(4bS,8aS)-1-Isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octa-hydro-phenan-thren-2-yl benzoate.

The title compound, C27H34O2, was hemisynthesized through direct benzoyl-ation of the naturally occurring meroterpene totarol. The central fused six-membered ring has a half-chair conformation, whereas the terminal six-membered ring displays a chair conformation. The dihedral angle between the fused benzene ring and the benzoyl benzene ring is 73.05 (14)°. The S,S chirality of the mol-ecule is consistent with the synthetic pathway, and confirmed by the refinement of the Flack parameter.

Related literature

For the synthesis and biological activity of totarol [systematic name: (4bS,8aS)-4b,8,8-trimethyl-1-propan-2-yl-5,6,7,8a,9,10-hexa­hydro­phenanthren-2-ol], see: Short & Stromberg (1937 ▶); Barrero et al. (2003 ▶); Haraguchi et al. (1996 ▶); Bernabeu et al. (2002 ▶); Marcos et al. (2003 ▶); Tacon et al. (2012 ▶). For conformational analysis and absolute configuration determination, see: Cremer & Pople (1975 ▶); Flack (1983 ▶); Flack & Bernardinelli (2000 ▶); Parsons et al. (2013 ▶); Spek (2009 ▶). For related structures, see: Zeroual et al. (2008 ▶); Oubabi et al. (2014 ▶); Pettit et al. (2004 ▶).

Experimental

Crystal data

C27H34O2

M = 390.54

Monoclinic,

a = 7.7369 (3) Å

b = 7.2079 (4) Å

c = 20.2499 (9) Å

β = 99.816 (4)°

V = 1112.74 (9) Å3

Z = 2

Cu Kα radiation

μ = 0.55 mm−1

T = 180 K

0.50 × 0.25 × 0.07 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.689, T max = 1.0

9197 measured reflections

3116 independent reflections

2926 reflections with I > 2σ(I)

R int = 0.033

θmax = 60.8°

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.095

S = 1.04

3116 reflections

267 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack x determined using 1138 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: −0.11 (17)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814015827/bh2501sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015827/bh2501Isup2.hkl

CCDC reference: 1012402

Additional supporting information: crystallographic information; 3D view; checkCIF report

C27H34O2	F(000) = 424
Mr = 390.54	Dx = 1.166 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 7.7369 (3) Å	Cell parameters from 4294 reflections
b = 7.2079 (4) Å	θ = 4.4–60.4°
c = 20.2499 (9) Å	µ = 0.55 mm−1
β = 99.816 (4)°	T = 180 K
V = 1112.74 (9) Å3	Flattened, colourless
Z = 2	0.50 × 0.25 × 0.07 mm

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	3116 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2926 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
Detector resolution: 16.1978 pixels mm-1	θmax = 60.8°, θmin = 4.4°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→7
Tmin = 0.689, Tmax = 1.0	l = −22→22
9197 measured reflections

