New limonoids from Harrisonia perforata (Blanco) Merr.

Two minor compounds were isolated from a sample of Harrisonia perforata leaves collected in central Vietnam, namely haperforin B₁, C₂₇H₃₂O₉, and haperforin D, C₂₇H₃₄O₁₀. Biogenetically, haperforin D and haperforin B₁ can be derived from each other by addition or elimination of water.

Computing details

For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NONIUS (Riche, 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: R3M (Riche, 1983) and ORTEP (Johnson, 1965).

(B1) methyl 4-(3,6-dihydro-2,2-dimethyl-6-oxo-2H-pyran-3-ylideneacetyl)-8- furanoyl-5-(1-hydroxyethyl)-4,8-dimethyl-1-oxaspiro[2.5]octane-2-carboxylate

Crystal data

C27H32O9	Dx = 1.301 Mg m^−3
Mr = 500.53	Cu Kα radiation, λ = 1.54180 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 12.216 (4) Å	θ = 14.0–22.1°
b = 12.463 (5) Å	µ = 0.81 mm^−1
c = 16.781 (7) Å	T = 293 K
V = 2554.9 (17) Å^3	Prism, colorless
Z = 4	0.53 × 0.26 × 0.2 mm
F(000) = 1064

Data collection

Nonius CAD4 diffractometer	Rint = 0.026
Radiation source: fine-focus sealed tube	θmax = 66.9°, θmin = 4.4°
Graphite monochromator	h = −10→14
θ/2θ scans	k = 0→14
3271 measured reflections	l = 0→19
2327 independent reflections	3 standard reflections every 120 min
2192 reflections with I > 2σ(I)	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.08	Calculated w = 1/[σ^2(Fo^2) + (0.0859P)^2 + 0.5597P] where P = (Fo^2 + 2Fc^2)/3
2327 reflections	(Δ/σ)max = −0.004
325 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.0596 (3)	0.0522 (2)	0.1814 (2)	0.0393 (7)
C2	0.0238 (3)	0.1355 (3)	0.1232 (2)	0.0448 (8)
H2	0.0486	0.2052	0.1310	0.054*
C3	−0.0409 (3)	0.1173 (3)	0.0609 (2)	0.0427 (7)
C4	−0.0764 (3)	0.2090 (3)	0.0070 (2)	0.0495 (8)
C5	−0.2185 (4)	0.0890 (4)	−0.0459 (2)	0.0654 (11)
C6	−0.1524 (4)	−0.0003 (4)	−0.0205 (3)	0.0687 (12)
H6	−0.1654	−0.0677	−0.0423	0.082*
C7	−0.0732 (4)	0.0107 (3)	0.0334 (2)	0.0567 (10)
H7	−0.0382	−0.0497	0.0537	0.068*
C8	0.1694 (2)	0.0694 (2)	0.2253 (2)	0.0332 (6)
C9	0.2135 (3)	−0.0419 (2)	0.2518 (2)	0.0373 (7)
H9	0.1539	−0.0800	0.2788	0.045*
C10	0.2522 (3)	−0.1117 (3)	0.1818 (2)	0.0555 (9)
H10	0.3275	−0.0899	0.1697	0.067*
C11	0.3086 (3)	−0.0301 (2)	0.3113 (2)	0.0447 (8)
H11A	0.3269	−0.1006	0.3320	0.054*
H11B	0.3722	−0.0033	0.2830	0.054*
C12	0.2851 (3)	0.0437 (2)	0.3808 (2)	0.0435 (8)
H12A	0.3510	0.0508	0.4126	0.052*
H12B	0.2294	0.0111	0.4141	0.052*
C13	0.2462 (3)	0.1566 (2)	0.3560 (2)	0.0370 (7)
C14	0.1466 (2)	0.1366 (2)	0.3015 (2)	0.0302 (6)
C15	0.0341 (3)	0.1297 (2)	0.3362 (2)	0.0384 (7)
H15	−0.0148	0.0812	0.3073	0.046*
C16	−0.0005 (3)	0.1508 (3)	0.4200 (2)	0.0447 (8)
C17	0.3415 (3)	0.2205 (3)	0.3173 (2)	0.0406 (7)
C18	0.2210 (3)	0.2221 (3)	0.4325 (2)	0.0469 (8)
H18A	0.1966	0.2927	0.4179	0.056*
H18B	0.2861	0.2276	0.4643	0.056*
H18C	0.1647	0.1867	0.4625	0.056*
C19	0.2559 (5)	−0.2296 (3)	0.2035 (3)	0.089 (2)
H19A	0.2803	−0.2704	0.1583	0.107*
H19B	0.1841	−0.2531	0.2188	0.107*
H19C	0.3057	−0.2400	0.2471	0.107*
C20	0.3264 (3)	0.3311 (3)	0.2884 (2)	0.0402 (7)
C21	0.2381 (3)	0.3964 (3)	0.2856 (3)	0.0558 (10)
H21	0.1677	0.3759	0.3003	0.067*
C22	0.4146 (3)	0.3953 (3)	0.2594 (2)	0.0517 (9)
H22	0.4869	0.3733	0.2533	0.062*
C23	0.3755 (4)	0.4915 (3)	0.2427 (3)	0.0619 (11)
H23	0.4165	0.5484	0.2229	0.074*
C28	−0.0912 (5)	0.3139 (3)	0.0502 (3)	0.0765 (14)
H28A	−0.1410	0.3041	0.0939	0.092*
H28B	−0.1203	0.3665	0.0142	0.092*
H28C	−0.0218	0.3379	0.0702	0.092*
C29	0.0011 (4)	0.2205 (4)	−0.0620 (2)	0.0668 (11)
