Three new di­hydro-β-agaro­furan sesquiterpenes from the seeds of Maytenus boaria

Paz, C.; Heydenreich, M.; Schmidt, B.; Vadra, N.; Baggio, R.

doi:10.1107/S2053229618005429

Three new dihydro-β-agarofuran sesquiterpenes from the seeds of Maytenus boaria

C. Paz, M. Heydenreich, B. Schmidt, N. Vadra and R. Baggio

As part of a project studying the secondary metabolites extracted from the Chilean flora, we report herein three new β-agarofuran sesquiterpenes, namely (1S,4S,5S,6R,7R,8R,9R,10S)-6-acetoxy-4,9-dihydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b]oxepine-5,10-diyl bis(furan-3-carboxylate), C₂₇H₃₂O₁₁, (II), (1S,4S,5S,6R,7R,9S,10S)-6-acetoxy-9-hydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b]oxepine-5,10-diyl bis(furan-3-carboxylate), C₂₇H₃₂O₁₀, (III), and (1S,4S,5S,6R,7R,9S,10S)-6-acetoxy-10-(benzoyloxy)-9-hydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b]oxepin-5-yl furan-3-carboxylate, C₂₉H₃₄O₉, (IV), obtained from the seeds of Maytenus boaria and closely associated with a recently published relative [Paz et al. (2017). Acta Cryst. C73, 451–457]. In the (isomorphic) structures of (II) and (III), the central decalin system is esterified with an acetate group at site 1 and furoate groups at sites 6 and 9, and differ at site 8, with an OH group in (II) and no substituent in (III). This position is also unsubstituted in (IV), with site 6 being occupied by a benzoate group. The chirality of the skeletons is described as 1S,4S,5S,6R,7R,8R,9R,10S in (II) and 1S,4S,5S,6R,7R,9S,10S in (III) and (IV), matching the chirality suggested by NMR studies. This difference in the chirality sequence among the title structures (in spite of the fact that the three skeletons are absolutely isostructural) is due to the differences in the environment of site 8, i.e. OH in (II) and H in (III) and (IV). This diversity in substitution, in turn, is responsible for the differences in the hydrogen-bonding schemes, which is discussed.

Keywords: Celastraceae; Maytenus boaria; sesquiterpene; dihydro-β-agarofuran; crystal structure; NMR; DSC.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618005429/lg3223sup1.cif Contains datablocks II, III, IV, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618005429/lg3223IIsup2.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618005429/lg3223IIIsup3.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618005429/lg3223IVsup4.hkl Contains datablock IV
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618005429/lg3223sup5.pdf Notes on AIM analysis and Tables of NMR data

CCDC references: 1835260; 1835259; 1835258

Computing details top

For all structures, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

(1S,4S,5S,6R,7R,8R,9R,10S)-6-Acetoxy-4,9-dihydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b]oxepine-5,10-diyl bis(furan-3-carboxylate) (II) top

Crystal data top

C₂₇H₃₂O₁₁	F(000) = 564
M_r = 532.52	D_x = 1.360 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.7107 Å
a = 11.2664 (3) Å	Cell parameters from 2709 reflections
b = 9.6575 (3) Å	θ = 4.2–20.4°
c = 12.0758 (4) Å	µ = 0.11 mm⁻¹
β = 98.262 (3)°	T = 294 K
V = 1300.28 (6) Å³	Block, colourless
Z = 2	0.28 × 0.18 × 0.14 mm