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)] = 0.038	H-atom parameters constrained
wR(F2) = 0.095	w = 1/[σ2(Fo2) + (0.0501P)2 + 0.1662P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3116 reflections	Δρmax = 0.13 e Å−3
267 parameters	Δρmin = −0.21 e Å−3
1 restraint	Absolute structure: Flack x determined using 1138 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 constraints	Absolute structure parameter: −0.11 (17)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
O1	1.0825 (2)	0.2023 (3)	0.33409 (8)	0.0388 (5)
O2	1.2632 (2)	0.2265 (4)	0.25828 (10)	0.0661 (7)
C1	0.8685 (3)	0.4403 (4)	0.29484 (14)	0.0413 (7)
C2	0.9421 (3)	0.2698 (4)	0.28549 (13)	0.0359 (6)
C3	0.8814 (3)	0.1570 (4)	0.23162 (13)	0.0385 (7)
H3	0.9338	0.0395	0.2270	0.046*
C4	0.7432 (3)	0.2179 (4)	0.18449 (13)	0.0374 (6)
H4	0.7019	0.1416	0.1468	0.045*
C4A	0.6625 (3)	0.3879 (4)	0.19052 (12)	0.0319 (6)
C4B	0.5137 (3)	0.4506 (4)	0.13429 (12)	0.0330 (6)
C5	0.4014 (3)	0.2837 (4)	0.10522 (14)	0.0405 (7)
H5A	0.4730	0.2022	0.0812	0.049*
H5B	0.3675	0.2113	0.1426	0.049*
C6	0.2361 (4)	0.3401 (5)	0.05730 (15)	0.0462 (8)
H6A	0.2691	0.4028	0.0178	0.055*
H6B	0.1676	0.2279	0.0415	0.055*
C7	0.1239 (3)	0.4697 (4)	0.09132 (14)	0.0425 (7)
H7A	0.0835	0.4024	0.1285	0.051*
H7B	0.0188	0.5050	0.0587	0.051*
C8	0.2197 (3)	0.6458 (4)	0.11908 (13)	0.0390 (7)
C8A	0.3948 (3)	0.5887 (4)	0.16448 (12)	0.0334 (6)
H8A	0.3585	0.5209	0.2030	0.040*
C9	0.5059 (4)	0.7494 (4)	0.19617 (15)	0.0431 (7)
H9A	0.5673	0.8071	0.1623	0.052*
H9B	0.4290	0.8445	0.2113	0.052*
C10	0.6400 (4)	0.6854 (4)	0.25540 (15)	0.0470 (7)
H10A	0.5817	0.6768	0.2952	0.056*
H10B	0.7328	0.7810	0.2649	0.056*
C10A	0.7261 (3)	0.5000 (4)	0.24594 (13)	0.0379 (6)
C11	0.9377 (5)	0.5598 (5)	0.35593 (17)	0.0653 (11)
H11	0.8681	0.6774	0.3505	0.078*
C12	1.1296 (6)	0.6161 (8)	0.36183 (19)	0.0941 (16)
H12A	1.2045	0.5079	0.3745	0.141*
H12B	1.1568	0.7127	0.3961	0.141*
H12C	1.1508	0.6641	0.3186	0.141*
C13	0.9041 (5)	0.4715 (8)	0.42098 (18)	0.0814 (14)
H13A	0.7788	0.4440	0.4174	0.122*
H13B	0.9404	0.5574	0.4583	0.122*
H13C	0.9716	0.3562	0.4290	0.122*
C14	0.6051 (3)	0.5319 (5)	0.07852 (14)	0.0494 (8)
H14A	0.6672	0.6460	0.0947	0.074*
H14B	0.5170	0.5598	0.0390	0.074*
H14C	0.6892	0.4414	0.0666	0.074*
C15	0.2425 (4)	0.7775 (5)	0.06206 (17)	0.0540 (8)
H15A	0.2917	0.7092	0.0277	0.081*
H15B	0.3222	0.8783	0.0796	0.081*
H15C	0.1283	0.8293	0.0423	0.081*
C16	0.1036 (4)	0.7443 (6)	0.16232 (18)	0.0629 (10)
H16A	−0.0121	0.7680	0.1355	0.094*
H16B	0.1580	0.8622	0.1785	0.094*
H16C	0.0907	0.6655	0.2006	0.094*
C17	1.2417 (3)	0.1844 (4)	0.31324 (14)	0.0413 (7)
C18	1.3781 (3)	0.1078 (4)	0.36592 (13)	0.0366 (6)
C19	1.3442 (4)	0.0440 (5)	0.42702 (13)	0.0424 (7)
H19	1.2289	0.0526	0.4371	0.051*
C20	1.4771 (4)	−0.0320 (5)	0.47326 (15)	0.0546 (8)
H20	1.4535	−0.0762	0.5150	0.066*
C21	1.6455 (4)	−0.0433 (5)	0.45829 (16)	0.0532 (8)
H21	1.7372	−0.0958	0.4899	0.064*
C22	1.6800 (4)	0.0207 (5)	0.39825 (16)	0.0513 (8)
H22	1.7957	0.0133	0.3886	0.062*
C23	1.5477 (3)	0.0959 (5)	0.35175 (14)	0.0457 (7)
H23	1.5721	0.1395	0.3100	0.055*