H29A	0.0089	0.1525	−0.0884	0.080*
H29B	0.0712	0.2438	−0.0429	0.080*
H29C	−0.0273	0.2724	−0.0989	0.080*
C30	0.2491 (3)	0.1279 (3)	0.1690 (2)	0.0421 (7)
H30A	0.3177	0.1391	0.1956	0.051*
H30B	0.2185	0.1960	0.1540	0.051*
H30C	0.2607	0.0852	0.1221	0.051*
C31	−0.0265 (4)	0.0677 (4)	0.5448 (2)	0.0664 (11)
H31A	−0.0126	0.0005	0.5709	0.080*
H31B	−0.1038	0.0816	0.5446	0.080*
H31C	0.0105	0.1243	0.5728	0.080*
O1	0.0010 (2)	−0.0229 (2)	0.19693 (15)	0.0531 (6)
O4	−0.1860 (2)	0.1882 (2)	−0.0261 (2)	0.0660 (8)
O7	−0.3039 (3)	0.0793 (4)	−0.0824 (2)	0.0964 (12)
O10	0.1900 (3)	−0.0965 (2)	0.11050 (15)	0.0639 (7)
HO10	0.1324	−0.1300	0.11372	0.077*
O14	0.0676 (2)	0.2218 (2)	0.29068 (13)	0.0397 (5)
O16	−0.0422 (2)	0.2327 (2)	0.4432 (2)	0.0601 (7)
O16'	0.0131 (2)	0.0629 (2)	0.46411 (14)	0.0504 (6)
O17	0.4332 (2)	0.1828 (2)	0.3173 (2)	0.0582 (7)
O21	0.2651 (2)	0.4948 (2)	0.2589 (2)	0.0685 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.041 (2)	0.043 (2)	0.034 (2)	−0.0027 (14)	−0.0045 (15)	−0.0004 (13)
C2	0.053 (2)	0.041 (2)	0.041 (2)	−0.0009 (15)	−0.008 (2)	0.0019 (13)
C3	0.051 (2)	0.046 (2)	0.031 (2)	0.0026 (15)	−0.004 (2)	0.0019 (14)
C4	0.053 (2)	0.047 (2)	0.048 (2)	0.007 (2)	−0.008 (2)	0.002 (2)
C5	0.057 (2)	0.086 (3)	0.053 (2)	−0.009 (2)	−0.005 (2)	0.011 (2)
C6	0.088 (3)	0.062 (2)	0.056 (2)	−0.020 (2)	−0.025 (2)	0.002 (2)
C7	0.077 (3)	0.049 (2)	0.044 (2)	−0.002 (2)	−0.015 (2)	0.002 (2)
C8	0.0352 (14)	0.0333 (13)	0.0313 (15)	−0.0009 (11)	−0.0008 (14)	−0.0013 (12)
C9	0.0359 (15)	0.0344 (15)	0.042 (2)	0.0020 (12)	0.0006 (14)	0.0005 (13)
C10	0.055 (2)	0.046 (2)	0.065 (2)	0.003 (2)	0.004 (2)	−0.017 (2)
C11	0.039 (2)	0.0404 (15)	0.054 (2)	0.0051 (13)	−0.008 (2)	0.0029 (14)
C12	0.044 (2)	0.040 (2)	0.047 (2)	0.0021 (14)	−0.008 (2)	0.0057 (14)
C13	0.0366 (15)	0.0377 (14)	0.037 (2)	−0.0019 (13)	−0.0053 (14)	0.0023 (13)
C14	0.0279 (12)	0.0307 (12)	0.032 (2)	−0.0005 (11)	−0.0004 (13)	0.0008 (11)
C15	0.0350 (14)	0.0383 (15)	0.042 (2)	0.0005 (12)	0.0029 (14)	−0.0014 (13)
C16	0.042 (2)	0.042 (2)	0.050 (2)	0.0033 (15)	0.003 (2)	0.0005 (14)
C17	0.0360 (15)	0.044 (2)	0.042 (2)	−0.0023 (13)	−0.0009 (15)	−0.0059 (14)
C18	0.050 (2)	0.051 (2)	0.039 (2)	−0.010 (2)	−0.004 (2)	−0.0059 (15)
C19	0.116 (4)	0.048 (2)	0.102 (4)	0.026 (3)	−0.027 (4)	−0.023 (2)
C20	0.038 (2)	0.043 (2)	0.039 (2)	−0.0077 (13)	0.0006 (14)	−0.0022 (14)
C21	0.050 (2)	0.037 (2)	0.081 (3)	−0.0021 (15)	0.006 (2)	0.006 (2)
C22	0.046 (2)	0.057 (2)	0.052 (2)	−0.012 (2)	0.003 (2)	0.001 (2)
C23	0.064 (2)	0.055 (2)	0.066 (3)	−0.018 (2)	0.006 (2)	0.008 (2)
C28	0.106 (4)	0.051 (2)	0.072 (3)	0.024 (2)	−0.018 (3)	−0.004 (2)
C29	0.076 (3)	0.074 (3)	0.051 (2)	0.003 (2)	0.002 (2)	0.018 (2)
C30	0.046 (2)	0.047 (2)	0.034 (2)	−0.0084 (14)	0.006 (2)	0.0021 (13)
C31	0.082 (3)	0.073 (2)	0.044 (2)	0.006 (2)	0.016 (2)	0.007 (2)
O1	0.0506 (13)	0.0567 (13)	0.0521 (14)	−0.0171 (11)	−0.0092 (13)	0.0090 (12)
O4	0.058 (2)	0.069 (2)	0.071 (2)	0.0086 (14)	−0.0160 (15)	0.0051 (15)
O7	0.067 (2)	0.134 (3)	0.088 (2)	−0.021 (2)	−0.030 (2)	0.018 (2)
O10	0.085 (2)	0.0597 (15)	0.0475 (14)	−0.0137 (15)	0.004 (2)	−0.0097 (12)
O14	0.0389 (11)	0.0360 (10)	0.0441 (12)	0.0073 (9)	0.0013 (10)	0.0034 (9)
O16	0.069 (2)	0.0582 (14)	0.0536 (15)	0.0233 (14)	0.0154 (14)	−0.0015 (12)
O16'	0.0587 (14)	0.0461 (12)	0.0463 (13)	0.0029 (11)	0.0134 (13)	0.0031 (10)
O17	0.0327 (11)	0.0545 (14)	0.088 (2)	0.0006 (10)	−0.0012 (13)	−0.0017 (14)
O21	0.067 (2)	0.0425 (12)	0.096 (2)	−0.0025 (12)	0.007 (2)	0.0121 (14)

