organic papers
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Sara L. Crockettet al. C16H14O4 doi: 10.1107/S1600536804026819 Acta Cryst.(2004). E60, o2174±o2176 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
Hyperolactone C
Sara L. Crockett,aWolfgang SchuÈhly,bFerdinand Belajc* and Ikhlas A. Khand
aDepartment of Pharmacognosy, School of
Pharmacy, University of Mississippi, Oxford, MS 38677, USA,bInstitute for Pharmacognosy,
Karl-Franzens University Graz, Schubertstr. 1, A-8010 Graz, Austria,cInstitute of Chemistry,
Karl-Franzens University Graz, Schubertstr. 1, A-8010 Graz, Austria, anddNational Center for
Natural Products Research, Research Institute for Pharmaceutical Sciences, University of Missis-sippi, Oxford, MS 38677, USA
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 95 K
Mean(C±C) = 0.009 AÊ Rfactor = 0.068 wRfactor = 0.154 Data-to-parameter ratio = 7.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The crystal structure of a known spirolactone, hyperolactone C [systematic name: (5S,9S )-9-methyl-2-phenyl-9-vinyl-1,7-dioxaspiro[4.4]non-2-ene-4,6-dione], isolated fromHypericum
lloydii (Svenson) P. Adams (Sandhill St John's Wort,
Clusiaceae), native to the southeastern USA, is presented.
Comment
Hypericum lloydii, (Svenson) P. Adams, section Myriandra
(Sandhill St John's Wort, Clusiaceae) is one of 57 species of
Hypericumthat occur in the USA (USDA±NCRS, 2002). This
native low shrub frequently occurs on sandy or eroding granitic soils in dry woods and pinelands, particularly in the Appalachian Mountain region of the southeastern USA (Radfordet al., 1968; Robson, 1996). Fractionation of the di-chloromethane extract of the aerial parts ofH. lloydiihas led to the isolation of the known spirolactone, (ÿ)-hyperolactone C.
This compound was previously isolated (Aramaki et al., 1995) fromH. monogynum(published asH. chinense, section Ascyreia) along with three related structures, hyperolactones A (Tada et al., 1989), B and D (see scheme). The hyper-olactones A, B and C have also been reported from synthesis (Uekiet al., 1998, 2000). This paper represents the ®rst report of this type of spirolactone from a species of Hypericum
sectionMyriandraand the ®rst X-ray crystallographic report for hyperolactone C (Fig. 1). The furan-3-one ring is planar and is inclined at an angle of 9.9 (3) to the plane of the
benzene ring. The furan-2-one ring adopts a conformation intermediate between an envelope and a half-chair.
Experimental
The aerial portions ofH. lloydiiwere collected while in ¯ower, and a voucher specimen was stored with the University of Georgia
Herbarium in Athens, GA. The dried ground aerial parts ofH. lloydii
were extracted with dichloromethane, yielding a crude extract that was subjected to vacuum liquid chromatography. Fractions of 25 ml each were eluted from the column using a gradient from 100% hexane to 100% ethyl acetate, with a ®nal column wash of methanol, and were combined on the basis of similarity of TLC pro®les to give 16 fractions. Fraction 12 (eluted at 20% ethyl acetate) displayed a prominent violet spot in TLC. Upon standing, this fraction yielded a ¯aky green±gold mica-like precipitate, which was then ®ltered and further puri®ed by preparative TLC. Recrystallization from ethyl acetate of the puri®ed material gave 120 mg of crystals, which were subsequently identi®ed using spectroscopic measurements as hyper-olactone C. Crystals suitable for X-ray diffraction were obtained from chloroform. Hyperolactone C was isolated as long clear prismatic crystals (m.p. 370 K). Optical rotation []D(295 K)ÿ270.7(CHCl3,
c0.11). This value differs from that (ÿ356.0, EtOH,c0.02) reported
by Aramakiet al.(1995), but this difference may be attributed to the use of different solvents. EIMS indicated a molecular formula of C16H14O4 (m/z 270.09). UV max absorptions at 304 and 254 nm indicated the presence of a chromophore with extended conjugation. The IR spectrum showed two strong bands indicating carbonyl groups at 1782 and 1705 cmÿ1. Hyperolactone C was poorly soluble in hexane and ethanol, but fully soluble in ethyl acetate, acetone, chloroform and chloroform/methanol (1:1).
