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Ajees and Balakrishna C30H48O5 DOI: 10.1107/S1600536802006451 Acta Cryst.(2002). E58, o682±o684 Acta Crystallographica Section EStructure Reports
Online ISSN 1600-5368
Arjunolic acid
A. Abdul Ajeesa* and K. Balakrishnab
aDepartment of Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, andbCentral Research Institute for Siddha, Arumbakkam, Chennai 600 106, India
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.008 AÊ
Rfactor = 0.050
wRfactor = 0.164 Data-to-parameter ratio = 9.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, 2,3-24-trihydroxyolean-12-en-28-oic acid, C30H48O5, is a stereoisomer of hyptatic acid A (2,3
-24-trihydroxyolean-12-en-28-oic methanolate). The central ring, which is ¯attened due to the presence of a C C double bond, adopts a sofa conformation. All other six-membered rings adopt distorted chair conformations. The crystal structure is stabilized by OÐH O hydrogen bonds.
Comment
Arjunolic acid, (I), is the principal constituent ofTerminalia Arjuna, which belongs to the family combretaceaeand is an important medicinal plant found in India (Chopraet al., 1956; Nadkarni & Nadkarni, 1976). It was ®rst isolated from the plant by Kinget al.(1954).Terminalia Arjunais used in the indigenous system of medicine, primarily as a cardiotonic.
Clinical evaluation of this plant indicates that it can be of bene®t in the treatment of coronary artery disease, heart failures and possibly hypercholesterolemia, and it has also been found to have antibacterial and antimutagenic properties (Tripathi et al., 1996). Arjunolic acid has been shown to provide signi®cant cardiac protection in isoproterenol-induced myocardial necrosis in rats. Arjunolic acid treatment is also shown to prevent the decrease in the levels of super-oxide dismutase, catalase, glutathione peroxidase, cerulo-plasmin, -tocopherol, reduced glutathione, ascorbic acid, lipid peroxide and myeloperoxidase, and the cardioprotection is con®rmed by histopathological studies (Sumitraet al., 2001). Arjunolic acid isolated from the rhizome ofCocholspermum tinctorium, its triacetate derivative and its methyl esters were tested using the short-term in vitro assay on EBV±EA acti-vation in Raji cells induced by 12-O -tetradecanoylphorbol-13-acetate (TPA). Their inhibitory effects on skin-tumor promotors were found to be greater than those of the previously studied natural products (Dialloet al., 1989). Also
the compound demonstrated signi®cantin vitrocytotoxicity in human colon HCT-8 tumor cells (Yamagishiet al., 1988). In view of its medical importance, the crystal and molecular structure of arjunolic acid, (I), was determined.
The structure determination shows that (I) is a stereoisomer of hyptatic acid A (2,3 24-trihydroxyolean-12-en-28-oic methanolate), isolated fromHyptis Capitata, with the ÐCH3
and ÐCH2OH attachments at the C4 atom interchanged (Fig.
1). Hyptatic acid A has been found to crystallize with two molecules (AandB) per asymmetric unit, with methanol as solvent of crystallization (Yamagishi et al., 1988). Super-position of the non-H atoms of the arjunolic acid molecule (except O3) with each of the two independent molecules of hyptatic acid A, using BIOSYM (Biosym/MSI, 1995) shows that the r.m.s. deviation is 0.26 AÊ for moleculeAand 0.28 AÊ for moleculeB. Some of the bond lengths in (I) are found to be longer than the normal values and some angles are also widened due to steric overcrowding of axial methyl groups. However, these values are comparable with the corresponding values observed for molecules containing the same steroid skeleton. In the Cambridge Structural Database (1992), 29 structures were found to have the same steroid skeleton as arjunolic acid. Of these, 19 structures had anRfactor less than 6.0% and, from the data for these structures, the mean geometry of the molecular skeleton was determined. The bond lengths and angles which have large values in arjunolic acid are compared with the corresponding values of the average molecular skeleton and are listed Table 1. This shows that the geometry of arjunolic acid is similar to the average molecular skeleton.
The puckering parameters, evaluated using PARST (Nardelli, 1995), show that the six-membered ringsA andE adopt chair conformations [QT= 0.552 (6),q2= 0.040 (6) AÊ,'2
= 96 (7) for ring A; Q
T= 0.535 (6), q2 = 0.066 (6) AÊ,'2 =
ÿ3 (5)for ringE] and ringsBandDadopt slightly distorted chair conformations [QT= 0.579 (6), q2 = 0.158 (6) AÊ,'2 =
4 (2)for ringB;Q
T= 0.513 (6),q2= 0.158 (6) AÊ,'2= 29 (2)
for ringD]. RingCis in a slightly distorted sofa conformation due to the ¯attening caused by the C12 C13 double bond [QT= 0.545 (6),q2= 0.404 (6) AÊ,'2= 14.0 (9)]. All the fused
rings havetransfusion exceptD/E, which is incisfusion. The H atom at C18 and the carboxyl group at C17 are in posi-tions. The non-bonded distances between C atoms of diaxial methyl groups C24 C25 and C25 C26 are 3.323 (9) and 3.307 (9) AÊ, respectively. In a six-membered ring, the non-bonded distances between 1,3 diaxial methyl groups would be 2.52 AÊ if the ring adopted a regular chair form (Spirletet al., 1980). The structure is stabilized by OÐH O intra- and intermolecular hydrogen bonds (Table 2).