Data collection top

CCD Oxford Diffraction Xcalibur, Eos, Gemini diffractometer	4132 reflections with I > 2σ(I)
thick slices scans	R_int = 0.053
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	θ_max = 26.5°, θ_min = 3.8°
T_min = 0.95, T_max = 0.98	h = −14→14
32072 measured reflections	k = −12→12
5376 independent reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0748P)² + 0.0201P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.120	(Δ/σ)_max < 0.001
S = 0.96	Δρ_max = 0.14 e Å⁻³
5376 reflections	Δρ_min = −0.21 e Å⁻³
356 parameters	Absolute structure: Absolute structure assigned by comparison with related compounds of the same origin.
3 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.45046 (17)	0.6039 (2)	0.34735 (16)	0.0334 (5)
O2	0.6670 (2)	0.5638 (3)	0.2980 (2)	0.0499 (6)
H2	0.634 (3)	0.557 (5)	0.357 (2)	0.060*
O3	0.2374 (2)	0.9090 (3)	0.1659 (2)	0.0545 (7)
H3	0.239 (4)	0.990 (2)	0.194 (4)	0.065*
O1A	0.59613 (18)	0.8357 (2)	0.2523 (2)	0.0418 (5)
O2A	0.5480 (2)	1.0554 (3)	0.2082 (3)	0.0638 (8)
O1B	0.19077 (17)	0.5805 (2)	0.28708 (18)	0.0380 (5)
O2B	−0.0007 (2)	0.6249 (3)	0.2174 (3)	0.0800 (11)
O1C	0.2103 (2)	0.4054 (3)	0.0955 (2)	0.0517 (6)
O2C	0.1984 (3)	0.2083 (3)	0.1905 (3)	0.0734 (9)
C1	0.3244 (3)	0.4389 (3)	0.1630 (3)	0.0392 (7)
H1	0.320942	0.411590	0.240687	0.047*
C2	0.4263 (3)	0.3614 (3)	0.1210 (3)	0.0501 (9)
H2A	0.433815	0.390627	0.045456	0.060*
H2B	0.410725	0.262621	0.120163	0.060*
C3	0.5405 (3)	0.3936 (4)	0.1990 (3)	0.0481 (9)
H3A	0.606173	0.342888	0.174195	0.058*
H3B	0.532014	0.360960	0.273453	0.058*
C4	0.5725 (3)	0.5480 (3)	0.2055 (3)	0.0396 (7)
C5	0.4620 (3)	0.6349 (3)	0.2307 (3)	0.0313 (6)
C6	0.4723 (3)	0.7931 (3)	0.2263 (3)	0.0348 (7)
H6	0.437557	0.827560	0.152415	0.042*
C7	0.3935 (3)	0.8342 (3)	0.3142 (3)	0.0374 (7)
H7	0.408612	0.929997	0.338994	0.045*
C8	0.2632 (3)	0.8149 (3)	0.2566 (3)	0.0404 (8)
H8	0.208723	0.833577	0.311189	0.049*
C9	0.2347 (3)	0.6705 (3)	0.2053 (3)	0.0378 (7)
H9	0.169328	0.681945	0.143086	0.045*
C10	0.3393 (3)	0.5961 (3)	0.1582 (2)	0.0329 (6)
C11	0.4333 (3)	0.7309 (3)	0.4096 (3)	0.0375 (7)
C12	0.5521 (3)	0.7714 (4)	0.4810 (3)	0.0500 (9)
H12A	0.575543	0.700266	0.535334	0.075*
H12B	0.542126	0.857203	0.518665	0.075*
H12C	0.613095	0.781916	0.433658	0.075*
C13	0.3436 (3)	0.7035 (4)	0.4900 (3)	0.0500 (9)
H13A	0.268664	0.674376	0.448562	0.075*
H13B	0.331718	0.786692	0.530470	0.075*
H13C	0.373989	0.632033	0.541737	0.075*
C14	0.6270 (3)	0.5915 (4)	0.1023 (3)	0.0531 (9)
H14A	0.630732	0.690740	0.099054	0.080*
H14B	0.578035	0.557348	0.036262	0.080*
H14C	0.706356	0.553934	0.106463	0.080*
C15	0.3310 (3)	0.6448 (4)	0.0347 (3)	0.0452 (8)
H15A	0.405550	0.626044	0.007803	0.068*
H15B	0.315087	0.742435	0.030496	0.068*
H15C	0.267380	0.595966	−0.010421	0.068*
C1A	0.6222 (3)	0.9681 (3)	0.2339 (3)	0.0408 (8)
C2A	0.7521 (3)	0.9887 (4)	0.2479 (3)	0.0475 (8)
C3A	0.8141 (4)	1.1171 (5)	0.2624 (4)	0.0708 (12)
H3A1	0.779723	1.204158	0.266957	0.085*
C4A	0.9283 (4)	1.0899 (6)	0.2680 (4)	0.0828 (15)
H4A	0.989115	1.155694	0.277454	0.099*
O3A	0.9459 (3)	0.9473 (5)	0.2576 (4)	0.1034 (13)
C5A	0.8354 (4)	0.8903 (5)	0.2446 (4)	0.0724 (13)
H5A	0.819348	0.796261	0.234627	0.087*
C1B	0.0713 (3)	0.5645 (4)	0.2814 (3)	0.0421 (8)
C2B	0.0443 (3)	0.4647 (4)	0.3649 (3)	0.0439 (8)
C3B	0.1226 (4)	0.3784 (5)	0.4343 (4)	0.0637 (11)
H3B1	0.205316	0.374118	0.436409	0.076*
C4B	0.0591 (5)	0.3046 (5)	0.4960 (4)	0.0828 (16)
H4B	0.089763	0.238766	0.548658	0.099*
O3B	−0.0620 (3)	0.3407 (4)	0.4699 (3)	0.0945 (11)
C5B	−0.0669 (3)	0.4355 (5)	0.3889 (4)	0.0618 (11)
H5B	−0.137226	0.475996	0.353658	0.074*
C1C	0.1570 (4)	0.2864 (4)	0.1177 (4)	0.0579 (10)
C2C	0.0417 (5)	0.2669 (7)	0.0407 (4)	0.100 (2)
H2C1	0.018985	0.171030	0.040006	0.150*
H2C2	0.051981	0.295148	−0.033493	0.150*
H2C3	−0.019903	0.321947	0.066362	0.150*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0370 (11)	0.0319 (10)	0.0314 (11)	−0.0009 (9)	0.0057 (8)	0.0016 (9)
O2	0.0388 (13)	0.0532 (14)	0.0571 (16)	0.0075 (11)	0.0047 (11)	0.0050 (12)
O3	0.0593 (15)	0.0332 (12)	0.0689 (17)	0.0090 (12)	0.0019 (13)	0.0091 (12)
O1A	0.0342 (12)	0.0332 (12)	0.0577 (15)	−0.0069 (9)	0.0058 (10)	0.0031 (10)
O2A	0.0524 (16)	0.0354 (13)	0.101 (2)	−0.0025 (12)	0.0037 (14)	0.0143 (14)
O1B	0.0295 (11)	0.0399 (12)	0.0437 (12)	−0.0046 (9)	0.0017 (9)	0.0059 (10)
O2B	0.0340 (14)	0.098 (2)	0.106 (3)	0.0133 (15)	0.0024 (15)	0.050 (2)
O1C	0.0589 (15)	0.0429 (13)	0.0503 (14)	−0.0162 (12)	−0.0028 (11)	−0.0028 (11)
O2C	0.094 (2)	0.0451 (15)	0.081 (2)	−0.0225 (15)	0.0138 (18)	0.0006 (16)
C1	0.0467 (19)	0.0296 (16)	0.0397 (17)	−0.0070 (13)	0.0006 (14)	−0.0025 (13)
C2	0.070 (2)	0.0316 (17)	0.051 (2)	0.0025 (16)	0.0168 (18)	−0.0078 (15)
C3	0.055 (2)	0.0353 (17)	0.056 (2)	0.0097 (16)	0.0157 (18)	0.0024 (15)
C4	0.0410 (17)	0.0358 (16)	0.0431 (18)	0.0074 (14)	0.0101 (14)	0.0031 (14)
C5	0.0345 (15)	0.0285 (15)	0.0316 (16)	−0.0001 (12)	0.0068 (12)	0.0009 (12)
C6	0.0303 (15)	0.0296 (15)	0.0441 (18)	−0.0022 (12)	0.0044 (13)	0.0011 (13)
C7	0.0355 (17)	0.0282 (15)	0.0487 (19)	−0.0038 (13)	0.0071 (14)	−0.0059 (14)
C8	0.0360 (17)	0.0314 (16)	0.054 (2)	0.0040 (13)	0.0067 (14)	0.0014 (14)
C9	0.0341 (16)	0.0365 (17)	0.0410 (18)	−0.0024 (13)	−0.0004 (13)	0.0058 (13)
C10	0.0382 (16)	0.0274 (15)	0.0329 (16)	−0.0015 (13)	0.0046 (12)	−0.0009 (13)
C11	0.0348 (17)	0.0374 (17)	0.0402 (18)	−0.0021 (13)	0.0049 (13)	−0.0083 (14)
C12	0.048 (2)	0.059 (2)	0.0407 (19)	−0.0083 (16)	0.0004 (15)	−0.0101 (16)
C13	0.050 (2)	0.059 (2)	0.043 (2)	−0.0051 (17)	0.0124 (16)	−0.0085 (17)
C14	0.055 (2)	0.051 (2)	0.058 (2)	0.0070 (17)	0.0252 (17)	0.0043 (18)
C15	0.058 (2)	0.0423 (19)	0.0333 (18)	−0.0036 (16)	0.0001 (15)	0.0053 (14)
C1A	0.0453 (19)	0.0370 (18)	0.0405 (18)	−0.0096 (15)	0.0069 (14)	0.0008 (14)
C2A	0.0435 (19)	0.055 (2)	0.0450 (19)	−0.0119 (17)	0.0097 (15)	0.0022 (16)
C3A	0.065 (3)	0.065 (3)	0.080 (3)	−0.026 (2)	0.004 (2)	0.005 (2)
C4A	0.060 (3)	0.093 (4)	0.097 (4)	−0.042 (3)	0.018 (2)	−0.008 (3)
O3A	0.0449 (18)	0.133 (4)	0.134 (3)	−0.015 (2)	0.0189 (18)	−0.019 (3)
C5A	0.044 (2)	0.070 (3)	0.103 (4)	−0.010 (2)	0.009 (2)	−0.010 (3)
C1B	0.0313 (17)	0.0405 (18)	0.054 (2)	0.0020 (14)	0.0041 (14)	−0.0001 (16)
C2B	0.0353 (17)	0.0445 (19)	0.052 (2)	−0.0061 (14)	0.0074 (15)	−0.0041 (15)
C3B	0.048 (2)	0.070 (3)	0.070 (3)	−0.0044 (19)	−0.0008 (19)	0.026 (2)
C4B	0.078 (3)	0.089 (4)	0.078 (3)	−0.018 (3)	−0.002 (3)	0.042 (3)
O3B	0.084 (3)	0.105 (3)	0.099 (3)	−0.034 (2)	0.030 (2)	0.014 (2)
C5B	0.043 (2)	0.068 (3)	0.077 (3)	−0.0085 (19)	0.0146 (19)	0.002 (2)
C1C	0.071 (3)	0.048 (2)	0.055 (2)	−0.022 (2)	0.009 (2)	−0.0141 (19)
C2C	0.100 (4)	0.117 (5)	0.076 (3)	−0.065 (4)	−0.010 (3)	−0.006 (3)

Geometric parameters (Å, º) top

O1—C5	1.464 (4)	C10—C15	1.554 (4)
O1—C11	1.466 (4)	C11—C13	1.521 (5)
O2—C4	1.437 (4)	C11—C12	1.535 (4)
O2—H2	0.852 (14)	C12—H12A	0.9600
O3—C8	1.421 (4)	C12—H12B	0.9600
O3—H3	0.851 (14)	C12—H12C	0.9600
O1A—C1A	1.338 (4)	C13—H13A	0.9600
O1A—C6	1.445 (4)	C13—H13B	0.9600
O2A—C1A	1.197 (4)	C13—H13C	0.9600
O1B—C1B	1.347 (4)	C14—H14A	0.9600
O1B—C9	1.454 (4)	C14—H14B	0.9600
O2B—C1B	1.190 (4)	C14—H14C	0.9600
O1C—C1C	1.342 (5)	C15—H15A	0.9600
O1C—C1	1.456 (4)	C15—H15B	0.9600
O2C—C1C	1.201 (5)	C15—H15C	0.9600
C1—C2	1.518 (5)	C1A—C2A	1.462 (5)
C1—C10	1.530 (4)	C2A—C5A	1.341 (6)
C1—H1	0.9800	C2A—C3A	1.422 (6)
C2—C3	1.514 (5)	C3A—C4A	1.306 (6)
C2—H2A	0.9700	C3A—H3A1	0.9300
C2—H2B	0.9700	C4A—O3A	1.399 (8)
C3—C4	1.534 (5)	C4A—H4A	0.9300
C3—H3A	0.9700	O3A—C5A	1.350 (5)
C3—H3B	0.9700	C5A—H5A	0.9300
C4—C14	1.526 (5)	C1B—C2B	1.458 (5)
C4—C5	1.567 (4)	C2B—C5B	1.356 (5)
C5—C6	1.533 (4)	C2B—C3B	1.400 (5)
C5—C10	1.572 (4)	C3B—C4B	1.315 (6)
C6—C7	1.531 (5)	C3B—H3B1	0.9300
C6—H6	0.9800	C4B—O3B	1.399 (6)
C7—C11	1.541 (5)	C4B—H4B	0.9300
C7—C8	1.543 (4)	O3B—C5B	1.334 (6)
C7—H7	0.9800	C5B—H5B	0.9300
C8—C9	1.541 (5)	C1C—C2C	1.496 (6)
C8—H8	0.9800	C2C—H2C1	0.9600
C9—C10	1.556 (4)	C2C—H2C2	0.9600
C9—H9	0.9800	C2C—H2C3	0.9600