Crystal data
C16H14O4 Mr= 270.27 Monoclinic,P21 a= 6.215 (7) AÊ b= 7.491 (7) AÊ c= 14.461 (15) AÊ = 98.68 (8) V= 665.5 (12) AÊ3 Z= 2
Dx= 1.349 Mg mÿ3 MoKradiation Cell parameters from 35
re¯ections = 4.4±10.6 = 0.10 mmÿ1 T= 95 (2) K Prism, colorless 0.420.250.12 mm
Data collection
Stoe four-circle diffractometer !scans
Absorption correction: none 1612 measured re¯ections 1270 independent re¯ections 943 re¯ections withI> 2(I) Rint= 0.087
max= 25.0 h=ÿ7!7 k=ÿ3!8 l=ÿ1!17 3 standard re¯ections
every 100 re¯ections intensity decay: 0.1%
Refinement
Re®nement onF2 R[F2> 2(F2)] = 0.068 wR(F2) = 0.154 S= 1.08 1270 re¯ections 175 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0556P)2 + 0.1091P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.28 e AÊÿ3 min=ÿ0.28 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
O1ÐC2 1.383 (7)
O1ÐC5 1.424 (7)
C2ÐC3 1.348 (9)
C2ÐC21 1.462 (7)
C3ÐC4 1.439 (8)
C4ÐO4 1.225 (7)
C4ÐC5 1.576 (8)
C5ÐC6 1.521 (9)
C5ÐC9 1.551 (9)
C6ÐO6 1.193 (8)
C6ÐO7 1.331 (8)
O7ÐC8 1.482 (9)
C8ÐC9 1.530 (9)
C9ÐC91 1.550 (8)
C9ÐC92 1.513 (9)
C92ÐC93 1.347 (10)
C2ÐO1ÐC5 108.2 (5)
C3ÐC2ÐO1 114.0 (5)
C3ÐC2ÐC21 130.6 (5) O1ÐC2ÐC21 115.2 (5)
C2ÐC3ÐC4 108.8 (5)
O4ÐC4ÐC3 132.7 (6)
O4ÐC4ÐC5 123.0 (5)
C3ÐC4ÐC5 104.2 (5)
O1ÐC5ÐC6 112.4 (5)
O1ÐC5ÐC9 114.3 (6)
C6ÐC5ÐC9 102.6 (5)
O1ÐC5ÐC4 104.7 (4)
C6ÐC5ÐC4 109.6 (6)
C9ÐC5ÐC4 113.3 (5)
O6ÐC6ÐO7 123.9 (6)
O6ÐC6ÐC5 126.9 (6)
O7ÐC6ÐC5 109.1 (5)
C6ÐO7ÐC8 110.2 (5)
O7ÐC8ÐC9 105.7 (5)
C92ÐC9ÐC8 112.7 (5) C92ÐC9ÐC91 114.4 (6) C8ÐC9ÐC91 109.8 (5) C92ÐC9ÐC5 111.3 (5)
C8ÐC9ÐC5 99.3 (5)
C91ÐC9ÐC5 108.2 (5) C93ÐC92ÐC9 124.7 (6)
C atoms of the phenyl ring were ®tted to a regular hexagon with CÐC = 1.39 AÊ. The rotational orientation of the methyl group was re®ned. All H atoms were placed at idealized positions, with CÐH = 0.95±0.99 AÊ.Uiso(H) values of the phenyl ring were re®ned with a common parameter.Uiso(H) of the methyl and methylene groups and of H atoms attached to C93 were re®ned in the same manner. Other
Uiso(H) values were re®ned independently. The absolute con®gura-tion could not be determined from the diffraccon®gura-tion data due to the absence of heavy atoms, but was assigned asSS according to the con®guration attributed by Tadaet al.(1989) to hyperolactone A; the Friedel pairs were merged.
Data collection: local software; cell re®nement: local software; data reduction: local software; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: (Johnson, 1965); software used to prepare material for publication:SHELXL97.
We thank Dr Olaf Kunert (Institute of Pharmaceutical Sciences, University of Graz) for recording and discussing NMR spectra. This work was funded in part by the United States Department of Agriculture, ARS, Speci®c Cooperative Agreement No. 58-6408-7-01, and the Food and Drug Administration, FD-U-002071-01.
organic papers
Acta Cryst.(2004). E60, o2174±o2176 Sara L. Crockettet al. C16H14O4
o2175
Figure 1Stereoscopic ORTEP (Johnson, 1965) plot of hyperolactone C.
References
Aramaki, Y., Chiba, K. & Tada, M. (1995). Phytochemistry, 38, 1419± 1421.