Experimental
The title compound was successively extracted from the dried and powdered heartwood (4 kg) of the plantTerminalia Arjunawith ethyl acetate in the cold (72 h). The extract was diluted with a little ethyl acetate and heated on a water bath to produce a dark red±brown solution which was allowed to stand overnight at room temperature. The pale-yellow solid which precipitated was ®ltered and washed with ethyl acetate (yield: 48 g). The crude arjunolic acid thus obtained was passed through a column of silica gel packed in chloroform. The column was eluted with chloroform and then with chloroform containing methanol in increasing proportions. Elution of the column with a chloroform±methanol (9:1) solvent mixture gave arjunolic acid (m.p. 569 K, 43 g) and crystals suitable for X-ray diffraction analysis were grown by slow evaporation from a methanol solution.
Crystal data
C30H48O5 Mr= 488.68
Orthorhombic,P212121 a= 11.580 (2) AÊ b= 14.623 (2) AÊ c= 15.952 (4) AÊ V= 2701.2 (9) AÊ3 Z= 4
Dx= 1.202 Mg mÿ3
CuKradiation Cell parameters from 25
re¯ections
= 14±25
= 0.63 mmÿ1 T= 293 (2) K Needle, colorless 0.220.130.10 mm
Data collection
Enraf±Nonius CAD-4 diffractometer
!±2scans
Absorption correction: none 2962 measured re¯ections 2962 independent re¯ections 1388 re¯ections withI> 2(I)
max= 71.9 h= 0!14 k= 0!17 l= 0!19
3 standard re¯ections frequency: 120 min intensity decay:<1%
Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.050 wR(F2) = 0.164 S= 0.96 2962 re¯ections 317 parameters
H-atom parameters constrained
w= 1/[2(Fo2) + (0.0781P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.23 e AÊÿ3 min=ÿ0.19 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.0021 (4)
Acta Cryst.(2002). E58, o682±o684 Ajees and Balakrishna C30H48O5
o683
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Figure 1
organic papers
o684
Ajees and Balakrishna C30H48O5 Acta Cryst.(2002). E58, o682±o684Table 1
Comparison of the unusually large bond lengths and angles (AÊ,) in the
skleton of arjunolic acid with those found in the average skeleton of related structures.
Bond Arjunolic Acid Average
C4ÐC5 1.570 (7) 1.563 (9)
C5ÐC10 1.557 (8) 1.552 (8)
C9ÐC10 1.562 (7) 1.570 (10)
C7ÐC8 1.551 (8) 1.541 (8)
C8ÐC9 1.565 (8) 1.553 (8)
C8ÐC14 1.578 (8) 1.589 (6)
C17ÐC22 1.559 (7) 1.546 (13)
C2ÐC3ÐC4 114.6 (5) 114.2 (12) C1ÐC2ÐC3 110.9 (5) 111.0 (12) C10ÐC1ÐC2 113.4 (5) 113.5 (11) C4ÐC5ÐC10 117.1 (5) 117.0 (9) C4ÐC5ÐC6 115.0 (4) 114.4 (5) C6ÐC7ÐC8 115.5 (5) 114.1 (7) C7ÐC8ÐC14 110.7 (4) 110.5 (5) C8ÐC9ÐC10 118.2 (5) 117.5 (8) C10ÐC9ÐC11 113.8 (4) 113.2 (6) C14ÐC15ÐC16 115.7 (5) 114.6 (5) C15ÐC16ÐC17 110.9 (5) 112.4 (7) C16ÐC17ÐC18 109.9 (5) 108.7 (11) C16ÐC17ÐC22 110.8 (5) 112.0 (13) C18ÐC17ÐC22 111.7 (5) 110.2 (12) C17ÐC18ÐC13 110.9 (5) 112.3 (9) C17ÐC18ÐC19 112.5 (5) 112.8 (10) C13ÐC18ÐC19 114.2 (5) 111.9 (15) C18ÐC19ÐC20 114.1 (5) 114 (2) C20ÐC21ÐC22 112.9 (5) 112.8 (14) C21ÐC22ÐC17 114.0 (5) 114.4 (10)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O1ÐH1O O5i 0.82 1.96 2.744 (6) 160 O3ÐH3O O2 0.82 1.93 2.665 (6) 148 O4ÐH4O O3ii 0.82 1.82 2.642 (7) 174 Symmetry codes: (i)1
2ÿx;ÿy;zÿ12; (ii)21x;12ÿy;ÿz.