Geometric parameters (Å, º)

C1—O1	1.207 (4)	C11—C12	1.513 (5)
C1—C2	1.490 (4)	C12—C13	1.541 (4)
C1—C8	1.547 (4)	C13—C14	1.543 (4)
C2—C3	1.330 (5)	C13—C18	1.552 (5)
C3—C7	1.460 (5)	C13—C17	1.554 (4)
C3—C4	1.521 (5)	C14—O14	1.446 (3)
C4—O4	1.472 (5)	C14—C15	1.494 (4)
C4—C29	1.503 (6)	C15—O14	1.438 (4)
C4—C28	1.506 (5)	C15—C16	1.492 (5)
C5—O7	1.216 (5)	C16—O16	1.206 (4)
C5—O4	1.340 (5)	C16—O16'	1.332 (4)
C5—C6	1.440 (6)	C17—O17	1.215 (4)
C6—C7	1.332 (6)	C17—C20	1.473 (5)
C8—C30	1.540 (4)	C20—C21	1.351 (5)
C8—C14	1.553 (4)	C20—C22	1.429 (5)
C8—C9	1.553 (4)	C21—O21	1.347 (4)
C9—C10	1.537 (5)	C22—C23	1.320 (6)
C9—C11	1.538 (4)	C23—O21	1.377 (5)
C10—O10	1.429 (5)	C31—O16'	1.439 (5)
C10—C19	1.515 (6)
O1—C1—C2	120.5 (3)	C12—C13—C14	104.9 (2)
O1—C1—C8	121.3 (3)	C12—C13—C18	108.6 (3)
C2—C1—C8	118.1 (3)	C14—C13—C18	114.8 (3)
C3—C2—C1	124.8 (3)	C12—C13—C17	110.4 (3)
C2—C3—C7	124.3 (3)	C14—C13—C17	115.2 (3)
C2—C3—C4	120.6 (3)	C18—C13—C17	103.0 (2)
C7—C3—C4	114.8 (3)	O14—C14—C15	58.5 (2)
O4—C4—C29	107.4 (3)	O14—C14—C13	118.9 (2)
O4—C4—C28	103.0 (3)	C15—C14—C13	120.1 (3)
C29—C4—C28	111.4 (4)	O14—C14—C8	114.4 (2)
O4—C4—C3	110.5 (3)	C15—C14—C8	117.1 (2)
C29—C4—C3	110.5 (3)	C13—C14—C8	115.7 (2)
C28—C4—C3	113.6 (3)	O14—C15—C16	116.2 (3)
O7—C5—O4	118.1 (4)	O14—C15—C14	59.0 (2)
O7—C5—C6	123.6 (5)	C16—C15—C14	128.2 (3)
O4—C5—C6	118.3 (4)	O16—C16—O16'	124.7 (3)
C7—C6—C5	121.9 (4)	O16—C16—C15	124.9 (3)
C6—C7—C3	120.3 (4)	O16'—C16—C15	110.1 (3)
C30—C8—C1	108.7 (2)	O17—C17—C20	118.6 (3)
C30—C8—C14	111.3 (2)	O17—C17—C13	119.5 (3)
C1—C8—C14	108.1 (2)	C20—C17—C13	121.5 (3)
C30—C8—C9	112.3 (2)	C21—C20—C22	104.6 (3)
C1—C8—C9	108.3 (2)	C21—C20—C17	132.5 (3)
C14—C8—C9	108.0 (2)	C22—C20—C17	122.8 (3)
C10—C9—C11	108.6 (3)	O21—C21—C20	111.4 (3)
C10—C9—C8	113.2 (3)	C23—C22—C20	108.0 (3)
C11—C9—C8	111.3 (2)	C22—C23—O21	109.9 (3)
O10—C10—C19	110.2 (3)	C5—O4—C4	121.7 (3)
O10—C10—C9	113.7 (3)	C15—O14—C14	62.4 (2)
C19—C10—C9	112.0 (4)	C16—O16'—C31	116.5 (3)
C12—C11—C9	114.5 (3)	C21—O21—C23	106.1 (3)
C11—C12—C13	114.0 (3)
O1—C1—C2—C3	−31.3 (5)	C18—C13—C14—C8	−179.0 (2)
C8—C1—C2—C3	153.1 (3)	C17—C13—C14—C8	61.7 (3)
C1—C2—C3—C7	−9.7 (6)	C30—C8—C14—O14	79.6 (3)
C1—C2—C3—C4	177.4 (3)	C1—C8—C14—O14	−39.7 (3)
C7—C3—C4—O4	37.8 (4)	C9—C8—C14—O14	−156.7 (2)
C3—C4—O4—C5	−35.9 (5)	C30—C8—C14—C15	145.3 (3)
C4—O4—C5—C6	11.6 (6)	C1—C8—C14—C15	25.9 (3)
O4—C5—C6—C7	12.6 (7)	C9—C8—C14—C15	−91.0 (3)
C5—C6—C7—C3	−8.2 (7)	C30—C8—C14—C13	−64.1 (3)
C6—C7—C3—C4	−18.2 (6)	C1—C8—C14—C13	176.6 (2)
C8—C9—C10—O10	−33.8 (4)	C9—C8—C14—C13	59.6 (3)
C13—C14—C15—C16	6.8 (4)	O14—C14—C15—O14	0.0
C14—C15—C16—O16	99.9 (4)	C13—C14—C15—O14	107.4 (3)
C2—C3—C4—O4	−148.7 (3)	C8—C14—C15—O14	−103.4 (3)
C2—C3—C4—C29	92.6 (4)	O14—C14—C15—C16	−100.6 (3)
C7—C3—C4—C29	−80.9 (4)	C13—C14—C15—C16	6.8 (4)
C2—C3—C4—C28	−33.4 (5)	C8—C14—C15—C16	156.1 (3)
C7—C3—C4—C28	153.0 (4)	O14—C15—C16—O16	30.0 (5)
O7—C5—C6—C7	−165.2 (5)	C14—C15—C16—O16	99.9 (4)
C2—C3—C7—C6	168.6 (4)	O14—C15—C16—O16'	−155.1 (3)
O1—C1—C8—C30	151.0 (3)	C14—C15—C16—O16'	−85.1 (4)
C2—C1—C8—C30	−33.4 (4)	C12—C13—C17—O17	−6.8 (4)
O1—C1—C8—C9	28.7 (4)	C14—C13—C17—O17	−125.3 (3)
C2—C1—C8—C9	−155.7 (3)	C18—C13—C17—O17	109.0 (3)
O1—C1—C8—C14	−88.0 (3)	C12—C13—C17—C20	−179.9 (3)
C2—C1—C8—C14	87.6 (3)	C14—C13—C17—C20	61.6 (4)
C30—C8—C9—C10	−50.1 (3)	C18—C13—C17—C20	−64.1 (4)
C1—C8—C9—C10	69.9 (3)	O17—C17—C20—C21	−175.3 (4)
C14—C8—C9—C10	−173.3 (3)	C13—C17—C20—C21	−2.1 (6)
C30—C8—C9—C11	72.4 (3)	O17—C17—C20—C22	0.8 (5)
C1—C8—C9—C11	−167.6 (3)	C13—C17—C20—C22	174.0 (3)
C14—C8—C9—C11	−50.7 (3)	C22—C20—C21—O21	−1.0 (5)
C11—C9—C10—O10	−157.8 (3)	C17—C20—C21—O21	175.6 (3)
C8—C9—C10—O10	−33.8 (4)	C21—C20—C22—C23	0.7 (5)
C11—C9—C10—C19	76.4 (4)	C17—C20—C22—C23	−176.3 (3)
C8—C9—C10—C19	−159.5 (4)	C20—C22—C23—O21	−0.2 (5)
C10—C9—C11—C12	175.7 (3)	O7—C5—O4—C4	−170.5 (4)
C8—C9—C11—C12	50.5 (4)	C29—C4—O4—C5	84.8 (4)
C9—C11—C12—C13	−53.9 (4)	C28—C4—O4—C5	−157.5 (4)
C11—C12—C13—C14	54.7 (3)	C16—C15—O14—C14	120.6 (3)
C11—C12—C13—C18	177.9 (3)	C14—C15—O14—C14	0.0
C11—C12—C13—C17	−69.9 (3)	C15—C14—O14—C15	0.0
C12—C13—C14—O14	158.1 (3)	C13—C14—O14—C15	−109.6 (3)
C18—C13—C14—O14	39.0 (4)	C8—C14—O14—C15	108.0 (3)
C17—C13—C14—O14	−80.3 (3)	O16—C16—O16'—C31	0.6 (6)
C12—C13—C14—C15	89.8 (3)	C15—C16—O16'—C31	−174.4 (3)
C18—C13—C14—C15	−29.3 (4)	C20—C21—O21—C23	0.9 (5)
C17—C13—C14—C15	−148.6 (3)	C22—C23—O21—C21	−0.5 (5)
C12—C13—C14—C8	−59.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—HO10···O16^i	0.82	2.25	2.933 (4)	141

Symmetry code: (i) −x, y−1/2, −z+1/2.