C5—O1—C11	111.0 (2)	O1—C11—C7	101.8 (2)
C4—O2—H2	106 (3)	C13—C11—C7	116.2 (3)
C8—O3—H3	107 (3)	C12—C11—C7	113.1 (3)
C1A—O1A—C6	117.7 (2)	C11—C12—H12A	109.5
C1B—O1B—C9	118.0 (2)	C11—C12—H12B	109.5
C1C—O1C—C1	117.6 (3)	H12A—C12—H12B	109.5
O1C—C1—C2	110.6 (3)	C11—C12—H12C	109.5
O1C—C1—C10	107.0 (2)	H12A—C12—H12C	109.5
C2—C1—C10	112.6 (3)	H12B—C12—H12C	109.5
O1C—C1—H1	108.9	C11—C13—H13A	109.5
C2—C1—H1	108.9	C11—C13—H13B	109.5
C10—C1—H1	108.9	H13A—C13—H13B	109.5
C1—C2—C3	107.9 (3)	C11—C13—H13C	109.5
C1—C2—H2A	110.1	H13A—C13—H13C	109.5
C3—C2—H2A	110.1	H13B—C13—H13C	109.5
C1—C2—H2B	110.1	C4—C14—H14A	109.5
C3—C2—H2B	110.1	C4—C14—H14B	109.5
H2A—C2—H2B	108.4	H14A—C14—H14B	109.5
C2—C3—C4	113.8 (3)	C4—C14—H14C	109.5
C2—C3—H3A	108.8	H14A—C14—H14C	109.5
C4—C3—H3A	108.8	H14B—C14—H14C	109.5
C2—C3—H3B	108.8	C10—C15—H15A	109.5
C4—C3—H3B	108.8	C10—C15—H15B	109.5
H3A—C3—H3B	107.7	H15A—C15—H15B	109.5
O2—C4—C14	105.4 (3)	C10—C15—H15C	109.5
O2—C4—C3	106.6 (3)	H15A—C15—H15C	109.5
C14—C4—C3	110.2 (3)	H15B—C15—H15C	109.5
O2—C4—C5	108.2 (3)	O2A—C1A—O1A	123.7 (3)
C14—C4—C5	115.8 (3)	O2A—C1A—C2A	125.7 (3)
C3—C4—C5	110.1 (3)	O1A—C1A—C2A	110.6 (3)
O1—C5—C6	104.8 (2)	C5A—C2A—C3A	106.8 (4)
O1—C5—C4	105.1 (2)	C5A—C2A—C1A	126.4 (4)
C6—C5—C4	117.4 (3)	C3A—C2A—C1A	126.8 (4)
O1—C5—C10	107.1 (2)	C4A—C3A—C2A	107.0 (4)
C6—C5—C10	106.4 (2)	C4A—C3A—H3A1	126.5
C4—C5—C10	115.1 (2)	C2A—C3A—H3A1	126.5
O1A—C6—C7	114.5 (3)	C3A—C4A—O3A	110.2 (4)
O1A—C6—C5	110.6 (2)	C3A—C4A—H4A	124.9
C7—C6—C5	100.4 (2)	O3A—C4A—H4A	124.9
O1A—C6—H6	110.4	C5A—O3A—C4A	105.7 (4)
C7—C6—H6	110.4	C2A—C5A—O3A	110.2 (4)
C5—C6—H6	110.4	C2A—C5A—H5A	124.9
C6—C7—C11	102.4 (2)	O3A—C5A—H5A	124.9
C6—C7—C8	105.4 (3)	O2B—C1B—O1B	124.0 (3)
C11—C7—C8	114.5 (3)	O2B—C1B—C2B	125.7 (3)
C6—C7—H7	111.3	O1B—C1B—C2B	110.3 (3)
C11—C7—H7	111.3	C5B—C2B—C3B	105.6 (4)
C8—C7—H7	111.3	C5B—C2B—C1B	125.2 (3)
O3—C8—C9	105.2 (3)	C3B—C2B—C1B	129.1 (3)
O3—C8—C7	110.3 (3)	C4B—C3B—C2B	108.4 (4)
C9—C8—C7	114.9 (3)	C4B—C3B—H3B1	125.8
O3—C8—H8	108.8	C2B—C3B—H3B1	125.8
C9—C8—H8	108.8	C3B—C4B—O3B	109.2 (4)
C7—C8—H8	108.8	C3B—C4B—H4B	125.4
O1B—C9—C8	109.9 (3)	O3B—C4B—H4B	125.4
O1B—C9—C10	108.8 (2)	C5B—O3B—C4B	105.8 (3)
C8—C9—C10	116.1 (3)	O3B—C5B—C2B	110.9 (4)
O1B—C9—H9	107.3	O3B—C5B—H5B	124.5
C8—C9—H9	107.3	C2B—C5B—H5B	124.5
C10—C9—H9	107.3	O2C—C1C—O1C	123.1 (4)
C1—C10—C15	110.2 (3)	O2C—C1C—C2C	126.0 (4)
C1—C10—C9	110.6 (3)	O1C—C1C—C2C	111.0 (4)
C15—C10—C9	105.5 (3)	C1C—C2C—H2C1	109.5
C1—C10—C5	108.0 (2)	C1C—C2C—H2C2	109.5
C15—C10—C5	112.9 (2)	H2C1—C2C—H2C2	109.5
C9—C10—C5	109.8 (2)	C1C—C2C—H2C3	109.5
O1—C11—C13	109.3 (3)	H2C1—C2C—H2C3	109.5
O1—C11—C12	109.4 (2)	H2C2—C2C—H2C3	109.5
C13—C11—C12	106.9 (3)

(1S,4S,5S,6R,7R,9S,10S)-6-Acetoxy-9-hydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a- methanobenzo[b]oxepine-5,10-diyl bis(furan-3-carboxylate) (III) top

Crystal data top

C₂₇H₃₂O₁₀	F(000) = 548
M_r = 516.52	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 11.2999 (3) Å	Cell parameters from 8169 reflections
b = 9.6363 (3) Å	θ = 4.0–23.4°
c = 12.1306 (4) Å	µ = 0.10 mm⁻¹
β = 97.539 (3)°	T = 294 K
V = 1309.47 (7) Å³	Block, colourless
Z = 2	0.42 × 0.22 × 0.12 mm