Johnson, C. K. (1965).ORTEP.Report ORNL-3794. Oak Ridge National Laboratory, Tennessee, USA.
Radford, A. E., Ahles, H. E. & Bell, C. R. (1968). InManual of the Vascular Flora of the Carolinas. Chapel Hill, North Carolina: University of North Carolina Press.
Robson, N. K. B. (1996).Bull. Br. Mus. Nat. Hist.(Bot.),26, 75±217.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Tada, M., Nagai, M., Okumura, C., Osano, Y. & Matsuzaki, T. (1989).Chem. Lett.pp. 683±686.
Ueki, T., Doe, M., Tanaka, T., Morimoto, Y., Yoshihara, K. & Kinoshita, T. (2000).J. Heterocycl. Chem.38, 165±172.
Ueki, T., Ichinari, D., Yoshihara, K., Morimoto, Y. & Kinoshita, T. (1998). Tetrahedron Lett.39, 667±668.
USDA-NRCS. (2002). The PLANTS Database. Version 3.5. Retrieved between January and November, 2003 from http://plants.usda.gov. Baton Rouge, Lousiana: National Plant Data Center.
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Acta Cryst. (2004). E60, o2174–o2176
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Acta Cryst. (2004). E60, o2174–o2176 [https://doi.org/10.1107/S1600536804026819]
Hyperolactone C
Sara L. Crockett, Wolfgang Sch
ü
hly, Ferdinand Belaj and Ikhlas A. Khan
(5S,9S)-9-methyl-2-phenyl-9-vinyl-1,7-dioxaspiro[4.4]non-2-ene-4,6-dione
Crystal data
C16H14O4 Mr = 270.27
Monoclinic, P21
Hall symbol: P 2yb
a = 6.215 (7) Å
b = 7.491 (7) Å
c = 14.461 (15) Å
β = 98.68 (8)°
V = 665.5 (12) Å3 Z = 2
F(000) = 284
Dx = 1.349 Mg m−3
Melting point: 370 K
Mo Kα radiation, λ = 0.71069 Å Cell parameters from 35 reflections
θ = 4.4–10.6°
µ = 0.10 mm−1 T = 95 K Needle, colorless 0.42 × 0.25 × 0.12 mm
Data collection
Stoe
diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
1612 measured reflections 1270 independent reflections 943 reflections with I > 2σ(I)
Rint = 0.087
θmax = 25.0°, θmin = 2.9°
h = −7→7
k = −3→8
l = −1→17
3 standard reflections every 100 reflections intensity decay: 0.1%
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.068 wR(F2) = 0.154 S = 1.08 1270 reflections 175 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0556P)2 + 0.1091P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.28 e Å−3
Δρmin = −0.28 e Å−3
Special details
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Acta Cryst. (2004). E60, o2174–o2176
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. The non-hydrogen atoms were refined with anisotropic displacement parameters.
The C atoms of the phenyl rings were fitted to a regular hexagon with C—C distances of 1.39 Å (AFIX 66 of
SHELXL97). The H atoms of the phenyl rings were put at the external bisector of the C—C—C angle at a C—H distance of 0.95 Å and common isotropic displacement parameters were refined for the H atoms of the same phenyl group (AFIX 43 of SHELXL97).
The H-atoms H3 and H92 were put at the external bisector of the C—C—C angle at a C—H distance of 0.95 Å (AFIX 43 of SHELXL97). The H-atoms bonded to C8 were refined with an idealized geometry with approximately tetrahedral angles and C—H distances of 0.99 Å (AFIX 23 of SHELXL97). The H-atoms bonded to C3 and C8 were refined with a common isotropic displacement parameter. The individual isotropic displacement parameter of H92 was free to refine. The H-atoms bonded to C93 were refined with common isotropic displacement parameters and idealized geometry with the H-atoms in the C9—C92—C93 plane, angles of 120°, and C—H distances of 0.95 Å (AFIX 93 of SHELXL97). The H-atoms of the methyl group were refined with one common isotropic displacement parameter and idealized geometry with tetrahedral angles, enabling rotation around the X—C bond, and C—H distances of 0.98 Å (AFIX 137 of
SHELXL97).
