Bispuupehenone from the South Chinese Sea sponge Dysidea sp.

Bispuupehenone, C(42)H(54)O(6), formally results from dimerization of puupehenone, which is constructed of sesquiterpene and benzene units. Bispuupehenone was isolated from the South China Sea sponge Dysidea sp. and the single-crystal X-ray diffraction analysis confirmed the previously reported structure. The mol-ecule is located on a twofold axis and the dimerization forms two fused dibenzopyran systems related by symmetry. In the asymmetric unit, the two cyclohexane rings adopt chair conformations, while the two pyran rings adopt half-chair conformations. The relative stereochemistry and configurations for the ring junctions are in agreement with the structure reported previously.

Related literature

The title compound was first isolated from the Pacific marine sponge Heteronema sp., see Amade et al. (1983 ▶). For the biological and pharmaceutical activity of puupehenone, see: Barrero et al. (1998 ▶, 1999 ▶); Castro et al. (2004 ▶); Ciavatta et al. (2007 ▶); Longley et al. (1993 ▶); Kohmoto et al. (1987 ▶); Takamatsu et al. (2003 ▶). For the synthesis and semi-synthesis of puupehenone and its derivatives, see: Hamann (2003 ▶); Alvarez-Manzaneda et al. (2005 ▶, 2007 ▶).

Experimental

Crystal data

C42H54O6

M = 654.85

Tetragonal,

a = 13.5981 (10) Å

c = 18.7260 (19) Å

V = 3462.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 293 (2) K

0.39 × 0.24 × 0.14 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.743, T max = 0.990

20532 measured reflections

2219 independent reflections

1644 reflections with I > 2σ(I)

R int = 0.110

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.113

S = 0.94

2219 reflections

225 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808011987/bh2164sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011987/bh2164Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C42H54O6	Z = 4
Mr = 654.85	F000 = 1416
Tetragonal, P41212	Dx = 1.256 Mg m−3
Hall symbol: P 4abw 2nw	Mo Kα radiation λ = 0.71073 Å
a = 13.5981 (10) Å	Cell parameters from 4034 reflections
b = 13.5981 (10) Å	θ = 4.8–54.2º
c = 18.7260 (19) Å	µ = 0.08 mm−1
α = 90º	T = 293 (2) K
β = 90º	Prismatic, colourless
γ = 90º	0.39 × 0.24 × 0.14 mm
V = 3462.6 (5) Å3

Bruker APEX CCD area-detector diffractometer	2219 independent reflections
Radiation source: fine-focus sealed tube	1644 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.110
T = 293(2) K	θmax = 27.0º
φ and ω scans	θmin = 1.9º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −16→17
Tmin = 0.743, Tmax = 0.990	k = −17→17
20532 measured reflections	l = −11→23

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3
S = 0.95	(Δ/σ)max = 0.007
2219 reflections	Δρmax = 0.23 e Å−3
225 parameters	Δρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