All H atoms were placed in calculated positions, re®ned using a riding model, and given an isotropic displacement parameter equal to 1.2 times the equivalent isotropic parameter of their parent C atoms and 1.5 times the equivalent isotropic parameter of their parent O atoms. The CÐH and OÐH distances used depend on the type of atom. As a result of the poor diffraction quality of the crystal, the ratio of observed to unique re¯ections is low. The absolute
con®g-uration could not be determined by standard re®nement of the Flack (1983) parameter in the absence of strong anomalous dispersion effects and Friedel opposites. It was established by a new technique based on re¯ections that are most affected by the anomalous dispersion of the O atoms (Parthasarathy & Abdul Ajees, 2002); the main conclusions of this report do not depend on the absolute con®guration.
Data collection: CAD-4 Software (Enraf±Nonius, 1989); cell re®nement: SDP (Frenz, 1978); data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: PARST97 (Nardelli, 1995) and
PLATON(Spek, 2000).
Thanks are due to the Council of Scienti®c and Industrial Research, India for the award of a Senior Research Fellowship to AAA.
References
Biosym/MSI (1995).BIOSYM. Release 95.0. Biosym/MSI, San Diego, CA 92121-3752, USA.
Cambridge Structural Database (1992). CSD Users Manual. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England. Chopra, R. N., Nayar, S. L. & Chopra, I. C. (1956).Glossary of Indian Medical
Plants, pp. 251. New Delhi: CSIR.
Diallo, B., Vanhaelen, M., Vanhaelen-Fastre, R., Konoshima, T., Kozuka, M. & Tokuda, H. (1989).J. Nat. Prod.52, 879±881.
Enraf±Nonius (1989).CAD-4Software. Version 5.0. Enraf±Nonius, Delft, The Netherlands.
Flack, H. D. (1983).Acta Cryst.A39, 876±881.
Frenz, B. A. (1978).The Enraf±Nonius CAD-4SDP. Computing in Crystal-lography, edited by H. Schenk, R. Olthof-Hazekamp, H. van Koningsveld and G. C. Bassi, pp. 64±71.
King, F. E., King, T. J. & Ross, J. M. (1954).J. Chem. Soc.pp. 3995±4003. Nadkarni, K. M. & Nadkarni, A. K. (1976).Indian Materia Medica, Vol. I, pp.
1198. Bombay: Popular Prakashan Pvt. Ltd. Nardelli, M. (1995).J. Appl. Cryst.28, 659.
Parthasarathy, S. & Abdul Ajees, A. (2002). Unpublished work.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Spek, A. L. (2000).PLATON.University of Utrecht, The Netherlands. Spirlet, M. R., Dupont, L., Dideberg, O. & Kapundu, M. (1980).Acta Cryst.
B36, 1593±1598.
Sumitra, M., Manikandan, P., Kumar, D. A., Arutselvan, N., Balakrishna, K., Manohar, B. M. & Puvanakrishnan, R. (2001).Mol. Cell Biochem.224, 135± 142.
Tripathi, V. K., Singh, B., Tripathi, R. C., Upadhyay, R. K. & Pandey, V. B. (1996). OrientalJ. Chem.12, 1±16.
Yamagishi, T., Zhang, D. C., Chang, J. J., McPhail, D. R., McPhail, A. T. & Lee, K. H. (1988).Phytochemistry,27, 3213±3216.
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Acta Cryst. (2002). E58, o682–o684