Data collection top

CCD Oxford Diffraction Xcalibur, Eos, Gemini diffractometer	4065 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.045
thick slices scans	θ_max = 25.5°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −13→13
T_min = 0.95, T_max = 0.98	k = −11→11
29871 measured reflections	l = −14→14
4858 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0428P)² + 0.0872P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.13 e Å⁻³
4858 reflections	Δρ_min = −0.20 e Å⁻³
343 parameters	Absolute structure: Absolute structure assigned by comparison with related compounds of the same origin.
2 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.44939 (14)	0.59663 (18)	0.34937 (13)	0.0366 (4)
O2	0.66369 (17)	0.5550 (2)	0.29462 (17)	0.0523 (5)
H2	0.631 (3)	0.556 (4)	0.3545 (17)	0.063*
O1A	0.59914 (15)	0.83361 (19)	0.26145 (16)	0.0450 (5)
O2A	0.5524 (2)	1.0489 (2)	0.2004 (2)	0.0673 (6)
O1B	0.19019 (15)	0.5841 (2)	0.29323 (15)	0.0477 (5)
O2B	0.00065 (19)	0.6212 (3)	0.2181 (2)	0.0836 (9)
O1C	0.2049 (2)	0.4249 (3)	0.08952 (18)	0.0681 (7)
O2C	0.1788 (3)	0.2253 (4)	0.1761 (3)	0.1038 (10)
C1	0.3179 (3)	0.4480 (3)	0.1586 (2)	0.0496 (7)
H1	0.311296	0.414926	0.233981	0.060*
C2	0.4175 (3)	0.3695 (3)	0.1145 (3)	0.0613 (9)
H2A	0.426643	0.401991	0.040366	0.074*
H2B	0.399057	0.271202	0.110328	0.074*
C3	0.5314 (3)	0.3937 (3)	0.1922 (3)	0.0539 (8)
H3A	0.595370	0.342033	0.165060	0.065*
H3B	0.521486	0.357345	0.264939	0.065*
C4	0.5680 (2)	0.5456 (3)	0.2043 (2)	0.0434 (7)
C5	0.4615 (2)	0.6353 (3)	0.2350 (2)	0.0343 (6)
C6	0.4755 (2)	0.7933 (3)	0.2379 (2)	0.0389 (6)
H6	0.440045	0.833271	0.166895	0.047*
C7	0.3994 (2)	0.8292 (3)	0.3287 (2)	0.0461 (7)
H7	0.416886	0.923080	0.357333	0.055*
C8	0.2696 (2)	0.8175 (3)	0.2733 (3)	0.0524 (8)
H8A	0.254683	0.891197	0.218726	0.063*
H8B	0.217334	0.832854	0.329435	0.063*
C9	0.2358 (2)	0.6784 (3)	0.2153 (2)	0.0463 (7)
H9	0.170725	0.696706	0.155345	0.056*
C10	0.3378 (2)	0.6053 (3)	0.1627 (2)	0.0395 (6)
C11	0.4380 (2)	0.7200 (3)	0.4177 (2)	0.0424 (6)
C12	0.5575 (3)	0.7521 (4)	0.4876 (2)	0.0556 (8)
H12A	0.579446	0.676583	0.537699	0.083*
H12B	0.550462	0.835624	0.529341	0.083*
H12C	0.617784	0.764291	0.439461	0.083*
C13	0.3486 (3)	0.6894 (4)	0.4988 (3)	0.0594 (9)
H13A	0.273121	0.664284	0.457835	0.089*
H13B	0.338827	0.770524	0.542658	0.089*
H13C	0.377655	0.614229	0.546777	0.089*
C14	0.6230 (3)	0.5944 (4)	0.1019 (3)	0.0585 (8)
H14A	0.629535	0.693740	0.102916	0.088*
H14B	0.573026	0.565777	0.035636	0.088*
H14C	0.700903	0.554230	0.102953	0.088*
C15	0.3308 (3)	0.6638 (4)	0.0428 (2)	0.0576 (8)
H15A	0.404958	0.646725	0.014479	0.086*
H15B	0.316131	0.761860	0.043713	0.086*
H15C	0.267094	0.618870	−0.004092	0.086*
C1A	0.6263 (3)	0.9637 (3)	0.2333 (2)	0.0438 (7)
C2A	0.7548 (3)	0.9829 (3)	0.2451 (2)	0.0494 (7)
C3A	0.8184 (4)	1.1109 (4)	0.2486 (3)	0.0764 (11)
H3A1	0.785810	1.199663	0.245904	0.092*
C4A	0.9325 (4)	1.0788 (5)	0.2562 (3)	0.0888 (14)
H4A	0.994105	1.143345	0.260146	0.107*
O3A	0.9484 (2)	0.9377 (4)	0.2576 (3)	0.0988 (10)
C5A	0.8378 (3)	0.8840 (4)	0.2511 (3)	0.0744 (11)
H5A	0.821370	0.789451	0.250817	0.089*
C1B	0.0716 (2)	0.5632 (3)	0.2841 (3)	0.0490 (7)
C2B	0.0425 (2)	0.4605 (3)	0.3648 (3)	0.0487 (7)
C3B	0.1186 (3)	0.3748 (5)	0.4341 (3)	0.0768 (11)
H3B1	0.201450	0.374010	0.438920	0.092*
C4B	0.0556 (4)	0.2963 (5)	0.4907 (3)	0.0936 (15)
H4B	0.085303	0.227647	0.540671	0.112*
O3B	−0.0663 (3)	0.3326 (4)	0.4636 (3)	0.1098 (11)
C5B	−0.0690 (3)	0.4290 (4)	0.3862 (3)	0.0703 (10)
H5B	−0.138336	0.469995	0.350889	0.084*
C1C	0.1440 (4)	0.3079 (5)	0.1076 (3)	0.0799 (12)
C2C	0.0282 (5)	0.3032 (7)	0.0312 (4)	0.126 (2)
H2C1	0.002485	0.208623	0.020853	0.189*
H2C2	0.039296	0.342774	−0.039373	0.189*
H2C3	−0.031185	0.355289	0.063216	0.189*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0391 (9)	0.0379 (10)	0.0330 (9)	−0.0035 (8)	0.0062 (7)	0.0008 (8)
O2	0.0388 (11)	0.0600 (13)	0.0581 (13)	0.0073 (9)	0.0070 (9)	0.0062 (11)
O1A	0.0358 (10)	0.0377 (11)	0.0608 (12)	−0.0084 (8)	0.0034 (8)	0.0083 (9)
O2A	0.0607 (14)	0.0388 (12)	0.0999 (18)	−0.0041 (11)	0.0014 (12)	0.0132 (12)
O1B	0.0306 (9)	0.0622 (13)	0.0496 (11)	−0.0050 (9)	0.0022 (8)	0.0124 (10)
O2B	0.0355 (12)	0.097 (2)	0.116 (2)	0.0060 (13)	0.0000 (13)	0.0438 (18)
O1C	0.0699 (14)	0.0768 (16)	0.0550 (13)	−0.0363 (13)	−0.0021 (11)	−0.0053 (12)
O2C	0.108 (2)	0.093 (2)	0.110 (2)	−0.0574 (19)	0.0115 (19)	0.011 (2)
C1	0.0559 (18)	0.0509 (18)	0.0418 (16)	−0.0184 (15)	0.0054 (13)	−0.0041 (13)
C2	0.086 (2)	0.0470 (18)	0.0556 (19)	−0.0142 (17)	0.0262 (18)	−0.0114 (15)
C3	0.068 (2)	0.0362 (16)	0.061 (2)	0.0054 (15)	0.0238 (17)	−0.0016 (14)
C4	0.0452 (16)	0.0429 (16)	0.0439 (15)	0.0038 (13)	0.0133 (12)	0.0023 (13)
C5	0.0357 (13)	0.0342 (14)	0.0334 (14)	−0.0056 (11)	0.0069 (11)	0.0043 (11)
C6	0.0306 (13)	0.0370 (15)	0.0478 (15)	−0.0037 (11)	0.0006 (11)	0.0051 (12)
C7	0.0418 (15)	0.0381 (15)	0.0587 (18)	−0.0012 (12)	0.0077 (13)	−0.0091 (13)
C8	0.0408 (15)	0.0463 (17)	0.071 (2)	0.0082 (13)	0.0089 (14)	0.0076 (15)
C9	0.0343 (14)	0.0539 (18)	0.0490 (17)	−0.0026 (12)	−0.0010 (12)	0.0140 (14)
C10	0.0388 (14)	0.0443 (16)	0.0350 (14)	−0.0080 (12)	0.0033 (11)	0.0045 (12)
C11	0.0412 (15)	0.0447 (16)	0.0418 (15)	−0.0028 (13)	0.0076 (12)	−0.0074 (13)
C12	0.0524 (18)	0.064 (2)	0.0486 (18)	−0.0130 (16)	0.0012 (14)	−0.0088 (16)
C13	0.0549 (19)	0.078 (2)	0.0477 (18)	−0.0073 (16)	0.0154 (15)	−0.0094 (16)
C14	0.0595 (18)	0.062 (2)	0.0595 (19)	0.0003 (16)	0.0272 (15)	0.0054 (17)
C15	0.0602 (19)	0.070 (2)	0.0402 (17)	−0.0147 (16)	−0.0019 (14)	0.0131 (15)
C1A	0.0503 (17)	0.0384 (16)	0.0430 (15)	−0.0112 (14)	0.0079 (13)	0.0004 (13)
C2A	0.0496 (17)	0.0528 (19)	0.0463 (16)	−0.0161 (15)	0.0088 (13)	0.0013 (14)
C3A	0.074 (3)	0.068 (2)	0.084 (3)	−0.033 (2)	−0.0007 (19)	0.008 (2)
C4A	0.070 (3)	0.105 (4)	0.092 (3)	−0.048 (3)	0.011 (2)	0.007 (3)
O3A	0.0479 (15)	0.115 (3)	0.135 (3)	−0.0221 (16)	0.0191 (16)	−0.010 (2)
C5A	0.0453 (19)	0.071 (3)	0.108 (3)	−0.0168 (19)	0.0126 (19)	−0.005 (2)
C1B	0.0278 (14)	0.0575 (19)	0.0611 (18)	−0.0008 (13)	0.0038 (13)	−0.0020 (16)
C2B	0.0339 (15)	0.0585 (19)	0.0545 (17)	−0.0070 (14)	0.0093 (13)	−0.0021 (15)
C3B	0.0507 (19)	0.101 (3)	0.077 (2)	−0.011 (2)	0.0018 (17)	0.032 (2)
C4B	0.085 (3)	0.115 (4)	0.077 (3)	−0.029 (3)	−0.004 (2)	0.045 (3)
O3B	0.103 (3)	0.133 (3)	0.100 (2)	−0.047 (2)	0.0371 (19)	0.012 (2)
C5B	0.0440 (18)	0.085 (3)	0.085 (3)	−0.0101 (17)	0.0181 (18)	−0.005 (2)
C1C	0.086 (3)	0.091 (3)	0.064 (2)	−0.048 (2)	0.013 (2)	−0.017 (2)
C2C	0.115 (4)	0.176 (6)	0.082 (3)	−0.094 (4)	−0.011 (3)	−0.011 (3)