(D) methyl 6'-furanoyl-3-hydroxy-4,4,3',6',7a'-pentamethylperhydro-4H-furo[2,1-c]- pyran-2-spiro-1'-perhydroisobenzofuran-7'-spiro-2''-oxirane-3''-carboxylate

Crystal data

C27H34O10	F(000) = 552
Mr = 518.54	Dx = 1.350 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54180 Å
a = 10.148 (5) Å	Cell parameters from 25 reflections
b = 11.225 (7) Å	θ = 15.2–21.0°
c = 11.356 (8) Å	µ = 0.86 mm^−1
β = 99.44 (2)°	T = 293 K
V = 1276.1 (14) Å^3	Prism, colourless
Z = 2	0.35 × 0.35 × 0.20 mm

Data collection

Nonius CAD4 diffractometer	Rint = 0.061
Radiation source: fine-focus sealed tube	θmax = 66.9°, θmin = 4.4°
Graphite monochromator	h = −11→11
θ/2θ scans	k = 0→13
3411 measured reflections	l = 0→13
2389 independent reflections	3 standard reflections every 120 min
2368 reflections with I > 2σ(I)	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.09	Calculated w = 1/[σ^2(Fo^2) + (0.1223P)^2 + 0.1273P] where P = (Fo^2 + 2Fc^2)/3
2385 reflections	(Δ/σ)max = −0.023
334 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