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Acta Cryst. (2002). E58, o682–o684 [https://doi.org/10.1107/S1600536802006451]
Arjunolic acid
A. Abdul Ajees and K. Balakrishna
2α,3β-24-trihydroxyolean-12-en-28-oic acid
Crystal data
C30H48O5
Mr = 488.68
Orthorhombic, P212121
a = 11.580 (2) Å b = 14.623 (2) Å c = 15.952 (4) Å V = 2701.2 (9) Å3
Z = 4
F(000) = 1072
Dx = 1.202 Mg m−3
Cu Kα radiation, λ = 1.5418 Å Cell parameters from 25 reflections θ = 14–25°
µ = 0.63 mm−1
T = 293 K Needle, colourless 0.22 × 0.13 × 0.10 mm
Data collection
Enraf-Nonius CAD-4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω–2θ scans
2962 measured reflections 2962 independent reflections 1388 reflections with I > 2σ(I)
Rint = 0.000
θmax = 71.9°, θmin = 4.1°
h = 0→14 k = 0→17 l = 0→19
3 standard reflections every 120 min intensity decay: <1%
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.050
wR(F2) = 0.164
S = 0.96 2962 reflections 317 parameters 9 restraints
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) + (0.0781P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
Δρmax = 0.23 e Å−3 Δρmin = −0.19 e Å−3
Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.0021 (4)
Special details
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Acta Cryst. (2002). E58, o682–o684
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.0538 (4) −0.1668 (3) −0.1689 (3) 0.0534 (12)
H1O 0.1148 −0.1954 −0.1696 0.080*
O2 −0.0234 (4) −0.0514 (3) −0.2862 (2) 0.0645 (14)
H2O 0.0338 −0.0332 −0.3116 0.097*
O3 −0.1564 (4) 0.0952 (3) −0.3095 (2) 0.0684 (15)
H3O −0.1236 0.0472 −0.3214 0.103*
O4 0.1286 (4) 0.3528 (3) 0.3376 (3) 0.0629 (14)
H4O 0.1938 0.3726 0.3291 0.094*
O5 0.2193 (4) 0.2209 (3) 0.3343 (4) 0.0727 (16)
C1 0.0799 (5) −0.0476 (4) −0.0637 (3) 0.0385 (14)
H1A 0.1443 −0.0790 −0.0376 0.046*
H1B 0.0095 −0.0699 −0.0378 0.046*
C2 0.0776 (5) −0.0711 (4) −0.1564 (3) 0.0396 (15)
H2 0.1518 −0.0553 −0.1821 0.048*
C3 −0.0177 (6) −0.0214 (4) −0.2000 (3) 0.0417 (15)
H3 −0.0902 −0.0395 −0.1731 0.050*
C4 −0.0097 (5) 0.0833 (4) −0.1947 (3) 0.0390 (15)
C5 −0.0024 (5) 0.1072 (4) −0.0989 (3) 0.0352 (14)
H5 −0.0761 0.0861 −0.0757 0.042*
C6 0.0013 (6) 0.2094 (4) −0.0788 (3) 0.0452 (16)
H6A 0.0789 0.2326 −0.0873 0.054*
H6B −0.0504 0.2423 −0.1159 0.054*
C7 −0.0348 (6) 0.2244 (4) 0.0115 (3) 0.0437 (16)
H7A −0.1150 0.2063 0.0173 0.052*
H7B −0.0303 0.2894 0.0236 0.052*
C8 0.0373 (5) 0.1724 (4) 0.0781 (4) 0.0354 (14)
C9 0.0576 (5) 0.0720 (4) 0.0474 (3) 0.0310 (13)
H9 −0.0174 0.0419 0.0539 0.037*
C10 0.0910 (5) 0.0564 (4) −0.0464 (3) 0.0351 (14)
C11 0.1374 (5) 0.0229 (4) 0.1098 (4) 0.0430 (16)
H11A 0.1317 −0.0426 0.1009 0.052*
H11B 0.2166 0.0409 0.0989 0.052*
C12 0.1084 (5) 0.0439 (4) 0.1992 (3) 0.0379 (14)
H12 0.1434 0.0077 0.2398 0.046*
C13 0.0373 (5) 0.1095 (4) 0.2266 (3) 0.0348 (14)
C14 −0.0298 (5) 0.1675 (4) 0.1641 (3) 0.0360 (14)
C15 −0.0471 (6) 0.2648 (4) 0.2007 (3) 0.0487 (17)