	x	y	z	Uiso*/Ueq
O1	0.15743 (13)	0.55657 (12)	0.08619 (8)	0.0429 (5)
O2	0.12262 (16)	0.48461 (14)	0.33312 (11)	0.0530 (5)
O3	0.34879 (12)	0.77308 (13)	0.13171 (8)	0.0415 (4)
C1	0.1684 (2)	0.87117 (19)	−0.00763 (14)	0.0499 (7)
H1A	0.1694	0.9034	0.0386	0.060*
H1B	0.2340	0.8757	−0.0277	0.060*
C2	0.0968 (3)	0.9254 (2)	−0.05633 (14)	0.0637 (9)
H2A	0.0322	0.9261	−0.0345	0.076*
H2B	0.1183	0.9930	−0.0619	0.076*
C3	0.0904 (3)	0.8771 (2)	−0.12908 (15)	0.0681 (9)
H3A	0.1538	0.8820	−0.1525	0.082*
H3B	0.0430	0.9126	−0.1580	0.082*
C4	0.0601 (3)	0.7683 (2)	−0.12559 (14)	0.0573 (8)
C5	0.1302 (2)	0.71542 (19)	−0.07258 (12)	0.0431 (6)
H5	0.1954	0.7217	−0.0944	0.052*
C6	0.1141 (2)	0.6044 (2)	−0.06599 (13)	0.0474 (7)
H6A	0.0577	0.5915	−0.0356	0.057*
H6B	0.1010	0.5765	−0.1127	0.057*
C7	0.2055 (2)	0.5575 (2)	−0.03409 (13)	0.0484 (7)
H7A	0.1950	0.4871	−0.0303	0.058*
H7B	0.2604	0.5679	−0.0664	0.058*
C8	0.2325 (2)	0.59716 (19)	0.03840 (13)	0.0411 (6)
C9	0.23190 (19)	0.71109 (17)	0.04069 (12)	0.0371 (6)
H9	0.2905	0.7323	0.0145	0.045*
C10	0.14213 (18)	0.76213 (18)	0.00287 (13)	0.0389 (6)
C11	0.0747 (3)	0.7242 (3)	−0.20075 (15)	0.0850 (12)
H11A	0.0422	0.7649	−0.2354	0.127*
H11B	0.0472	0.6592	−0.2022	0.127*
H11C	0.1436	0.7211	−0.2115	0.127*
C12	−0.0502 (2)	0.7571 (3)	−0.10853 (18)	0.0746 (10)
H12A	−0.0662	0.7956	−0.0672	0.112*
H12B	−0.0647	0.6892	−0.0993	0.112*
H12C	−0.0884	0.7795	−0.1485	0.112*
C13	0.0492 (2)	0.7539 (2)	0.04922 (13)	0.0462 (6)
H13A	0.0646	0.7722	0.0975	0.069*
H13B	0.0257	0.6873	0.0483	0.069*
H13C	−0.0006	0.7969	0.0308	0.069*
C14	0.24566 (18)	0.74743 (19)	0.11748 (12)	0.0365 (5)
H14	0.2065	0.8074	0.1231	0.044*
C15	0.3325 (2)	0.5555 (2)	0.06039 (15)	0.0539 (7)
H15A	0.3455	0.5721	0.1093	0.081*
H15B	0.3829	0.5829	0.0305	0.081*
H15C	0.3319	0.4852	0.0551	0.081*
C16	0.21009 (17)	0.67425 (18)	0.17229 (12)	0.0355 (6)
C17	0.22961 (17)	0.69613 (18)	0.24324 (13)	0.0351 (5)
C18	0.20089 (17)	0.63566 (18)	0.29797 (12)	0.0359 (5)
C19	0.15135 (18)	0.54863 (18)	0.28072 (13)	0.0384 (6)
C20	0.13528 (19)	0.52376 (18)	0.21062 (13)	0.0401 (6)
H20	0.1029	0.4655	0.1997	0.048*
C21	0.16728 (18)	0.58544 (18)	0.15546 (13)	0.0367 (6)
H2	0.149 (3)	0.513 (3)	0.3750 (19)	0.086 (11)*