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 on F² for ALL reflections except for 4 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3417 (3)	0.3796 (4)	0.8838 (2)	0.0413 (6)
C2	0.2893 (3)	0.3384 (4)	0.9969 (2)	0.0435 (6)
H2	0.3609	0.3015	1.0535	0.052*
C3	0.2482 (3)	0.4577 (4)	1.0446 (3)	0.0478 (7)
H3	0.3296	0.4960	1.0861	0.057*
C4	0.1472 (3)	0.4560 (5)	1.1306 (3)	0.0557 (8)
C5	−0.0262 (3)	0.4443 (6)	0.9550 (4)	0.0698 (11)
C6	0.0488 (4)	0.5422 (6)	0.9025 (4)	0.0761 (13)
H6A	0.0236	0.6183	0.9326	0.091*
H6B	0.0218	0.5426	0.8165	0.091*
C7	0.2003 (4)	0.5298 (4)	0.9308 (3)	0.0552 (8)
H7	0.2415	0.6090	0.9380	0.066*
C8	0.3746 (3)	0.2872 (4)	0.7896 (2)	0.0400 (6)
C9	0.4618 (3)	0.3705 (4)	0.7256 (3)	0.0450 (7)
H9	0.4027	0.4321	0.6849	0.054*
C10	0.5506 (3)	0.4301 (4)	0.8297 (3)	0.0496 (7)
H10	0.6263	0.3776	0.8582	0.060*
C11	0.5254 (4)	0.3063 (4)	0.6305 (3)	0.0531 (8)
H11A	0.5739	0.3629	0.5893	0.064*
H11B	0.5880	0.2468	0.6678	0.064*
C12	0.4170 (4)	0.2472 (4)	0.5423 (3)	0.0550 (8)
H12A	0.4587	0.2042	0.4842	0.066*
H12B	0.3612	0.3087	0.4999	0.066*
C13	0.3263 (3)	0.1594 (4)	0.5987 (3)	0.0468 (7)
C14	0.2683 (3)	0.2296 (4)	0.6958 (2)	0.0406 (6)
C15	0.1306 (3)	0.2815 (4)	0.6744 (3)	0.0486 (7)
H15	0.1221	0.3519	0.7235	0.058*
C16	0.0269 (4)	0.2765 (5)	0.5647 (3)	0.0589 (9)
C17	0.4072 (3)	0.0464 (4)	0.6414 (3)	0.0482 (7)
C18	0.2206 (4)	0.1108 (5)	0.4972 (3)	0.0618 (9)
H18A	0.1637	0.1747	0.4635	0.093*
H18B	0.1679	0.0512	0.5283	0.093*
H18C	0.2642	0.0763	0.4365	0.093*
C19	0.6028 (5)	0.5517 (5)	0.8063 (5)	0.0731 (11)
H19A	0.6574	0.5809	0.8775	0.110*
H19B	0.5291	0.6050	0.7831	0.110*
H19C	0.6552	0.5467	0.7433	0.110*
C20	0.3526 (3)	−0.0513 (4)	0.7058 (3)	0.0492 (7)
C21	0.2329 (5)	−0.0688 (5)	0.7469 (6)	0.088 (2)
H21	0.1626	−0.0147	0.7398	0.105*
C22	0.4252 (4)	−0.1539 (5)	0.7385 (4)	0.0608 (9)
H22	0.5097	−0.1706	0.7211	0.073*
C23	0.3551 (4)	−0.2249 (5)	0.7990 (4)	0.0655 (10)
H23	0.3848	−0.2964	0.8354	0.079*
C28	0.1360 (5)	0.5813 (6)	1.1824 (5)	0.0831 (15)
H28A	0.1145	0.6374	1.1184	0.125*
H28B	0.2195	0.6028	1.2303	0.125*
H28C	0.0669	0.5818	1.2309	0.125*
C29	0.1811 (4)	0.3630 (7)	1.2279 (3)	0.0768 (13)
H29A	0.1154	0.3649	1.2798	0.115*
H29B	0.2676	0.3797	1.2732	0.115*
H29C	0.1818	0.2854	1.1923	0.115*
C30	0.4587 (3)	0.1895 (4)	0.8634 (3)	0.0440 (6)
H30A	0.5252	0.2262	0.9221	0.066*
H30B	0.5016	0.1410	0.8112	0.066*
H30C	0.4013	0.1407	0.9026	0.066*
C31	−0.1611 (6)	0.1723 (9)	0.4668 (5)	0.108 (2)
H31A	−0.2122	0.1023	0.4773	0.162*
H31B	−0.1251	0.1657	0.3939	0.162*
H31C	−0.2177	0.2412	0.4630	0.162*
O1	0.2442 (2)	0.4654 (3)	0.8336 (2)	0.0480 (5)
O2	0.1793 (2)	0.2612 (4)	0.9714 (2)	0.0530 (6)
HO2	0.1650	0.2465	0.8997	0.051*
O4	0.0151 (2)	0.4182 (4)	1.0686 (2)	0.0618 (7)
O7	−0.1231 (4)	0.3961 (7)	0.9026 (4)	0.110 (2)
O10	0.4660 (2)	0.4386 (4)	0.9212 (2)	0.0546 (6)
O14	0.1587 (2)	0.1745 (3)	0.7438 (2)	0.0473 (5)