Geometric parameters (Å, º) top

O1—C5	1.460 (3)	C11—C13	1.528 (4)
O1—C11	1.465 (3)	C11—C12	1.529 (4)
O2—C4	1.437 (4)	C12—H12A	0.9600
O2—H2	0.856 (13)	C12—H12B	0.9600
O1A—C1A	1.346 (3)	C12—H12C	0.9600
O1A—C6	1.442 (3)	C13—H13A	0.9600
O2A—C1A	1.201 (4)	C13—H13B	0.9600
O1B—C1B	1.345 (3)	C13—H13C	0.9600
O1B—C9	1.453 (3)	C14—H14A	0.9600
O2B—C1B	1.195 (4)	C14—H14B	0.9600
O1C—C1C	1.354 (5)	C14—H14C	0.9600
O1C—C1	1.450 (4)	C15—H15A	0.9600
O2C—C1C	1.180 (5)	C15—H15B	0.9600
C1—C2	1.510 (4)	C15—H15C	0.9600
C1—C10	1.533 (4)	C1A—C2A	1.452 (4)
C1—H1	0.9800	C2A—C5A	1.333 (5)
C2—C3	1.511 (5)	C2A—C3A	1.426 (5)
C2—H2A	0.9700	C3A—C4A	1.317 (6)
C2—H2B	0.9700	C3A—H3A1	0.9300
C3—C4	1.523 (4)	C4A—O3A	1.371 (6)
C3—H3A	0.9700	C4A—H4A	0.9300
C3—H3B	0.9700	O3A—C5A	1.345 (4)
C4—C14	1.535 (4)	C5A—H5A	0.9300
C4—C5	1.566 (4)	C1B—C2B	1.460 (4)
C5—C6	1.530 (4)	C2B—C5B	1.354 (4)
C5—C10	1.576 (3)	C2B—C3B	1.392 (5)
C6—C7	1.523 (4)	C3B—C4B	1.296 (5)
C6—H6	0.9800	C3B—H3B1	0.9300
C7—C11	1.529 (4)	C4B—O3B	1.417 (5)
C7—C8	1.535 (4)	C4B—H4B	0.9300
C7—H7	0.9800	O3B—C5B	1.318 (5)
C8—C9	1.538 (4)	C5B—H5B	0.9300
C8—H8A	0.9700	C1C—C2C	1.501 (6)
C8—H8B	0.9700	C2C—H2C1	0.9600
C9—C10	1.558 (4)	C2C—H2C2	0.9600
C9—H9	0.9800	C2C—H2C3	0.9600
C10—C15	1.553 (4)

C5—O1—C11	110.90 (19)	O1—C11—C7	101.3 (2)
C4—O2—H2	107 (2)	C13—C11—C7	115.8 (2)
C1A—O1A—C6	116.6 (2)	C12—C11—C7	113.7 (2)
C1B—O1B—C9	118.3 (2)	C11—C12—H12A	109.5
C1C—O1C—C1	117.5 (3)	C11—C12—H12B	109.5
O1C—C1—C2	111.0 (2)	H12A—C12—H12B	109.5
O1C—C1—C10	106.5 (2)	C11—C12—H12C	109.5
C2—C1—C10	113.2 (2)	H12A—C12—H12C	109.5
O1C—C1—H1	108.7	H12B—C12—H12C	109.5
C2—C1—H1	108.7	C11—C13—H13A	109.5
C10—C1—H1	108.7	C11—C13—H13B	109.5
C1—C2—C3	108.3 (2)	H13A—C13—H13B	109.5
C1—C2—H2A	110.0	C11—C13—H13C	109.5
C3—C2—H2A	110.0	H13A—C13—H13C	109.5
C1—C2—H2B	110.0	H13B—C13—H13C	109.5
C3—C2—H2B	110.0	C4—C14—H14A	109.5
H2A—C2—H2B	108.4	C4—C14—H14B	109.5
C2—C3—C4	114.0 (3)	H14A—C14—H14B	109.5
C2—C3—H3A	108.7	C4—C14—H14C	109.5
C4—C3—H3A	108.7	H14A—C14—H14C	109.5
C2—C3—H3B	108.7	H14B—C14—H14C	109.5
C4—C3—H3B	108.7	C10—C15—H15A	109.5
H3A—C3—H3B	107.6	C10—C15—H15B	109.5
O2—C4—C3	107.6 (2)	H15A—C15—H15B	109.5
O2—C4—C14	104.7 (2)	C10—C15—H15C	109.5
C3—C4—C14	110.5 (3)	H15A—C15—H15C	109.5
O2—C4—C5	108.0 (2)	H15B—C15—H15C	109.5
C3—C4—C5	110.3 (2)	O2A—C1A—O1A	123.3 (3)
C14—C4—C5	115.4 (2)	O2A—C1A—C2A	126.1 (3)
O1—C5—C6	104.7 (2)	O1A—C1A—C2A	110.6 (3)
O1—C5—C4	104.82 (19)	C5A—C2A—C3A	105.6 (3)
C6—C5—C4	118.3 (2)	C5A—C2A—C1A	127.0 (3)
O1—C5—C10	107.17 (17)	C3A—C2A—C1A	127.4 (3)
C6—C5—C10	106.0 (2)	C4A—C3A—C2A	106.5 (4)
C4—C5—C10	114.8 (2)	C4A—C3A—H3A1	126.7
O1A—C6—C7	114.8 (2)	C2A—C3A—H3A1	126.7
O1A—C6—C5	111.5 (2)	C3A—C4A—O3A	111.0 (3)
C7—C6—C5	100.1 (2)	C3A—C4A—H4A	124.5
O1A—C6—H6	110.0	O3A—C4A—H4A	124.5
C7—C6—H6	110.0	C5A—O3A—C4A	105.2 (3)
C5—C6—H6	110.0	C2A—C5A—O3A	111.7 (3)
C6—C7—C11	102.6 (2)	C2A—C5A—H5A	124.2
C6—C7—C8	105.3 (2)	O3A—C5A—H5A	124.2
C11—C7—C8	115.3 (2)	O2B—C1B—O1B	124.0 (3)
C6—C7—H7	111.1	O2B—C1B—C2B	125.1 (3)
C11—C7—H7	111.1	O1B—C1B—C2B	110.9 (2)
C8—C7—H7	111.1	C5B—C2B—C3B	105.6 (3)
C7—C8—C9	115.5 (2)	C5B—C2B—C1B	125.3 (3)
C7—C8—H8A	108.4	C3B—C2B—C1B	129.1 (3)
C9—C8—H8A	108.4	C4B—C3B—C2B	109.1 (3)
C7—C8—H8B	108.4	C4B—C3B—H3B1	125.5
C9—C8—H8B	108.4	C2B—C3B—H3B1	125.5
H8A—C8—H8B	107.5	C3B—C4B—O3B	108.5 (4)
O1B—C9—C8	109.7 (2)	C3B—C4B—H4B	125.7
O1B—C9—C10	109.1 (2)	O3B—C4B—H4B	125.7
C8—C9—C10	115.3 (2)	C5B—O3B—C4B	105.7 (3)
O1B—C9—H9	107.5	O3B—C5B—C2B	111.0 (4)
C8—C9—H9	107.5	O3B—C5B—H5B	124.5
C10—C9—H9	107.5	C2B—C5B—H5B	124.5
C1—C10—C15	109.8 (2)	O2C—C1C—O1C	123.1 (4)
C1—C10—C9	110.3 (2)	O2C—C1C—C2C	126.7 (4)
C15—C10—C9	105.7 (2)	O1C—C1C—C2C	110.2 (4)
C1—C10—C5	108.3 (2)	C1C—C2C—H2C1	109.5
C15—C10—C5	112.8 (2)	C1C—C2C—H2C2	109.5
C9—C10—C5	109.8 (2)	H2C1—C2C—H2C2	109.5
O1—C11—C13	108.8 (2)	C1C—C2C—H2C3	109.5
O1—C11—C12	109.9 (2)	H2C1—C2C—H2C3	109.5
C13—C11—C12	107.1 (2)	H2C2—C2C—H2C3	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.86 (1)	2.08 (3)	2.625 (2)	120 (3)
C12—H12C···O1A	0.96	2.24	2.949 (4)	130
C13—H13A···O1B	0.96	2.23	3.047 (4)	142
C14—H14A···O1A	0.96	2.41	3.045 (4)	123
C4A—H4A···O2Cⁱ	0.93	2.56	3.375 (5)	146
C5B—H5B···O2ⁱⁱ	0.93	2.40	3.309 (4)	167

Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y, z.