H15A 0.0234 0.2993 0.1921 0.058*
H15B −0.1078 0.2949 0.1692 0.058*
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H16A −0.1531 0.2412 0.3022 0.056*
H16B −0.0827 0.3325 0.3110 0.056*
C17 0.0131 (5) 0.2188 (4) 0.3469 (4) 0.0405 (15)
C18 0.0194 (5) 0.1183 (4) 0.3207 (3) 0.0363 (14)
H18 0.0891 0.0935 0.3471 0.044*
C19 −0.0818 (5) 0.0623 (4) 0.3548 (3) 0.0451 (16)
H19A −0.1521 0.0824 0.3274 0.054*
H19B −0.0699 −0.0014 0.3402 0.054*
C20 −0.0980 (6) 0.0694 (5) 0.4497 (4) 0.0457 (17)
C21 −0.1131 (6) 0.1702 (4) 0.4723 (4) 0.0529 (18)
H21A −0.1844 0.1924 0.4478 0.063*
H21B −0.1196 0.1758 0.5327 0.063*
C22 −0.0141 (6) 0.2293 (4) 0.4421 (3) 0.0470 (17)
H22A 0.0546 0.2138 0.4739 0.056*
H22B −0.0323 0.2928 0.4536 0.056*
C23 −0.1273 (6) 0.1209 (5) −0.2258 (4) 0.0518 (18)
H23A −0.1876 0.0995 −0.1884 0.062*
H23B −0.1258 0.1872 −0.2224 0.062*
C24 0.0856 (6) 0.1231 (4) −0.2502 (4) 0.0573 (19)
H24A 0.0731 0.1048 −0.3073 0.086*
H24B 0.1593 0.1009 −0.2316 0.086*
H24C 0.0843 0.1886 −0.2466 0.086*
C25 0.2164 (5) 0.0842 (4) −0.0682 (4) 0.0480 (17)
H25A 0.2306 0.0724 −0.1265 0.072*
H25B 0.2692 0.0492 −0.0348 0.072*
H25C 0.2270 0.1481 −0.0570 0.072*
C26 0.1540 (5) 0.2230 (4) 0.0890 (4) 0.0552 (19)
H26A 0.1935 0.2253 0.0362 0.083*
H26B 0.2007 0.1909 0.1291 0.083*
H26C 0.1400 0.2840 0.1086 0.083*
C27 −0.1540 (5) 0.1257 (4) 0.1554 (4) 0.0495 (18)
H27A −0.1906 0.1244 0.2093 0.074*
H27B −0.1484 0.0646 0.1337 0.074*
H27C −0.1989 0.1625 0.1177 0.074*
C28 0.1311 (6) 0.2621 (5) 0.3372 (4) 0.0425 (15)
C29 0.0029 (7) 0.0267 (5) 0.4960 (4) 0.072 (2)
H29A 0.0728 0.0583 0.4814 0.108*
H29B 0.0096 −0.0365 0.4806 0.108*
H29C −0.0097 0.0314 0.5553 0.108*
C30 −0.2087 (7) 0.0182 (6) 0.4742 (4) 0.075 (3)
H30A −0.2195 0.0220 0.5338 0.112*
H30B −0.2021 −0.0448 0.4580 0.112*
H30C −0.2736 0.0453 0.4463 0.112*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Acta Cryst. (2002). E58, o682–o684
O2 0.077 (3) 0.082 (4) 0.035 (2) 0.019 (3) −0.008 (2) −0.012 (2)
O3 0.079 (3) 0.088 (4) 0.039 (3) 0.038 (3) −0.011 (2) −0.008 (3)
O4 0.062 (3) 0.039 (3) 0.087 (4) −0.006 (2) 0.010 (3) −0.002 (3)
O5 0.034 (2) 0.054 (3) 0.129 (5) 0.004 (2) 0.001 (3) −0.011 (3)
C1 0.034 (3) 0.044 (4) 0.037 (3) 0.007 (3) 0.000 (3) −0.001 (3)
C2 0.044 (3) 0.040 (4) 0.035 (3) 0.004 (3) 0.003 (3) −0.006 (3)
C3 0.046 (4) 0.054 (4) 0.025 (3) 0.013 (3) 0.001 (3) −0.003 (3)
C4 0.044 (4) 0.042 (4) 0.032 (3) 0.007 (3) 0.005 (3) −0.002 (3)
C5 0.038 (3) 0.039 (4) 0.029 (3) 0.000 (3) 0.002 (3) 0.007 (3)
C6 0.058 (4) 0.036 (4) 0.041 (3) 0.005 (3) −0.004 (3) 0.009 (3)
C7 0.057 (4) 0.037 (4) 0.037 (3) 0.006 (3) −0.004 (3) 0.003 (3)
C8 0.035 (3) 0.036 (4) 0.035 (3) 0.002 (3) 0.001 (3) −0.004 (3)
C9 0.031 (3) 0.029 (3) 0.033 (3) 0.000 (3) 0.001 (3) −0.003 (3)
C10 0.041 (3) 0.036 (4) 0.029 (3) −0.002 (3) 0.001 (2) 0.008 (3)
C11 0.050 (4) 0.040 (4) 0.038 (3) 0.009 (3) −0.003 (3) 0.002 (3)