O16	0.0167 (4)	0.3540 (4)	0.4901 (3)	0.0815 (9)
O16'	−0.0534 (3)	0.1840 (5)	0.5658 (2)	0.0725 (8)
O17	0.5166 (3)	0.0316 (4)	0.6119 (3)	0.0641 (7)
O21	0.2348 (4)	−0.1762 (5)	0.7988 (5)	0.111 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0345 (13)	0.0444 (14)	0.0479 (13)	0.0017 (11)	0.0149 (10)	0.0026 (12)
C2	0.0396 (14)	0.052 (2)	0.0413 (12)	0.0005 (12)	0.0128 (10)	0.0000 (12)
C3	0.0373 (13)	0.057 (2)	0.0533 (15)	−0.0058 (12)	0.0185 (11)	−0.0083 (13)
C4	0.041 (2)	0.076 (2)	0.054 (2)	−0.0005 (15)	0.0198 (13)	−0.012 (2)
C5	0.035 (2)	0.094 (3)	0.081 (2)	0.013 (2)	0.0119 (15)	−0.009 (2)
C6	0.070 (2)	0.086 (3)	0.078 (2)	0.038 (2)	0.029 (2)	0.018 (2)
C7	0.057 (2)	0.048 (2)	0.067 (2)	0.006 (2)	0.0290 (15)	0.000 (2)
C8	0.0356 (12)	0.0457 (15)	0.0420 (13)	0.0035 (11)	0.0161 (10)	0.0044 (12)
C9	0.0433 (14)	0.0437 (15)	0.0539 (15)	0.0038 (12)	0.0254 (12)	0.0089 (13)
C10	0.0429 (15)	0.045 (2)	0.067 (2)	−0.0009 (13)	0.0278 (13)	0.0007 (14)
C11	0.055 (2)	0.051 (2)	0.063 (2)	0.0017 (15)	0.0357 (14)	0.0058 (15)
C12	0.069 (2)	0.056 (2)	0.0468 (15)	0.006 (2)	0.0306 (14)	0.0086 (14)
C13	0.049 (2)	0.052 (2)	0.0423 (13)	0.0041 (14)	0.0177 (11)	0.0023 (13)
C14	0.0423 (14)	0.0441 (14)	0.0385 (12)	0.0009 (11)	0.0160 (10)	0.0062 (11)
C15	0.0419 (14)	0.057 (2)	0.0481 (14)	0.0055 (13)	0.0114 (11)	0.0031 (14)
C16	0.049 (2)	0.074 (2)	0.054 (2)	0.009 (2)	0.0080 (13)	0.005 (2)
C17	0.049 (2)	0.047 (2)	0.0524 (15)	0.0009 (13)	0.0181 (12)	−0.0024 (13)
C18	0.064 (2)	0.072 (2)	0.050 (2)	0.007 (2)	0.0117 (14)	−0.008 (2)
C19	0.082 (3)	0.050 (2)	0.098 (3)	−0.014 (2)	0.045 (2)	−0.004 (2)
C20	0.0431 (14)	0.046 (2)	0.060 (2)	−0.0001 (13)	0.0148 (12)	−0.0014 (14)
C21	0.062 (2)	0.053 (2)	0.157 (5)	0.003 (2)	0.045 (3)	0.031 (3)
C22	0.050 (2)	0.063 (2)	0.070 (2)	0.002 (2)	0.0126 (15)	0.014 (2)
C23	0.049 (2)	0.055 (2)	0.097 (3)	0.009 (2)	0.024 (2)	0.029 (2)
C28	0.068 (2)	0.102 (4)	0.087 (3)	0.001 (3)	0.033 (2)	−0.043 (3)
C29	0.069 (2)	0.115 (4)	0.054 (2)	0.015 (3)	0.030 (2)	0.011 (2)
C30	0.0415 (13)	0.0461 (15)	0.0461 (13)	0.0050 (13)	0.0120 (10)	0.0049 (13)
C31	0.080 (3)	0.137 (6)	0.093 (3)	−0.013 (4)	−0.028 (3)	−0.003 (4)
O1	0.0500 (11)	0.0454 (12)	0.0527 (11)	0.0071 (9)	0.0203 (9)	0.0047 (9)
O2	0.0571 (13)	0.0585 (13)	0.0489 (11)	−0.0117 (11)	0.0254 (9)	−0.0020 (10)
O4	0.0390 (11)	0.082 (2)	0.0696 (14)	−0.0042 (12)	0.0225 (10)	−0.0036 (13)
O7	0.055 (2)	0.163 (5)	0.106 (2)	−0.002 (2)	−0.005 (2)	−0.023 (3)
O10	0.0418 (11)	0.0639 (14)	0.0635 (13)	−0.0094 (11)	0.0245 (9)	−0.0145 (11)
O14	0.0415 (10)	0.0606 (13)	0.0420 (9)	−0.0036 (9)	0.0140 (8)	0.0074 (10)
O16	0.081 (2)	0.083 (2)	0.075 (2)	0.011 (2)	−0.0023 (15)	0.022 (2)
O16'	0.0589 (14)	0.094 (2)	0.0613 (14)	−0.010 (2)	0.0002 (11)	0.007 (2)
O17	0.0602 (14)	0.0558 (14)	0.086 (2)	0.0083 (12)	0.0417 (13)	0.0019 (13)
O21	0.090 (2)	0.084 (3)	0.175 (4)	0.013 (2)	0.069 (3)	0.047 (3)