(1S,4S,5S,6R,7R,9S,10S)-\ 6-Acetoxy-10-(benzoyloxy)-9-hydroxy-2,2,5a,9-tetramethyloctahydro-2H-\ 3,9a-methanobenzo[b]oxepin-5-yl furan-3-carboxylate (IV) top

Crystal data top

C₂₉H₃₄O₉	F(000) = 560
M_r = 526.56	D_x = 1.241 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.9045 (4) Å	Cell parameters from 2709 reflections
b = 9.2038 (5) Å	θ = 4.2–20.4°
c = 19.3935 (9) Å	µ = 0.09 mm⁻¹
β = 93.073 (4)°	T = 294 K
V = 1408.88 (12) Å³	Blocks, colourless
Z = 2	0.50 × 0.23 × 0.20 mm

Data collection top

CCD Oxford Diffraction Xcalibur, Eos, Gemini diffractometer	3436 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.095
thick slices scans	θ_max = 25.0°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→9
T_min = 0.96, T_max = 0.99	k = −10→10
22118 measured reflections	l = −23→23
4957 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.058	w = 1/[σ²(F_o²) + (0.0653P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.145	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.16 e Å⁻³
4957 reflections	Δρ_min = −0.17 e Å⁻³
352 parameters	Absolute structure: Absolute structure assigned by comparison with related compounds of the same origin
2 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.0248 (4)	1.0961 (3)	0.21889 (15)	0.0520 (8)
O2	0.2942 (4)	1.1168 (4)	0.30509 (17)	0.0647 (9)
H2	0.295 (6)	1.116 (7)	0.2617 (8)	0.078*
O1A	0.0848 (3)	0.8933 (4)	0.34684 (16)	0.0577 (8)
O2A	−0.0751 (5)	0.7790 (5)	0.4214 (2)	0.0928 (14)
O1B	−0.3168 (4)	1.1961 (4)	0.17183 (15)	0.0556 (8)
O2B	−0.5950 (4)	1.1608 (5)	0.15481 (19)	0.0902 (13)
O1C	−0.2916 (4)	1.4503 (4)	0.25353 (19)	0.0685 (10)
O2C	−0.2108 (6)	1.5734 (5)	0.1618 (2)	0.0903 (13)
C1	−0.1357 (5)	1.3667 (6)	0.2572 (3)	0.0554 (12)
H1A	−0.100464	1.351650	0.210076	0.067*
C2	0.0049 (7)	1.4439 (6)	0.2974 (3)	0.0705 (15)
H2A	−0.024269	1.456356	0.344936	0.085*
H2B	0.022696	1.539141	0.277618	0.085*
C3	0.1668 (7)	1.3525 (7)	0.2944 (3)	0.0761 (16)
H3C	0.197293	1.345427	0.246721	0.091*
H3D	0.258281	1.402147	0.320050	0.091*
C4	0.1497 (5)	1.1996 (6)	0.3236 (2)	0.0547 (12)
C5	−0.0144 (5)	1.1228 (5)	0.2903 (2)	0.0478 (11)
C6	−0.0618 (5)	0.9740 (5)	0.3191 (2)	0.0506 (12)
H6	−0.145201	0.985082	0.354345	0.061*
C7	−0.1427 (5)	0.9053 (5)	0.2550 (3)	0.0535 (11)
H7	−0.152155	0.799690	0.260079	0.064*
C8	−0.3177 (6)	0.9766 (6)	0.2449 (3)	0.0584 (13)
H8A	−0.386279	0.944656	0.282048	0.070*
H8B	−0.371181	0.940789	0.202050	0.070*
C9	−0.3213 (6)	1.1432 (5)	0.2429 (2)	0.0534 (12)
H9	−0.429346	1.174352	0.260621	0.064*
C10	−0.1777 (5)	1.2181 (5)	0.2877 (2)	0.0438 (10)
C11	−0.0211 (6)	0.9451 (5)	0.1992 (2)	0.0554 (12)
C12	0.1405 (6)	0.8529 (7)	0.2016 (3)	0.0705 (15)
H12A	0.220192	0.894588	0.171576	0.106*
H12B	0.113243	0.755817	0.186626	0.106*
H12C	0.189366	0.850391	0.247954	0.106*
C13	−0.0937 (7)	0.9451 (7)	0.1252 (3)	0.0756 (16)
H13A	−0.188213	1.010548	0.121042	0.113*
H13B	−0.130598	0.848786	0.112766	0.113*
H13C	−0.008165	0.975860	0.095086	0.113*
C14	0.1606 (6)	1.2019 (7)	0.4023 (2)	0.0729 (15)
H14A	0.127127	1.109054	0.419467	0.109*
H14B	0.086573	1.275794	0.418387	0.109*
H14C	0.274948	1.222471	0.418517	0.109*
C15	−0.2541 (6)	1.2399 (6)	0.3599 (2)	0.0658 (14)
H15A	−0.165309	1.265718	0.393399	0.099*
H15B	−0.306657	1.151293	0.373703	0.099*
H15C	−0.337074	1.316124	0.356861	0.099*
C1A	0.0603 (6)	0.7976 (5)	0.3975 (2)	0.0529 (12)
C2A	0.2169 (6)	0.7201 (6)	0.4179 (2)	0.0522 (11)
C3A	0.3725 (6)	0.7588 (6)	0.3934 (3)	0.0695 (15)
H3A	0.380130	0.837189	0.363455	0.083*
C4A	0.5171 (7)	0.6803 (8)	0.4137 (3)	0.0844 (17)
H4A	0.621311	0.705412	0.397100	0.101*
C5A	0.5055 (9)	0.5668 (8)	0.4580 (4)	0.092 (2)
H5A	0.602884	0.515738	0.471944	0.110*
C6A	0.3527 (9)	0.5259 (7)	0.4825 (3)	0.0842 (18)
H6A	0.346144	0.447350	0.512347	0.101*
C7A	0.2103 (7)	0.6026 (6)	0.4622 (2)	0.0644 (13)
H7A	0.106588	0.575161	0.478625	0.077*
C1B	−0.4618 (6)	1.2036 (6)	0.1345 (3)	0.0594 (12)
C2B	−0.4429 (7)	1.2696 (7)	0.0667 (3)	0.0689 (15)
C3B	−0.5647 (10)	1.2909 (11)	0.0169 (4)	0.129 (3)
H3B	−0.676901	1.263268	0.021008	0.155*
C4B	−0.5098 (10)	1.3543 (11)	−0.0378 (3)	0.116 (3)
H4B	−0.572834	1.379679	−0.077893	0.139*
O3B	−0.3399 (11)	1.3757 (11)	−0.0238 (4)	0.189 (3)
C5B	−0.2985 (9)	1.3237 (10)	0.0408 (3)	0.107 (3)
H5B	−0.191436	1.324767	0.063075	0.129*
C1C	−0.3168 (9)	1.5449 (6)	0.2006 (4)	0.0775 (17)
C2C	−0.4930 (8)	1.6027 (7)	0.1984 (4)	0.101 (2)
H2CA	−0.498547	1.690865	0.171930	0.152*
H2CB	−0.525040	1.622173	0.244531	0.152*
H2CC	−0.568925	1.532252	0.177284	0.152*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0489 (17)	0.057 (2)	0.0503 (17)	−0.0066 (16)	0.0075 (12)	−0.0016 (15)
O2	0.0402 (18)	0.083 (3)	0.070 (2)	−0.0003 (17)	0.0032 (16)	0.007 (2)
O1A	0.0417 (17)	0.063 (2)	0.068 (2)	0.0055 (15)	0.0036 (14)	0.0203 (17)
O2A	0.059 (2)	0.112 (3)	0.110 (3)	0.015 (2)	0.026 (2)	0.059 (3)
O1B	0.0469 (18)	0.063 (2)	0.0570 (18)	0.0009 (16)	0.0014 (14)	0.0052 (16)
O2B	0.053 (2)	0.134 (4)	0.082 (2)	−0.010 (2)	−0.0073 (18)	0.019 (2)
O1C	0.070 (2)	0.057 (2)	0.079 (2)	0.0140 (19)	0.0037 (17)	0.010 (2)
O2C	0.099 (3)	0.076 (3)	0.095 (3)	−0.004 (3)	0.002 (2)	0.025 (2)
C1	0.048 (3)	0.056 (3)	0.061 (3)	0.003 (2)	0.001 (2)	0.003 (2)
C2	0.074 (4)	0.056 (3)	0.080 (4)	−0.005 (3)	−0.009 (3)	−0.005 (3)
C3	0.075 (4)	0.075 (4)	0.077 (4)	−0.026 (3)	−0.011 (3)	0.005 (3)
C4	0.045 (3)	0.060 (3)	0.059 (3)	−0.008 (2)	−0.0020 (19)	0.002 (3)
C5	0.043 (2)	0.054 (3)	0.047 (3)	−0.006 (2)	0.0058 (18)	0.000 (2)
C6	0.037 (2)	0.051 (3)	0.064 (3)	0.002 (2)	0.005 (2)	0.012 (2)
C7	0.042 (2)	0.042 (3)	0.076 (3)	−0.006 (2)	−0.003 (2)	0.001 (2)
C8	0.048 (3)	0.058 (3)	0.069 (3)	−0.009 (2)	−0.002 (2)	0.008 (3)
C9	0.048 (3)	0.060 (3)	0.053 (3)	−0.010 (2)	0.0042 (19)	0.016 (2)
C10	0.045 (2)	0.043 (2)	0.044 (2)	−0.001 (2)	0.0054 (17)	0.001 (2)
C11	0.051 (3)	0.048 (3)	0.066 (3)	0.003 (2)	−0.002 (2)	−0.005 (2)
C12	0.068 (3)	0.075 (4)	0.069 (3)	0.018 (3)	0.010 (3)	0.003 (3)
C13	0.081 (4)	0.077 (4)	0.068 (3)	0.009 (3)	−0.006 (3)	−0.015 (3)
C14	0.066 (3)	0.088 (4)	0.063 (3)	0.000 (3)	−0.011 (2)	0.000 (3)
C15	0.066 (3)	0.071 (4)	0.061 (3)	0.015 (3)	0.007 (2)	0.005 (3)
C1A	0.047 (3)	0.055 (3)	0.057 (3)	−0.004 (2)	0.004 (2)	0.009 (2)
C2A	0.052 (3)	0.058 (3)	0.045 (2)	0.002 (2)	−0.0032 (19)	−0.006 (2)
C3A	0.048 (3)	0.077 (4)	0.083 (4)	0.004 (3)	−0.006 (2)	0.004 (3)
C4A	0.056 (3)	0.096 (5)	0.099 (4)	0.007 (3)	−0.009 (3)	0.001 (4)
C5A	0.085 (5)	0.096 (5)	0.091 (5)	0.035 (4)	−0.036 (4)	−0.019 (4)
C6A	0.106 (5)	0.068 (4)	0.076 (4)	0.029 (4)	−0.025 (4)	−0.006 (3)
C7A	0.078 (3)	0.065 (3)	0.050 (3)	0.005 (3)	0.001 (2)	−0.004 (3)
C1B	0.044 (3)	0.062 (3)	0.072 (3)	0.005 (3)	−0.001 (2)	0.005 (3)
C2B	0.068 (4)	0.082 (4)	0.055 (3)	0.007 (3)	−0.009 (3)	−0.001 (3)
C3B	0.099 (6)	0.177 (9)	0.108 (6)	−0.004 (5)	−0.028 (5)	0.043 (6)
C4B	0.097 (5)	0.190 (8)	0.056 (4)	−0.011 (5)	−0.030 (3)	0.042 (5)
O3B	0.258 (9)	0.213 (8)	0.098 (4)	−0.015 (8)	0.024 (5)	0.039 (5)
C5B	0.101 (5)	0.155 (8)	0.066 (4)	−0.015 (5)	0.007 (3)	0.020 (4)
C1C	0.093 (5)	0.054 (3)	0.084 (4)	0.002 (3)	−0.013 (4)	0.000 (3)
C2C	0.094 (5)	0.069 (4)	0.138 (6)	0.019 (4)	−0.019 (4)	0.010 (4)