C12 0.045 (3) 0.040 (4) 0.029 (3) 0.004 (3) −0.002 (3) 0.005 (3)
C13 0.034 (3) 0.039 (4) 0.031 (3) −0.006 (3) −0.002 (3) 0.000 (3)
C14 0.039 (3) 0.036 (3) 0.033 (3) 0.002 (3) −0.007 (3) −0.003 (3)
C15 0.058 (4) 0.043 (4) 0.045 (4) 0.013 (3) −0.003 (3) −0.006 (3)
C16 0.048 (4) 0.048 (4) 0.045 (4) 0.012 (3) −0.002 (3) −0.013 (3)
C17 0.039 (3) 0.041 (4) 0.041 (3) 0.003 (3) −0.002 (3) −0.005 (3)
C18 0.039 (3) 0.035 (3) 0.035 (3) 0.002 (3) −0.004 (3) −0.005 (3)
C19 0.048 (4) 0.049 (4) 0.038 (3) −0.009 (3) 0.008 (3) −0.005 (3)
C20 0.048 (4) 0.050 (4) 0.039 (4) −0.004 (4) 0.013 (3) −0.001 (3)
C21 0.054 (4) 0.062 (5) 0.043 (4) 0.003 (4) 0.008 (3) −0.013 (3)
C22 0.053 (4) 0.057 (4) 0.031 (3) −0.007 (4) 0.008 (3) −0.011 (3)
C23 0.059 (4) 0.060 (5) 0.037 (3) 0.013 (4) −0.006 (3) 0.001 (3)
C24 0.065 (5) 0.063 (5) 0.043 (4) −0.006 (4) 0.013 (4) 0.012 (4)
C25 0.038 (3) 0.057 (5) 0.049 (4) 0.002 (3) 0.004 (3) −0.002 (3)
C26 0.056 (4) 0.051 (4) 0.059 (4) −0.013 (4) 0.010 (4) −0.009 (4)
C27 0.038 (3) 0.069 (5) 0.041 (3) −0.002 (4) 0.001 (3) −0.009 (4)
C28 0.047 (4) 0.046 (4) 0.035 (3) −0.008 (3) −0.007 (3) −0.010 (3)
C29 0.089 (6) 0.082 (6) 0.045 (4) 0.012 (6) 0.002 (4) 0.001 (4)
C30 0.082 (6) 0.091 (6) 0.051 (4) −0.034 (5) 0.019 (4) −0.006 (4)
Geometric parameters (Å, º)
O1—C2 1.439 (7) C14—C27 1.569 (8)
O1—H1O 0.82 C15—C16 1.523 (8)
O2—C3 1.445 (6) C15—H15A 0.97
O2—H2O 0.82 C15—H15B 0.97
O3—C23 1.427 (7) C16—C17 1.542 (8)
O3—H3O 0.82 C16—H16A 0.97
O4—C28 1.326 (7) C16—H16B 0.97
O4—H4O 0.82 C17—C28 1.514 (8)
O5—C28 1.187 (7) C17—C18 1.529 (8)
C1—C2 1.518 (7) C17—C22 1.559 (7)
supporting information
sup-5
Acta Cryst. (2002). E58, o682–o684
C1—H1A 0.97 C18—H18 0.98
C1—H1B 0.97 C19—C20 1.529 (8)
C2—C3 1.494 (8) C19—H19A 0.97
C2—H2 0.98 C19—H19B 0.97
C3—C4 1.536 (8) C20—C29 1.518 (9)
C3—H3 0.98 C20—C21 1.527 (9)
C4—C24 1.530 (8) C20—C30 1.535 (9)
C4—C23 1.550 (8) C21—C22 1.514 (8)
C4—C5 1.570 (7) C21—H21A 0.97
C5—C6 1.530 (7) C21—H21B 0.97
C5—C10 1.557 (8) C22—H22A 0.97
C5—H5 0.98 C22—H22B 0.97
C6—C7 1.516 (8) C23—H23A 0.97
C6—H6A 0.97 C23—H23B 0.97
C6—H6B 0.97 C24—H24A 0.96
C7—C8 1.551 (8) C24—H24B 0.96
C7—H7A 0.97 C24—H24C 0.96
C7—H7B 0.97 C25—H25A 0.96
C8—C26 1.551 (8) C25—H25B 0.96
C8—C9 1.565 (8) C25—H25C 0.96
C8—C14 1.578 (8) C26—H26A 0.96
C9—C11 1.536 (7) C26—H26B 0.96
C9—C10 1.562 (7) C26—H26C 0.96
C9—H9 0.98 C27—H27A 0.96
C10—C25 1.547 (8) C27—H27B 0.96
C11—C12 1.497 (7) C27—H27C 0.96
C11—H11A 0.97 C29—H29A 0.96
C11—H11B 0.97 C29—H29B 0.96
C12—C13 1.338 (8) C29—H29C 0.96
C12—H12 0.93 C30—H30A 0.96
C13—C18 1.521 (7) C30—H30B 0.96
C13—C14 1.522 (8) C30—H30C 0.96
C14—C15 1.551 (8)
C2—O1—H1O 109.5 C15—C16—C17 110.9 (5)
C3—O2—H2O 109.5 C15—C16—H16A 109.5
C23—O3—H3O 109.5 C17—C16—H16A 109.5
C28—O4—H4O 109.5 C15—C16—H16B 109.5
C2—C1—C10 113.4 (5) C17—C16—H16B 109.5
C2—C1—H1A 108.9 H16A—C16—H16B 108.1
C10—C1—H1A 108.9 C28—C17—C18 109.3 (5)
C2—C1—H1B 108.9 C28—C17—C16 111.2 (5)