	U11	U22	U33	U12	U13	U23
O1	0.0538 (11)	0.0380 (9)	0.0370 (9)	−0.0081 (8)	0.0003 (8)	−0.0055 (8)
O2	0.0695 (13)	0.0420 (10)	0.0474 (11)	−0.0153 (10)	0.0097 (10)	0.0052 (9)
O3	0.0395 (9)	0.0490 (10)	0.0360 (9)	−0.0103 (8)	0.0026 (8)	−0.0008 (8)
C1	0.0642 (18)	0.0418 (14)	0.0436 (14)	−0.0107 (13)	−0.0004 (14)	0.0011 (13)
C2	0.087 (2)	0.0442 (16)	0.0597 (19)	−0.0007 (17)	−0.0084 (18)	0.0115 (14)
C3	0.092 (3)	0.0619 (19)	0.0507 (18)	−0.0038 (18)	−0.0139 (18)	0.0132 (16)
C4	0.072 (2)	0.0574 (18)	0.0421 (15)	−0.0089 (15)	−0.0117 (15)	0.0084 (15)
C5	0.0527 (15)	0.0435 (14)	0.0333 (13)	−0.0078 (13)	0.0020 (12)	−0.0012 (11)
C6	0.0624 (18)	0.0469 (15)	0.0329 (13)	−0.0116 (14)	−0.0030 (13)	−0.0100 (12)
C7	0.0604 (18)	0.0436 (15)	0.0412 (14)	0.0014 (13)	0.0053 (14)	−0.0076 (12)
C8	0.0461 (15)	0.0397 (13)	0.0373 (13)	0.0023 (12)	0.0052 (12)	−0.0056 (12)
C9	0.0410 (13)	0.0376 (12)	0.0328 (13)	−0.0041 (11)	0.0052 (11)	−0.0029 (11)
C10	0.0441 (14)	0.0387 (13)	0.0339 (12)	−0.0051 (11)	0.0019 (11)	0.0006 (11)
C11	0.134 (4)	0.081 (2)	0.0400 (18)	−0.012 (3)	−0.016 (2)	0.0019 (17)
C12	0.071 (2)	0.080 (2)	0.073 (2)	−0.0043 (19)	−0.0276 (18)	0.006 (2)
C13	0.0454 (15)	0.0527 (16)	0.0405 (14)	0.0016 (14)	0.0047 (12)	−0.0006 (13)
C14	0.0366 (12)	0.0396 (13)	0.0332 (13)	−0.0056 (11)	−0.0004 (10)	0.0001 (11)
C15	0.0551 (18)	0.0540 (17)	0.0526 (16)	0.0122 (14)	0.0044 (14)	−0.0041 (14)
C16	0.0325 (12)	0.0365 (13)	0.0375 (13)	−0.0026 (10)	0.0022 (11)	−0.0009 (11)
C17	0.0318 (12)	0.0374 (12)	0.0360 (13)	−0.0021 (10)	0.0019 (11)	−0.0025 (11)
C18	0.0353 (12)	0.0404 (13)	0.0321 (13)	−0.0011 (11)	0.0022 (10)	−0.0017 (11)
C19	0.0402 (14)	0.0343 (13)	0.0407 (13)	−0.0035 (11)	0.0071 (11)	0.0036 (11)
C20	0.0432 (14)	0.0341 (12)	0.0430 (14)	−0.0062 (11)	0.0003 (12)	−0.0051 (11)
C21	0.0380 (13)	0.0375 (13)	0.0345 (13)	−0.0014 (11)	0.0002 (11)	−0.0047 (11)