Geometric parameters (Å, º)

C1—O10	1.426 (4)	C10—O10	1.456 (3)
C1—O1	1.430 (4)	C10—C19	1.502 (5)
C1—C2	1.540 (4)	C11—C12	1.514 (6)
C1—C8	1.565 (4)	C12—C13	1.556 (5)
C2—O2	1.405 (4)	C13—C18	1.540 (5)
C2—C3	1.528 (5)	C13—C17	1.546 (5)
C3—C4	1.528 (4)	C13—C14	1.548 (4)
C3—C7	1.535 (5)	C14—O14	1.455 (3)
C4—O4	1.471 (4)	C14—C15	1.496 (4)
C4—C29	1.518 (6)	C15—O14	1.439 (4)
C4—C28	1.535 (7)	C15—C16	1.494 (5)
C5—O7	1.193 (6)	C16—O16	1.207 (5)
C5—O4	1.322 (5)	C16—O16'	1.322 (6)
C5—C6	1.514 (8)	C17—O17	1.223 (4)
C6—C7	1.524 (6)	C17—C20	1.475 (5)
C7—O1	1.449 (4)	C20—C22	1.385 (6)
C8—C14	1.530 (4)	C20—C21	1.385 (6)
C8—C9	1.548 (4)	C21—O21	1.341 (7)
C8—C30	1.549 (4)	C22—C23	1.332 (6)
C9—C10	1.519 (5)	C23—O21	1.337 (6)
C9—C11	1.526 (4)	C31—O16'	1.440 (5)
O10—C1—O1	109.0 (3)	C19—C10—C9	116.3 (3)
O10—C1—C2	107.5 (2)	C12—C11—C9	109.3 (3)
O1—C1—C2	102.9 (2)	C11—C12—C13	114.9 (3)
O10—C1—C8	103.5 (2)	C18—C13—C17	102.3 (3)
O1—C1—C8	112.6 (2)	C18—C13—C14	114.4 (3)
C2—C1—C8	120.9 (3)	C17—C13—C14	116.0 (2)
O2—C2—C3	111.1 (2)	C18—C13—C12	107.7 (3)
O2—C2—C1	112.7 (2)	C17—C13—C12	109.2 (3)
C3—C2—C1	100.6 (3)	C14—C13—C12	106.9 (3)
C2—C3—C4	117.8 (3)	O14—C14—C15	58.4 (2)
C2—C3—C7	103.3 (2)	O14—C14—C8	114.4 (2)
C4—C3—C7	113.1 (3)	C15—C14—C8	118.8 (3)
O4—C4—C29	103.3 (3)	O14—C14—C13	117.0 (3)
O4—C4—C3	110.6 (3)	C15—C14—C13	122.4 (3)
C29—C4—C3	112.2 (3)	C8—C14—C13	113.8 (2)
O4—C4—C28	109.2 (3)	O14—C15—C16	118.3 (3)
C29—C4—C28	111.9 (4)	O14—C15—C14	59.4 (2)
C3—C4—C28	109.5 (3)	C16—C15—C14	129.2 (3)
O7—C5—O4	119.4 (5)	O16—C16—O16'	126.2 (4)
O7—C5—C6	124.0 (5)	O16—C16—C15	121.7 (4)
O4—C5—C6	116.4 (4)	O16'—C16—C15	111.9 (3)
C5—C6—C7	113.9 (3)	O17—C17—C20	117.8 (3)
O1—C7—C6	108.1 (3)	O17—C17—C13	119.0 (3)
O1—C7—C3	106.5 (3)	C20—C17—C13	122.9 (3)
C6—C7—C3	113.3 (3)	C22—C20—C21	104.4 (3)
C14—C8—C9	108.7 (2)	C22—C20—C17	121.7 (3)
C14—C8—C30	109.9 (3)	C21—C20—C17	133.9 (4)
C9—C8—C30	112.1 (2)	O21—C21—C20	108.9 (4)
C14—C8—C1	123.4 (2)	C23—C22—C20	109.3 (3)
C9—C8—C1	97.1 (2)	C22—C23—O21	108.6 (4)
C30—C8—C1	105.1 (2)	C1—O1—C7	108.2 (2)
C10—C9—C11	119.5 (3)	C5—O4—C4	121.4 (3)
C10—C9—C8	102.3 (2)	C1—O10—C10	110.7 (2)
C11—C9—C8	112.8 (3)	C15—O14—C14	62.3 (2)
O10—C10—C19	109.4 (3)	C16—O16'—C31	117.0 (4)
O10—C10—C9	103.9 (2)	C23—O21—C21	108.5 (4)
O10—C1—C2—O2	−169.6 (3)	C30—C8—C14—O14	72.5 (3)
O1—C1—C2—O2	75.4 (3)	C1—C8—C14—O14	−52.3 (4)
C8—C1—C2—O2	−51.3 (3)	C9—C8—C14—C15	−98.6 (3)
O10—C1—C2—C3	72.0 (3)	C30—C8—C14—C15	138.4 (3)
O1—C1—C2—C3	−43.0 (3)	C1—C8—C14—C15	13.7 (4)
C8—C1—C2—C3	−169.6 (2)	C9—C8—C14—C13	57.2 (3)
O2—C2—C3—C4	39.4 (4)	C30—C8—C14—C13	−65.8 (3)