C10—C1—H1B 108.9 C18—C17—C16 109.9 (5)
H1A—C1—H1B 107.7 C28—C17—C22 103.9 (5)
O1—C2—C3 105.5 (5) C18—C17—C22 111.7 (5)
O1—C2—C1 111.0 (5) C16—C17—C22 110.8 (5)
C3—C2—C1 110.9 (5) C13—C18—C17 110.9 (5)
supporting information
sup-6
Acta Cryst. (2002). E58, o682–o684
C3—C2—H2 109.8 C17—C18—C19 112.5 (5)
C1—C2—H2 109.8 C13—C18—H18 106.2
O2—C3—C2 109.2 (5) C17—C18—H18 106.2
O2—C3—C4 111.0 (5) C19—C18—H18 106.2
C2—C3—C4 114.6 (5) C20—C19—C18 114.1 (5)
O2—C3—H3 107.3 C20—C19—H19A 108.7
C2—C3—H3 107.3 C18—C19—H19A 108.7
C4—C3—H3 107.3 C20—C19—H19B 108.7
C24—C4—C3 113.0 (5) C18—C19—H19B 108.7
C24—C4—C23 108.3 (5) H19A—C19—H19B 107.6
C3—C4—C23 106.5 (5) C29—C20—C21 111.7 (6)
C24—C4—C5 116.1 (5) C29—C20—C19 111.1 (5)
C3—C4—C5 106.2 (4) C21—C20—C19 108.3 (5)
C23—C4—C5 106.2 (5) C29—C20—C30 108.5 (6)
C6—C5—C10 109.4 (5) C21—C20—C30 108.4 (6)
C6—C5—C4 115.0 (4) C19—C20—C30 108.8 (6)
C10—C5—C4 117.1 (5) C22—C21—C20 112.9 (5)
C6—C5—H5 104.6 C22—C21—H21A 109.0
C10—C5—H5 104.6 C20—C21—H21A 109.0
C4—C5—H5 104.6 C22—C21—H21B 109.0
C7—C6—C5 109.5 (4) C20—C21—H21B 109.0
C7—C6—H6A 109.8 H21A—C21—H21B 107.8
C5—C6—H6A 109.8 C21—C22—C17 114.0 (5)
C7—C6—H6B 109.8 C21—C22—H22A 108.8
C5—C6—H6B 109.8 C17—C22—H22A 108.8
H6A—C6—H6B 108.2 C21—C22—H22B 108.8
C6—C7—C8 115.5 (5) C17—C22—H22B 108.8
C6—C7—H7A 108.4 H22A—C22—H22B 107.7
C8—C7—H7A 108.4 O3—C23—C4 114.3 (5)
C6—C7—H7B 108.4 O3—C23—H23A 108.7
C8—C7—H7B 108.4 C4—C23—H23A 108.7
H7A—C7—H7B 107.5 O3—C23—H23B 108.7
C7—C8—C26 108.2 (5) C4—C23—H23B 108.7
C7—C8—C9 109.1 (5) H23A—C23—H23B 107.6
C26—C8—C9 110.6 (5) C4—C24—H24A 109.5
C7—C8—C14 110.7 (4) C4—C24—H24B 109.5
C26—C8—C14 110.6 (5) H24A—C24—H24B 109.5
C9—C8—C14 107.7 (4) C4—C24—H24C 109.5
C11—C9—C10 113.8 (4) H24A—C24—H24C 109.5
C11—C9—C8 109.1 (4) H24B—C24—H24C 109.5
C10—C9—C8 118.2 (5) C10—C25—H25A 109.5
C11—C9—H9 104.8 C10—C25—H25B 109.5
C10—C9—H9 104.8 H25A—C25—H25B 109.5
C8—C9—H9 104.8 C10—C25—H25C 109.5
C25—C10—C1 107.1 (5) H25A—C25—H25C 109.5
C25—C10—C5 113.9 (4) H25B—C25—H25C 109.5
C1—C10—C5 108.3 (5) C8—C26—H26A 109.5
supporting information
sup-7
Acta Cryst. (2002). E58, o682–o684
C1—C10—C9 107.0 (4) H26A—C26—H26B 109.5
C5—C10—C9 105.9 (4) C8—C26—H26C 109.5
C12—C11—C9 112.7 (5) H26A—C26—H26C 109.5
C12—C11—H11A 109.0 H26B—C26—H26C 109.5
C9—C11—H11A 109.0 C14—C27—H27A 109.5
C12—C11—H11B 109.0 C14—C27—H27B 109.5
C9—C11—H11B 109.0 H27A—C27—H27B 109.5
H11A—C11—H11B 107.8 C14—C27—H27C 109.5
C13—C12—C11 126.6 (5) H27A—C27—H27C 109.5
C13—C12—H12 116.7 H27B—C27—H27C 109.5
C11—C12—H12 116.7 O5—C28—O4 121.8 (6)
C12—C13—C18 117.9 (5) O5—C28—C17 124.7 (6)
C12—C13—C14 119.9 (5) O4—C28—C17 113.4 (6)
C18—C13—C14 122.0 (5) C20—C29—H29A 109.5
C13—C14—C15 109.2 (5) C20—C29—H29B 109.5
C13—C14—C27 108.0 (5) H29A—C29—H29B 109.5
C15—C14—C27 105.8 (5) C20—C29—H29C 109.5
C13—C14—C8 110.1 (4) H29A—C29—H29C 109.5
C15—C14—C8 110.5 (5) H29B—C29—H29C 109.5
C27—C14—C8 113.1 (4) C20—C30—H30A 109.5