Geometric parameters (Å, º) top

O1—C5	1.457 (5)	C11—C12	1.533 (6)
O1—C11	1.480 (6)	C12—H12A	0.9600
O2—C4	1.435 (6)	C12—H12B	0.9600
O2—H2	0.842 (14)	C12—H12C	0.9600
O1A—C1A	1.341 (5)	C13—H13A	0.9600
O1A—C6	1.454 (5)	C13—H13B	0.9600
O2A—C1A	1.202 (5)	C13—H13C	0.9600
O1B—C1B	1.325 (5)	C14—H14A	0.9600
O1B—C9	1.464 (5)	C14—H14B	0.9600
O2B—C1B	1.209 (6)	C14—H14C	0.9600
O1C—C1C	1.353 (7)	C15—H15A	0.9600
O1C—C1	1.451 (6)	C15—H15B	0.9600
O2C—C1C	1.186 (7)	C15—H15C	0.9600
C1—C2	1.500 (7)	C1A—C2A	1.465 (6)
C1—C10	1.534 (7)	C2A—C7A	1.384 (7)
C1—H1A	0.9800	C2A—C3A	1.389 (7)
C2—C3	1.535 (8)	C3A—C4A	1.391 (7)
C2—H2A	0.9700	C3A—H3A	0.9300
C2—H2B	0.9700	C4A—C5A	1.358 (9)
C3—C4	1.526 (8)	C4A—H4A	0.9300
C3—H3C	0.9700	C5A—C6A	1.374 (10)
C3—H3D	0.9700	C5A—H5A	0.9300
C4—C14	1.525 (7)	C6A—C7A	1.368 (7)
C4—C5	1.583 (6)	C6A—H6A	0.9300
C5—C6	1.532 (6)	C7A—H7A	0.9300
C5—C10	1.559 (6)	C1B—C2B	1.464 (7)
C6—C7	1.507 (7)	C2B—C3B	1.340 (8)
C6—H6	0.9800	C2B—C5B	1.365 (8)
C7—C11	1.529 (7)	C3B—C4B	1.306 (10)
C7—C8	1.535 (6)	C3B—H3B	0.9300
C7—H7	0.9800	C4B—O3B	1.370 (9)
C8—C9	1.534 (7)	C4B—H4B	0.9300
C8—H8A	0.9700	O3B—C5B	1.364 (9)
C8—H8B	0.9700	C5B—H5B	0.9300
C9—C10	1.554 (6)	C1C—C2C	1.489 (9)
C9—H9	0.9800	C2C—H2CA	0.9600
C10—C15	1.567 (6)	C2C—H2CB	0.9600
C11—C13	1.517 (7)	C2C—H2CC	0.9600