C1—C2—C3—C4	158.9 (3)	C1—C8—C14—C13	169.5 (2)
O2—C2—C3—C7	−86.0 (3)	C18—C13—C14—O14	48.3 (4)
C1—C2—C3—C7	33.4 (3)	C17—C13—C14—O14	−70.5 (3)
C2—C3—C4—O4	−68.3 (4)	C12—C13—C14—O14	167.4 (2)
C2—C3—C4—C29	46.5 (4)	C18—C13—C14—C15	−19.8 (4)
C7—C3—C4—C29	167.0 (4)	C17—C13—C14—C15	−138.6 (3)
C2—C3—C4—C28	171.4 (3)	C12—C13—C14—C15	99.3 (3)
C7—C3—C4—C28	−68.1 (4)	C18—C13—C14—C8	−174.6 (3)
O7—C5—C6—C7	−137.4 (5)	C17—C13—C14—C8	66.6 (3)
C5—C6—C7—O1	93.2 (4)	C12—C13—C14—C8	−55.5 (3)
C2—C3—C7—O1	−13.2 (3)	O14—C14—C15—O14	0.000 (1)
C3—C7—O1—C1	−14.6 (3)	C8—C14—C15—O14	−102.5 (3)
C7—O1—C1—C2	36.3 (3)	C13—C14—C15—O14	103.9 (3)
C4—C3—C7—C6	−23.0 (5)	O14—C14—C15—C16	−103.2 (4)
C3—C7—C6—C5	−24.5 (5)	C8—C14—C15—C16	154.3 (3)
C7—C6—C5—O4	47.5 (5)	O14—C15—C16—O16	−165.0 (4)
C6—C5—O4—C4	−17.0 (6)	O14—C15—C16—O16'	19.3 (4)
C5—O4—C4—C3	−32.7 (5)	C14—C15—C16—O16'	91.4 (4)
O4—C4—C3—C7	52.3 (4)	C18—C13—C17—O17	103.3 (3)
O10—C1—C8—C9	−42.2 (3)	C14—C13—C17—O17	−131.5 (3)
C1—C8—C9—C10	45.1 (3)	C12—C13—C17—O17	−10.6 (4)
C8—C9—C10—O10	−32.9 (3)	C18—C13—C17—C20	−70.0 (4)
C9—C10—O10—C1	5.5 (3)	C14—C13—C17—C20	55.3 (4)
C10—O10—C1—C8	23.9 (3)	C12—C13—C17—C20	176.1 (3)
C13—C14—C15—C16	0.7 (5)	O17—C17—C20—C22	3.9 (5)
C14—C15—C16—O16	−92.8 (5)	C13—C17—C20—C22	177.2 (3)
C4—C3—C7—O1	−141.7 (3)	O17—C17—C20—C21	−176.3 (5)
C2—C3—C7—C6	105.5 (3)	C13—C17—C20—C21	−3.0 (7)
O10—C1—C8—C14	−160.1 (3)	C22—C20—C21—O21	−1.0 (7)
O1—C1—C8—C14	−42.5 (3)	C17—C20—C21—O21	179.1 (5)
C2—C1—C8—C14	79.6 (3)	C21—C20—C22—C23	−2.2 (6)
O1—C1—C8—C9	75.5 (3)	C17—C20—C22—C23	177.6 (4)
C2—C1—C8—C9	−162.4 (2)	C20—C22—C23—O21	4.7 (6)
O10—C1—C8—C30	73.0 (3)	O10—C1—O1—C7	−77.6 (3)
O1—C1—C8—C30	−169.3 (2)	C8—C1—O1—C7	168.1 (2)
C2—C1—C8—C30	−47.3 (3)	C6—C7—O1—C1	−136.6 (3)
C14—C8—C9—C10	174.0 (2)	O7—C5—O4—C4	167.7 (5)
C30—C8—C9—C10	−64.3 (3)	C29—C4—O4—C5	−153.0 (4)
C14—C8—C9—C11	−56.3 (3)	C28—C4—O4—C5	87.8 (4)
C30—C8—C9—C11	65.4 (3)	O1—C1—O10—C10	−96.2 (3)
C1—C8—C9—C11	174.8 (3)	C2—C1—O10—C10	152.9 (3)
C11—C9—C10—O10	−158.3 (3)	C19—C10—O10—C1	130.4 (3)
C11—C9—C10—C19	81.4 (4)	C16—C15—O14—C14	121.1 (3)
C8—C9—C10—C19	−153.3 (3)	C14—C15—O14—C14	0.000 (1)
C10—C9—C11—C12	175.8 (3)	C15—C14—O14—C15	0.000 (1)
C8—C9—C11—C12	55.6 (4)	C8—C14—O14—C15	110.0 (3)
C9—C11—C12—C13	−56.1 (4)	C13—C14—O14—C15	−113.2 (3)
C11—C12—C13—C18	178.5 (3)	O16—C16—O16'—C31	2.0 (7)
C11—C12—C13—C17	−71.1 (4)	C15—C16—O16'—C31	177.6 (5)
C11—C12—C13—C14	55.1 (4)	C22—C23—O21—C21	−5.4 (7)
C9—C8—C14—O14	−164.6 (2)	C20—C21—O21—C23	3.9 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—HO2···O14	0.82	1.94	2.738 (3)	165