C16—C15—C14 115.7 (5) C20—C30—H30B 109.5
C16—C15—H15A 108.3 H30A—C30—H30B 109.5
C14—C15—H15A 108.3 C20—C30—H30C 109.5
C16—C15—H15B 108.3 H30A—C30—H30C 109.5
C14—C15—H15B 108.3 H30B—C30—H30C 109.5
H15A—C15—H15B 107.4
C10—C1—C2—O1 −173.4 (5) C12—C13—C14—C27 97.1 (6)
C10—C1—C2—C3 −56.4 (7) C18—C13—C14—C27 −78.0 (6)
O1—C2—C3—O2 −54.8 (6) C12—C13—C14—C8 −26.8 (7)
C1—C2—C3—O2 −175.1 (5) C18—C13—C14—C8 158.1 (5)
O1—C2—C3—C4 −180.0 (5) C7—C8—C14—C13 175.3 (5)
C1—C2—C3—C4 59.7 (7) C26—C8—C14—C13 −64.8 (6)
O2—C3—C4—C24 −50.9 (7) C9—C8—C14—C13 56.1 (6)
C2—C3—C4—C24 73.3 (6) C7—C8—C14—C15 −63.9 (6)
O2—C3—C4—C23 67.8 (6) C26—C8—C14—C15 56.0 (6)
C2—C3—C4—C23 −167.9 (5) C9—C8—C14—C15 176.9 (5)
O2—C3—C4—C5 −179.3 (4) C7—C8—C14—C27 54.4 (6)
C2—C3—C4—C5 −55.0 (7) C26—C8—C14—C27 174.3 (5)
C24—C4—C5—C6 55.9 (7) C9—C8—C14—C27 −64.8 (6)
C3—C4—C5—C6 −177.6 (5) C13—C14—C15—C16 −41.5 (7)
C23—C4—C5—C6 −64.6 (7) C27—C14—C15—C16 74.5 (6)
C24—C4—C5—C10 −74.8 (7) C8—C14—C15—C16 −162.8 (5)
C3—C4—C5—C10 51.7 (7) C14—C15—C16—C17 55.9 (7)
C23—C4—C5—C10 164.7 (5) C15—C16—C17—C28 60.9 (7)
C10—C5—C6—C7 −66.0 (6) C15—C16—C17—C18 −60.2 (7)
C4—C5—C6—C7 159.7 (5) C15—C16—C17—C22 176.0 (5)
supporting information
sup-8
Acta Cryst. (2002). E58, o682–o684
C6—C7—C8—C26 76.6 (6) C14—C13—C18—C17 −43.9 (7)
C6—C7—C8—C9 −43.8 (6) C12—C13—C18—C19 −90.8 (6)
C6—C7—C8—C14 −162.1 (5) C14—C13—C18—C19 84.3 (7)
C7—C8—C9—C11 175.3 (5) C28—C17—C18—C13 −69.7 (6)
C26—C8—C9—C11 56.4 (6) C16—C17—C18—C13 52.6 (7)
C14—C8—C9—C11 −64.5 (5) C22—C17—C18—C13 175.9 (5)
C7—C8—C9—C10 43.2 (6) C28—C17—C18—C19 161.1 (5)
C26—C8—C9—C10 −75.6 (6) C16—C17—C18—C19 −76.6 (6)
C14—C8—C9—C10 163.4 (4) C22—C17—C18—C19 46.7 (7)
C2—C1—C10—C25 −72.7 (6) C13—C18—C19—C20 178.7 (5)
C2—C1—C10—C5 50.6 (6) C17—C18—C19—C20 −53.8 (7)
C2—C1—C10—C9 164.4 (5) C18—C19—C20—C29 −66.2 (7)
C6—C5—C10—C25 −64.6 (6) C18—C19—C20—C21 56.8 (7)
C4—C5—C10—C25 68.7 (7) C18—C19—C20—C30 174.4 (6)
C6—C5—C10—C1 176.4 (5) C29—C20—C21—C22 66.7 (7)
C4—C5—C10—C1 −50.4 (6) C19—C20—C21—C22 −55.9 (7)
C6—C5—C10—C9 61.8 (6) C30—C20—C21—C22 −173.7 (5)
C4—C5—C10—C9 −164.9 (5) C20—C21—C22—C17 53.1 (7)
C11—C9—C10—C25 −56.4 (7) C28—C17—C22—C21 −165.0 (5)
C8—C9—C10—C25 73.5 (6) C18—C17—C22—C21 −47.3 (7)
C11—C9—C10—C1 62.0 (6) C16—C17—C22—C21 75.5 (7)
C8—C9—C10—C1 −168.1 (5) C24—C4—C23—O3 62.5 (7)
C11—C9—C10—C5 177.3 (5) C3—C4—C23—O3 −59.3 (7)
C8—C9—C10—C5 −52.7 (6) C5—C4—C23—O3 −172.2 (5)
C10—C9—C11—C12 176.2 (5) C18—C17—C28—O5 −20.4 (8)
C8—C9—C11—C12 41.8 (7) C16—C17—C28—O5 −141.9 (7)
C9—C11—C12—C13 −11.9 (9) C22—C17—C28—O5 98.9 (7)
C11—C12—C13—C18 179.5 (6) C18—C17—C28—O4 163.8 (5)
C11—C12—C13—C14 4.2 (9) C16—C17—C28—O4 42.4 (7)
C12—C13—C14—C15 −148.3 (5) C22—C17—C28—O4 −76.8 (6)
C18—C13—C14—C15 36.6 (7)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1—H1O···O5i 0.82 1.96 2.744 (6) 160
O3—H3O···O2 0.82 1.93 2.665 (6) 148
O4—H4O···O3ii 0.82 1.82 2.642 (7) 174