O1—C21	1.362 (3)	C8—C9	1.550 (3)
O1—C8	1.465 (3)	C9—C14	1.532 (3)
O2—C19	1.369 (3)	C9—C10	1.573 (3)
O2—H2	0.95 (4)	C9—H9	0.9800
O3—C18i	1.380 (3)	C10—C13	1.537 (3)
O3—C14	1.469 (3)	C11—H11A	0.9600
C1—C2	1.524 (4)	C11—H11B	0.9600
C1—C10	1.538 (3)	C11—H11C	0.9600
C1—H1A	0.9700	C12—H12A	0.9600
C1—H1B	0.9700	C12—H12B	0.9600
C2—C3	1.515 (4)	C12—H12C	0.9600
C2—H2A	0.9700	C13—H13A	0.9600
C2—H2B	0.9700	C13—H13B	0.9600
C3—C4	1.536 (5)	C13—H13C	0.9600
C3—H3A	0.9700	C14—C16	1.509 (3)
C3—H3B	0.9700	C14—H14	0.9800
C4—C12	1.541 (5)	C15—H15A	0.9600
C4—C11	1.543 (4)	C15—H15B	0.9600
C4—C5	1.553 (4)	C15—H15C	0.9600
C5—C6	1.530 (4)	C16—C21	1.377 (3)
C5—C10	1.558 (3)	C16—C17	1.387 (3)
C5—H5	0.9800	C17—C18	1.371 (3)
C6—C7	1.520 (4)	C17—C17i	1.450 (5)
C6—H6A	0.9700	C18—O3i	1.380 (3)
C6—H6B	0.9700	C18—C19	1.399 (4)
C7—C8	1.506 (3)	C19—C20	1.373 (3)
C7—H7A	0.9700	C20—C21	1.400 (3)
C7—H7B	0.9700	C20—H20	0.9300
C8—C15	1.530 (4)
C21—O1—C8	113.87 (18)	C10—C9—H9	106.0
C19—O2—H2	103 (2)	C13—C10—C1	109.5 (2)
C18i—O3—C14	112.36 (18)	C13—C10—C5	113.4 (2)
C2—C1—C10	113.2 (2)	C1—C10—C5	107.5 (2)
C2—C1—H1A	108.9	C13—C10—C9	110.58 (19)
C10—C1—H1A	108.9	C1—C10—C9	107.6 (2)
C2—C1—H1B	108.9	C5—C10—C9	108.0 (2)
C10—C1—H1B	108.9	C4—C11—H11A	109.5
H1A—C1—H1B	107.7	C4—C11—H11B	109.5
C3—C2—C1	111.4 (3)	H11A—C11—H11B	109.5
C3—C2—H2A	109.3	C4—C11—H11C	109.5
C1—C2—H2A	109.3	H11A—C11—H11C	109.5
C3—C2—H2B	109.3	H11B—C11—H11C	109.5
C1—C2—H2B	109.3	C4—C12—H12A	109.5
H2A—C2—H2B	108.0	C4—C12—H12B	109.5
C2—C3—C4	113.2 (3)	H12A—C12—H12B	109.5
C2—C3—H3A	108.9	C4—C12—H12C	109.5
C4—C3—H3A	108.9	H12A—C12—H12C	109.5
C2—C3—H3B	108.9	H12B—C12—H12C	109.5
C4—C3—H3B	108.9	C10—C13—H13A	109.5
H3A—C3—H3B	107.7	C10—C13—H13B	109.5
C3—C4—C12	111.4 (3)	H13A—C13—H13B	109.5
C3—C4—C11	107.5 (3)	C10—C13—H13C	109.5
C12—C4—C11	106.0 (3)	H13A—C13—H13C	109.5
C3—C4—C5	108.0 (2)	H13B—C13—H13C	109.5
C12—C4—C5	114.8 (2)	O3—C14—C16	109.82 (18)
C11—C4—C5	108.9 (3)	O3—C14—C9	111.31 (19)
C6—C5—C4	114.9 (2)	C16—C14—C9	112.7 (2)
C6—C5—C10	110.1 (2)	O3—C14—H14	107.6
C4—C5—C10	117.1 (2)	C16—C14—H14	107.6
C6—C5—H5	104.4	C9—C14—H14	107.6
C4—C5—H5	104.4	C8—C15—H15A	109.5
C10—C5—H5	104.4	C8—C15—H15B	109.5
C7—C6—C5	109.2 (2)	H15A—C15—H15B	109.5
C7—C6—H6A	109.8	C8—C15—H15C	109.5
C5—C6—H6A	109.8	H15A—C15—H15C	109.5
C7—C6—H6B	109.8	H15B—C15—H15C	109.5
C5—C6—H6B	109.8	C21—C16—C17	119.2 (2)
H6A—C6—H6B	108.3	C21—C16—C14	123.9 (2)
C8—C7—C6	113.7 (2)	C17—C16—C14	116.7 (2)
C8—C7—H7A	108.8	C18—C17—C16	122.2 (2)