C5—O1—C11	110.0 (3)	C11—C12—H12A	109.5
C4—O2—H2	108 (4)	C11—C12—H12B	109.5
C1A—O1A—C6	117.6 (3)	H12A—C12—H12B	109.5
C1B—O1B—C9	117.9 (3)	C11—C12—H12C	109.5
C1C—O1C—C1	118.0 (4)	H12A—C12—H12C	109.5
O1C—C1—C2	112.2 (4)	H12B—C12—H12C	109.5
O1C—C1—C10	106.9 (3)	C11—C13—H13A	109.5
C2—C1—C10	113.1 (4)	C11—C13—H13B	109.5
O1C—C1—H1A	108.2	H13A—C13—H13B	109.5
C2—C1—H1A	108.2	C11—C13—H13C	109.5
C10—C1—H1A	108.2	H13A—C13—H13C	109.5
C1—C2—C3	108.5 (4)	H13B—C13—H13C	109.5
C1—C2—H2A	110.0	C4—C14—H14A	109.5
C3—C2—H2A	110.0	C4—C14—H14B	109.5
C1—C2—H2B	110.0	H14A—C14—H14B	109.5
C3—C2—H2B	110.0	C4—C14—H14C	109.5
H2A—C2—H2B	108.4	H14A—C14—H14C	109.5
C4—C3—C2	113.6 (4)	H14B—C14—H14C	109.5
C4—C3—H3C	108.8	C10—C15—H15A	109.5
C2—C3—H3C	108.8	C10—C15—H15B	109.5
C4—C3—H3D	108.8	H15A—C15—H15B	109.5
C2—C3—H3D	108.8	C10—C15—H15C	109.5
H3C—C3—H3D	107.7	H15A—C15—H15C	109.5
O2—C4—C3	108.1 (4)	H15B—C15—H15C	109.5
O2—C4—C14	104.7 (4)	O2A—C1A—O1A	122.9 (4)
C3—C4—C14	110.9 (5)	O2A—C1A—C2A	125.7 (4)
O2—C4—C5	107.9 (4)	O1A—C1A—C2A	111.4 (4)
C3—C4—C5	110.4 (4)	C7A—C2A—C3A	118.5 (5)
C14—C4—C5	114.5 (4)	C7A—C2A—C1A	119.3 (4)
O1—C5—C6	105.3 (3)	C3A—C2A—C1A	122.3 (4)
O1—C5—C10	106.4 (3)	C2A—C3A—C4A	119.9 (5)
C6—C5—C10	107.3 (3)	C2A—C3A—H3A	120.0
O1—C5—C4	104.5 (3)	C4A—C3A—H3A	120.0
C6—C5—C4	117.5 (4)	C5A—C4A—C3A	119.8 (6)
C10—C5—C4	114.9 (4)	C5A—C4A—H4A	120.1
O1A—C6—C7	112.6 (4)	C3A—C4A—H4A	120.1
O1A—C6—C5	112.7 (3)	C4A—C5A—C6A	121.3 (6)
C7—C6—C5	100.1 (4)	C4A—C5A—H5A	119.3
O1A—C6—H6	110.3	C6A—C5A—H5A	119.3
C7—C6—H6	110.3	C5A—C6A—C7A	119.0 (6)
C5—C6—H6	110.3	C5A—C6A—H6A	120.5
C6—C7—C11	103.2 (3)	C7A—C6A—H6A	120.5
C6—C7—C8	105.4 (4)	C6A—C7A—C2A	121.6 (5)
C11—C7—C8	113.8 (4)	C6A—C7A—H7A	119.2
C6—C7—H7	111.3	C2A—C7A—H7A	119.2
C11—C7—H7	111.3	O2B—C1B—O1B	123.2 (5)
C8—C7—H7	111.3	O2B—C1B—C2B	124.1 (4)
C7—C8—C9	116.5 (4)	O1B—C1B—C2B	112.7 (4)
C7—C8—H8A	108.2	C3B—C2B—C5B	105.3 (6)
C9—C8—H8A	108.2	C3B—C2B—C1B	127.1 (6)
C7—C8—H8B	108.2	C5B—C2B—C1B	127.6 (5)
C9—C8—H8B	108.2	C4B—C3B—C2B	113.2 (7)
H8A—C8—H8B	107.3	C4B—C3B—H3B	123.4
O1B—C9—C8	110.8 (4)	C2B—C3B—H3B	123.4
O1B—C9—C10	109.0 (3)	C3B—C4B—O3B	105.5 (6)
C8—C9—C10	114.7 (4)	C3B—C4B—H4B	127.2
O1B—C9—H9	107.4	O3B—C4B—H4B	127.2
C8—C9—H9	107.4	C5B—O3B—C4B	108.4 (6)
C10—C9—H9	107.4	O3B—C5B—C2B	107.6 (6)
C1—C10—C9	110.3 (3)	O3B—C5B—H5B	126.2
C1—C10—C5	108.6 (3)	C2B—C5B—H5B	126.2
C9—C10—C5	110.3 (4)	O2C—C1C—O1C	122.9 (6)
C1—C10—C15	109.4 (4)	O2C—C1C—C2C	126.5 (6)
C9—C10—C15	104.6 (3)	O1C—C1C—C2C	110.6 (6)
C5—C10—C15	113.6 (3)	C1C—C2C—H2CA	109.5
O1—C11—C13	108.6 (4)	C1C—C2C—H2CB	109.5
O1—C11—C7	101.4 (4)	H2CA—C2C—H2CB	109.5
C13—C11—C7	116.6 (4)	C1C—C2C—H2CC	109.5
O1—C11—C12	108.7 (4)	H2CA—C2C—H2CC	109.5
C13—C11—C12	107.5 (4)	H2CB—C2C—H2CC	109.5
C7—C11—C12	113.6 (4)

Experimental data top

	(II)	(III)	(IV)
Crystal Data
Chemical formula	C₂₇H₃₂O₁₁	C₂₇H₃₂O₁₀	C₂₉H₃₄O₉
M_r	532.52	516.52	526.56
Temperature (K)	294	294	294
a, b, c (Å)	11.2664 (3), 9.6575 (3), 12.0758 (4)	11.2999 (3), 9.6363 (3), 12.1306 (4)	7.9045 (4), 9.2038 (5), 19.3935 (9)
β (°)	98.262 (3)	97.539 (3)	93.073 (4)
V (Å³)	1300.28 (6)	1309.47 (7)	1408.88 (12)
Density Rx (Mg m^-3)	1.360	1.310	1.241

Data Collection
µ (mm^-1)	0.11	0.10	0.09
Crystal size (mm)	0.28 × 0.18 × 0.14	0.42 × 0.22 × 0.12	0.50 × 0.23 × 0.20
T_min, T_max	0.95, 0.98	0.95, 0.98	0.96, 0.99

Refinement
N_meas, N_indep, N_[_I _{> 2}_σ₍_I_)]	31774, 5295, 4103	31770, 5337, 4297	24363, 5718, 3559
R_int	0.053	0.047	0.099
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 0.95	0.039, 0.093, 1.04	0.060, 0.152, 1.00
No. of reflections	5295	5337	5718
No. of parameters	356	343	352
No. of restraints	3	2	2
Δρ_max, Δρ_min (e Å^-3)	0.13, -0.19	0.12, -0.16	0.16, -0.15

Thermal behaviour
T_f(onset) (K)	526	481	499
ΔH_f (kJ mol^-1)	44 (1)	34 (2)	17 (2)

Optical rotation
[α]_D	- 6.6	-5.4	-3.2
Concentration (c), solvent	0.5, CHCl₃	0.4, MeOH	0.2, MeOH

Crystal system: monoclinic; space group P2₁, T (K): 294; Z: 2; λ (Å): 0.7107 (Mo Kα). Diffractometer: CCD Oxford Diffraction Xcalibur Eos Gemini. Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009). '(sin θ/λ)_max (Å^-1)' 0.625. H atoms treated by a mixture of independent and constrained refinement. Absolute structure assigned by comparison with related compounds of the same origin.

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2018 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bonding interactions (Å, °) top

	Code	D—H···A	D—H	H···A	D···A	D—H···A	100*ρ(r) (a.u.)	100*\nabla²ρ(r) (a.u.)
(II)	#1	O2—H2···O1	0.85 (3)	2.10 (3)	2.623 (3)	119 (3)	2.23	1.01
	#2	C12—H12C···O1A	0.96	2.23	2.943 (4)	130	1.64	0.63
	#3	C13—H13A···O1B	0.96	2.21	3.029 (4)	142	1.65	0.62
	#4	C14—H14A···O1A	0.96	2.39	3.023 (4)	123	1.24	0.47
	#5	O3—H3···O2Cⁱ	0.85 (3)	2.17 (2)	2.945 (4)	152 (4)	1.39	0.58
	#6	C5B—H5B···O2ⁱⁱ	0.93	2.37	3.284 (5)	168	1.04	0.37

(III)	#1	O2—H2···O1	0.86 (3)	2.08 (3)	2.625 (2)	121 (2)	2.4	1.02
	#2	C12—H12C···O1A	0.96	2.25	2.949 (3)	129	1.6	0.62
	#3	C13—H13A···O1B	0.96	2.23	3.048 (3)	142	1.58	0.59
	#4	C14—H14A···O1A	0.96	2.41	3.046 (4)	123	1.21	0.45
	#5	C4A—H4A···O2Cⁱ	0.93	2.56	3.376 (5)	146	0.75	0.25
	#6	C5B—H5B···O2ⁱⁱ	0.93	2.40	3.310 (4)	167	0.97	0.34

(IV)	#1	O2—H2···O1	0.84 (2)	2.26 (4)	2.641 (4)	108 (4)	2.15	0.98
	#2	C12—H12C···O1A	0.96	2.16	2.898 (7)	132	1.67	0.65
	#3	C13—H13A···O1B	0.96	2.24	3.070 (7)	144	1.57	0.59
	#4	C14—H14A···O1A	0.96	2.45	3.085 (7)	124	1.19	0.43
	#5	O2—H2···O2Bⁱ	0.84 (2)	2.33 (3)	3.118 (5)	155 (4)	1.02	0.39
	#6	C9—H9···O2ⁱⁱ	0.98	2.45	3.335 (5)	150	0.94	0.33

Note: (*) Paz et al. (2017).

Symmetry codes for (II): (i) x, y+1, z; (ii) x-1, y, z. Symmetry codes for (III): (i) x+1, y+1, z; (ii) x-1, y, z. Symmetry codes for (IV): (i) x+1, y, z; (ii) x-1, y, z.

AIM analysis of the electron density has been performed at the PBEPBE-D/DGDZVP level of theory using the Multiwfn program (Lu & Chen, 2012).

Chiral centres in (I), (II), (III) and (IV) top

	(I)*	(II)	(III)	(IV)
C1	S	S	S	S
C4	S	S	S	S
C5	S	S	S	S
C6	R	R	R	R
C7	R	R	R	R
C8	R	R	n.a.	n.a.
C9	R	R	S	S
C10	S	S	S	S

Note: (*) Paz et al. (2017).

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Three new di­hydro-β-agaro­furan sesquiterpenes from the seeds of Maytenus boaria

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Three new dihydro-β-agarofuran sesquiterpenes from the seeds of Maytenus boaria