C3 C2 H2B (10) C16 C15 C (12) C1 C2 H2B (11) C16 C15 C (14) H2A C2 H2B (16) C13 C15 C (13) C2 C3 C (12) C16 C15 H15A C2 C3 H3A (10) C13 C15 H15A C4 C3 H3A (10) C17 C15 H15A C2 C3 H3B (12) C15 C16 H16A (13) C4 C3 H3B (12) C15 C16 H16B (12) H3A C3 H3B (15) H16A C16 H16B (16) C18 C4 C (13) C15 C16 H16C (13) C18 C4 C (12) H16A C16 H16C (18) C5 C4 C (12) H16B C16 H16C (17) C18 C4 C (12) C15 C17 H17A (11) C5 C4 C (12) C15 C17 H17B (12) C3 C4 C (12) H17A C17 H17B (16) C6 C5 C (12) C15 C17 H17C (10) C6 C5 C (13) H17A C17 H17C (15) C10 C5 C (12) H17B C17 H17C (16) C5 C6 O (13) C4 C18 H18A (11) C5 C6 C (13) C4 C18 H18B (10) O1 C6 C (12) H18A C18 H18B (15) O2 C7 C (12) C4 C18 H18C (11) O2 C7 C (12) H18A C18 H18C (16) C8 C7 C (12) H18B C18 H18C (16) C14 C8 C (12) C4 C19 H19A (11) C14 C8 C (12) C4 C19 H19B (12) C9 C8 C (12) H19A C19 H19B (16) C11 C9 C (12) C4 C19 H19C (10) C11 C9 C (12) H19A C19 H19C (15) C8 C9 C (12) H19B C19 H19C (14) C5 C10 C (11) C10 C20 H20A (11) C5 C10 C (12) C10 C20 H20B (11) C9 C10 C (12) H20A C20 H20B (15) C5 C10 C (12) C10 C20 H20C (11) C9 C10 C (12) H20A C20 H20C (16) C1 C10 C (11) H20B C20 H20C (16) sup-7

10 C10 C1 C2 C (17) C6 C5 C10 C (16) C1 C2 C3 C (16) C4 C5 C10 C (16) C2 C3 C4 C (12) C11 C9 C10 C (12) C2 C3 C4 C (16) C8 C9 C10 C5 7.9 (2) C2 C3 C4 C (15) C11 C9 C10 C (18) C18 C4 C5 C (19) C8 C9 C10 C (13) C3 C4 C5 C (14) C11 C9 C10 C (16) C19 C4 C5 C (2) C8 C9 C10 C (15) C18 C4 C5 C (15) C2 C1 C10 C (17) C3 C4 C5 C (19) C2 C1 C10 C (13) C19 C4 C5 C (14) C2 C1 C10 C (15) C10 C5 C6 O (14) C8 C9 C11 O (13) C4 C5 C6 O1 2.6 (2) C10 C9 C11 O4 1.6 (2) C10 C5 C6 C7 9.0 (2) C8 C9 C11 C (2) C4 C5 C6 C (15) C10 C9 C11 C (13) C5 C6 C7 O (14) O4 C11 C12 O3 2.3 (2) O1 C6 C7 O2 2.1 (2) C9 C11 C12 O (13) C5 C6 C7 C8 2.2 (3) O4 C11 C12 C (12) O1 C6 C7 C (12) C9 C11 C12 C (2) O2 C7 C8 C (2) O3 C12 C13 C (14) C6 C7 C8 C (14) C11 C12 C13 C (2) O2 C7 C8 C (16) O3 C12 C13 C (2) C6 C7 C8 C9 1.6 (2) C11 C12 C13 C (13) C14 C8 C9 C (2) C12 C13 C14 C8 0.1 (2) C7 C8 C9 C (14) C15 C13 C14 C (14) C14 C8 C9 C (13) C9 C8 C14 C (2) C7 C8 C9 C (2) C7 C8 C14 C (14) C6 C5 C10 C (2) C14 C13 C15 C (2) C4 C5 C10 C (12) C12 C13 C15 C (15) C6 C5 C10 C (15) C14 C13 C15 C (17) C4 C5 C10 C (18) C12 C13 C15 C (18) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O1 H1O1 O (2) 1.93 (2) (14) 128 (2) O3 H1O3 O2 i 0.85 (3) 1.87 (3) (14) 167 (2) O4 H1O4 O (3) 2.04 (3) (14) 123 (2) C14 H14A O3 ii (17) (17) (17) (14) C15 H15A O2 i (17) 132 C18 H18B O (18) (18) (19) (13) C19 H19A O (19) (19) (2) (14) C20 H20C O (2) (19) (18) (14) Symmetry codes: (i) x+1/2, y+1, z+1/2; (ii) x+1/2, y+1, z 1/2. sup-8