C6—C7—H7A	108.8	C18—C17—C17i	119.0 (3)
C8—C7—H7B	108.8	C16—C17—C17i	116.7 (3)
C6—C7—H7B	108.8	C17—C18—O3i	123.3 (2)
H7A—C7—H7B	107.7	C17—C18—C19	118.1 (2)
O1—C8—C7	104.3 (2)	O3i—C18—C19	118.3 (2)
O1—C8—C15	108.4 (2)	O2—C19—C20	118.9 (2)
C7—C8—C15	109.0 (2)	O2—C19—C18	120.6 (2)
O1—C8—C9	110.86 (19)	C20—C19—C18	120.4 (2)
C7—C8—C9	112.5 (2)	C19—C20—C21	120.6 (2)
C15—C8—C9	111.6 (2)	C19—C20—H20	119.7
C14—C9—C8	110.36 (19)	C21—C20—H20	119.7
C14—C9—C10	112.0 (2)	O1—C21—C16	120.8 (2)
C8—C9—C10	115.6 (2)	O1—C21—C20	120.0 (2)
C14—C9—H9	106.0	C16—C21—C20	119.2 (2)
C8—C9—H9	106.0
C10—C1—C2—C3	−57.4 (3)	C14—C9—C10—C1	67.9 (2)
C1—C2—C3—C4	57.2 (4)	C8—C9—C10—C1	−164.5 (2)
C2—C3—C4—C12	74.3 (3)	C14—C9—C10—C5	−176.30 (19)
C2—C3—C4—C11	−169.9 (3)	C8—C9—C10—C5	−48.7 (3)
C2—C3—C4—C5	−52.6 (4)	C18i—O3—C14—C16	−50.0 (2)
C3—C4—C5—C6	−176.6 (3)	C18i—O3—C14—C9	−175.53 (19)
C12—C4—C5—C6	58.5 (4)	C8—C9—C14—O3	97.3 (2)
C11—C4—C5—C6	−60.1 (3)	C10—C9—C14—O3	−132.3 (2)
C3—C4—C5—C10	52.0 (3)	C8—C9—C14—C16	−26.6 (3)
C12—C4—C5—C10	−73.0 (3)	C10—C9—C14—C16	103.8 (2)
C11—C4—C5—C10	168.4 (2)	O3—C14—C16—C21	−126.5 (2)
C4—C5—C6—C7	160.9 (2)	C9—C14—C16—C21	−1.7 (3)
C10—C5—C6—C7	−64.4 (3)	O3—C14—C16—C17	48.3 (3)
C5—C6—C7—C8	58.8 (3)	C9—C14—C16—C17	173.0 (2)
C21—O1—C8—C7	−178.8 (2)	C21—C16—C17—C18	−5.2 (4)
C21—O1—C8—C15	65.2 (3)	C14—C16—C17—C18	179.8 (2)
C21—O1—C8—C9	−57.6 (3)	C21—C16—C17—C17i	158.50 (17)
C6—C7—C8—O1	72.2 (3)	C14—C16—C17—C17i	−16.5 (2)
C6—C7—C8—C15	−172.2 (2)	C16—C17—C18—O3i	174.0 (2)
C6—C7—C8—C9	−47.9 (3)	C17i—C17—C18—O3i	10.7 (3)
O1—C8—C9—C14	55.9 (3)	C16—C17—C18—C19	0.8 (4)
C7—C8—C9—C14	172.2 (2)	C17i—C17—C18—C19	−162.49 (17)
C15—C8—C9—C14	−64.9 (3)	C17—C18—C19—O2	178.8 (2)
O1—C8—C9—C10	−72.5 (3)	O3i—C18—C19—O2	5.2 (3)
C7—C8—C9—C10	43.8 (3)	C17—C18—C19—C20	2.1 (4)
C15—C8—C9—C10	166.6 (2)	O3i—C18—C19—C20	−171.5 (2)
C2—C1—C10—C13	−70.9 (3)	O2—C19—C20—C21	−177.3 (2)
C2—C1—C10—C5	52.7 (3)	C18—C19—C20—C21	−0.6 (4)
C2—C1—C10—C9	168.9 (2)	C8—O1—C21—C16	28.2 (3)
C6—C5—C10—C13	−64.4 (3)	C8—O1—C21—C20	−150.7 (2)
C4—C5—C10—C13	69.2 (3)	C17—C16—C21—O1	−172.3 (2)
C6—C5—C10—C1	174.4 (2)	C14—C16—C21—O1	2.3 (4)
C4—C5—C10—C1	−52.0 (3)	C17—C16—C21—C20	6.5 (4)
C6—C5—C10—C9	58.5 (3)	C14—C16—C21—C20	−178.9 (2)
C4—C5—C10—C9	−167.9 (2)	C19—C20—C21—O1	175.1 (2)
C14—C9—C10—C13	−51.7 (3)	C19—C20—C21—C16	−3.7 (4)
C8—C9—C10—C13	75.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3i	0.95 (4)	2.16 (4)	2.753 (3)	120 (3)