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.3240 (6) 0.3111 (7) 0.7857 (3) 0.0168 (11) C2 0.1557 (10) 0.3580 (9) 0.8335 (4) 0.0139 (15) C3 −0.0286 (9) 0.4063 (10) 0.7776 (4) 0.0173 (15)
H3 −0.1612 0.4396 0.7980 0.015 (10)*
C4 0.0084 (9) 0.3990 (9) 0.6818 (4) 0.0124 (14) O4 −0.1047 (6) 0.4382 (7) 0.6077 (3) 0.0191 (11) C5 0.2496 (10) 0.3299 (10) 0.6881 (4) 0.0143 (14) C6 0.3834 (9) 0.4642 (10) 0.6422 (4) 0.0156 (15) O6 0.4724 (7) 0.5938 (7) 0.6773 (3) 0.0212 (12) O7 0.3816 (6) 0.4185 (7) 0.5531 (3) 0.0199 (12) C8 0.2756 (10) 0.2424 (10) 0.5343 (5) 0.0157 (15)
H81 0.3600 0.1669 0.4965 0.015 (10)*
H82 0.1262 0.2568 0.5000 0.015 (10)*
C9 0.2700 (9) 0.1581 (10) 0.6303 (4) 0.0134 (15) C21 0.2012 (6) 0.3355 (6) 0.93493 (19) 0.0152 (14) C22 0.0536 (5) 0.4003 (6) 0.9900 (2) 0.0211 (16)
H22 −0.0757 0.4581 0.9616 0.027 (9)*
C23 0.0953 (6) 0.3805 (7) 1.0866 (2) 0.0242 (18)
H23 −0.0056 0.4248 1.1243 0.027 (9)*
C24 0.2845 (7) 0.2960 (8) 1.12818 (19) 0.0222 (17)
H24 0.3130 0.2825 1.1942 0.027 (9)*
C25 0.4321 (5) 0.2312 (7) 1.0731 (3) 0.0227 (17)
H25 0.5615 0.1734 1.1015 0.027 (9)*
C26 0.3904 (6) 0.2509 (6) 0.9765 (2) 0.0199 (16)
H26 0.4913 0.2066 0.9388 0.027 (9)*
C91 0.4927 (10) 0.0702 (11) 0.6664 (5) 0.0212 (17)
H911 0.4991 0.0388 0.7325 0.031 (12)*
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H913 0.5096 −0.0380 0.6300 0.031 (12)*
C92 0.0759 (10) 0.0367 (10) 0.6315 (5) 0.0174 (16)
H92 −0.0573 0.0699 0.5943 0.03 (2)*
C93 0.0785 (11) −0.1152 (10) 0.6815 (4) 0.0190 (16)
H931 0.2088 −0.1526 0.7195 0.030 (14)*
H932 −0.0501 −0.1848 0.6788 0.030 (14)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.013 (2) 0.026 (3) 0.013 (2) 0.003 (2) 0.0068 (17) 0.003 (2) C2 0.020 (3) 0.006 (4) 0.019 (3) 0.000 (3) 0.010 (3) −0.002 (3) C3 0.019 (3) 0.019 (4) 0.016 (3) 0.002 (3) 0.013 (3) −0.003 (3) C4 0.017 (3) 0.006 (3) 0.013 (3) −0.001 (3) −0.003 (3) −0.002 (3) O4 0.020 (2) 0.023 (3) 0.016 (2) 0.006 (2) 0.0053 (18) −0.003 (2) C5 0.021 (3) 0.016 (4) 0.006 (3) −0.004 (3) 0.004 (2) −0.003 (3) C6 0.017 (3) 0.014 (4) 0.014 (4) −0.002 (3) −0.002 (3) −0.003 (3) O6 0.020 (2) 0.021 (3) 0.023 (3) −0.001 (2) 0.007 (2) −0.006 (2) O7 0.020 (2) 0.024 (3) 0.019 (3) −0.007 (2) 0.0118 (18) 0.000 (2) C8 0.017 (3) 0.018 (4) 0.014 (3) −0.003 (3) 0.008 (3) −0.002 (3) C9 0.013 (3) 0.018 (4) 0.010 (3) 0.005 (3) 0.005 (2) −0.003 (3) C21 0.016 (3) 0.013 (4) 0.018 (3) −0.006 (3) 0.008 (3) −0.004 (3) C22 0.023 (3) 0.021 (4) 0.020 (4) 0.002 (3) 0.005 (3) 0.001 (4) C23 0.032 (3) 0.028 (5) 0.015 (4) 0.000 (4) 0.010 (3) −0.008 (3) C24 0.038 (4) 0.021 (5) 0.007 (3) −0.004 (3) 0.000 (3) −0.002 (3) C25 0.025 (3) 0.021 (4) 0.022 (4) 0.001 (3) 0.003 (3) 0.002 (3) C26 0.023 (3) 0.019 (4) 0.019 (4) −0.004 (3) 0.010 (3) −0.002 (3) C91 0.019 (3) 0.027 (5) 0.018 (4) 0.001 (3) 0.005 (3) −0.011 (3) C92 0.017 (3) 0.018 (4) 0.018 (4) 0.006 (3) 0.008 (3) −0.002 (3) C93 0.026 (3) 0.016 (4) 0.017 (4) −0.004 (3) 0.011 (3) −0.003 (3)
Geometric parameters (Å, º)
O1—C2 1.383 (7) C21—C22 1.3900
O1—C5 1.424 (7) C21—C26 1.3900
C2—C3 1.348 (9) C22—C23 1.3900
C2—C21 1.462 (7) C22—H22 0.9500
C3—C4 1.439 (8) C23—C24 1.3900
C3—H3 0.9500 C23—H23 0.9500
C4—O4 1.225 (7) C24—C25 1.3900
C4—C5 1.576 (8) C24—H24 0.9500
C5—C6 1.521 (9) C25—C26 1.3900
C5—C9 1.551 (9) C25—H25 0.9500
C6—O6 1.193 (8) C26—H26 0.9500
C6—O7 1.331 (8) C91—H911 0.9800
O7—C8 1.482 (9) C91—H912 0.9800
C8—C9 1.530 (9) C91—H913 0.9800
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Acta Cryst. (2004). E60, o2174–o2176
C8—H82 0.9900 C92—H92 0.9500
C9—C91 1.550 (8) C93—H931 0.9500
C9—C92 1.513 (9) C93—H932 0.9500
C2—O1—C5 108.2 (5) C91—C9—C5 108.2 (5)
C3—C2—O1 114.0 (5) C22—C21—C26 120.0
C3—C2—C21 130.6 (5) C22—C21—C2 119.4 (3)
O1—C2—C21 115.2 (5) C26—C21—C2 120.6 (3)
C2—C3—C4 108.8 (5) C21—C22—C23 120.0
C2—C3—H3 125.6 C21—C22—H22 120.0
C4—C3—H3 125.6 C23—C22—H22 120.0
O4—C4—C3 132.7 (6) C24—C23—C22 120.0
O4—C4—C5 123.0 (5) C24—C23—H23 120.0
C3—C4—C5 104.2 (5) C22—C23—H23 120.0
O1—C5—C6 112.4 (5) C23—C24—C25 120.0
O1—C5—C9 114.3 (6) C23—C24—H24 120.0
C6—C5—C9 102.6 (5) C25—C24—H24 120.0
O1—C5—C4 104.7 (4) C26—C25—C24 120.0
C6—C5—C4 109.6 (6) C26—C25—H25 120.0
C9—C5—C4 113.3 (5) C24—C25—H25 120.0
O6—C6—O7 123.9 (6) C25—C26—C21 120.0
O6—C6—C5 126.9 (6) C25—C26—H26 120.0
O7—C6—C5 109.1 (5) C21—C26—H26 120.0
C6—O7—C8 110.2 (5) C9—C91—H911 109.5
O7—C8—C9 105.7 (5) C9—C91—H912 109.5
O7—C8—H81 110.6 H911—C91—H912 109.5
C9—C8—H81 110.6 C9—C91—H913 109.5
O7—C8—H82 110.6 H911—C91—H913 109.5
C9—C8—H82 110.6 H912—C91—H913 109.5
H81—C8—H82 108.7 C93—C92—C9 124.7 (6)
C92—C9—C8 112.7 (5) C93—C92—H92 117.7
C92—C9—C91 114.4 (6) C9—C92—H92 117.7
C8—C9—C91 109.8 (5) C92—C93—H931 120.0
C92—C9—C5 111.3 (5) C92—C93—H932 120.0
C8—C9—C5 99.3 (5) H931—C93—H932 120.0
C5—O1—C2—C3 0.5 (8) O7—C8—C9—C5 31.3 (5)
C5—O1—C2—C21 176.4 (5) O1—C5—C9—C92 84.6 (6) O1—C2—C3—C4 −1.7 (8) C6—C5—C9—C92 −153.4 (5) C21—C2—C3—C4 −176.8 (6) C4—C5—C9—C92 −35.3 (7) C2—C3—C4—O4 −176.0 (7) O1—C5—C9—C8 −156.5 (5)
C2—C3—C4—C5 2.0 (8) C6—C5—C9—C8 −34.5 (6)
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