	U11	U22	U33	U12	U13	U23
O1	0.0294 (9)	0.0476 (12)	0.0387 (9)	0.0043 (9)	0.0037 (7)	0.0049 (9)
O2	0.0380 (11)	0.110 (2)	0.0515 (13)	0.0043 (13)	0.0107 (9)	0.0304 (14)
C1	0.0373 (14)	0.0389 (17)	0.0442 (15)	0.0012 (13)	−0.0026 (12)	−0.0076 (13)
C2	0.0268 (12)	0.0423 (18)	0.0375 (14)	0.0014 (13)	0.0026 (10)	0.0028 (13)
C3	0.0338 (13)	0.0370 (17)	0.0453 (15)	0.0043 (13)	0.0085 (11)	−0.0029 (13)
C4	0.0334 (13)	0.0381 (17)	0.0406 (14)	0.0010 (13)	0.0064 (11)	−0.0082 (13)
C4A	0.0281 (13)	0.0335 (16)	0.0342 (14)	−0.0025 (11)	0.0059 (10)	−0.0010 (11)
C4B	0.0303 (13)	0.0361 (16)	0.0324 (12)	−0.0024 (12)	0.0047 (10)	0.0001 (12)
C5	0.0369 (14)	0.0390 (17)	0.0428 (15)	0.0014 (13)	−0.0008 (12)	−0.0081 (13)
C6	0.0404 (16)	0.0428 (19)	0.0500 (17)	−0.0026 (14)	−0.0078 (13)	−0.0094 (14)
C7	0.0303 (13)	0.0460 (18)	0.0491 (15)	−0.0025 (13)	0.0011 (11)	−0.0001 (14)
C8	0.0324 (13)	0.0398 (18)	0.0432 (14)	0.0010 (13)	0.0022 (11)	−0.0012 (13)
C8A	0.0324 (13)	0.0338 (16)	0.0336 (13)	0.0001 (12)	0.0049 (10)	−0.0004 (12)
C9	0.0420 (15)	0.0328 (17)	0.0509 (16)	0.0027 (13)	−0.0023 (12)	−0.0047 (13)
C10	0.0468 (16)	0.0366 (18)	0.0512 (16)	0.0047 (14)	−0.0100 (13)	−0.0096 (14)
C10A	0.0345 (13)	0.0347 (16)	0.0429 (15)	−0.0011 (12)	0.0018 (11)	−0.0053 (12)
C11	0.069 (2)	0.053 (2)	0.061 (2)	0.0181 (18)	−0.0263 (16)	−0.0213 (18)
C12	0.122 (4)	0.091 (3)	0.057 (2)	−0.063 (3)	−0.021 (2)	0.000 (2)
C13	0.056 (2)	0.129 (4)	0.060 (2)	−0.009 (2)	0.0117 (16)	−0.046 (3)
C14	0.0359 (14)	0.070 (2)	0.0441 (15)	0.0045 (16)	0.0121 (12)	0.0086 (16)
C15	0.0504 (17)	0.046 (2)	0.0610 (19)	0.0002 (15)	−0.0043 (14)	0.0134 (16)
C16	0.0399 (16)	0.076 (3)	0.071 (2)	0.0171 (18)	0.0046 (15)	−0.018 (2)
C17	0.0321 (13)	0.0477 (19)	0.0441 (16)	0.0019 (13)	0.0061 (11)	0.0081 (14)
C18	0.0345 (13)	0.0351 (16)	0.0391 (14)	−0.0002 (12)	0.0033 (11)	−0.0020 (12)
C19	0.0370 (14)	0.0466 (18)	0.0426 (15)	0.0003 (14)	0.0040 (12)	−0.0001 (14)
C20	0.0525 (18)	0.065 (2)	0.0442 (15)	0.0038 (17)	0.0011 (14)	0.0082 (16)
C21	0.0441 (16)	0.052 (2)	0.0562 (18)	0.0095 (16)	−0.0109 (14)	−0.0003 (16)
C22	0.0340 (15)	0.058 (2)	0.0602 (19)	0.0077 (15)	0.0039 (13)	−0.0046 (17)
C23	0.0344 (14)	0.055 (2)	0.0471 (15)	0.0033 (14)	0.0057 (12)	0.0011 (15)

O1—C17	1.374 (3)	C10—C10A	1.520 (4)
O1—C2	1.422 (3)	C10—H10A	0.9900
O2—C17	1.192 (3)	C10—H10B	0.9900
C1—C2	1.381 (4)	C11—C12	1.524 (6)
C1—C10A	1.417 (4)	C11—C13	1.524 (6)
C1—C11	1.528 (4)	C11—H11	1.0000
C2—C3	1.377 (4)	C12—H12A	0.9800
C3—C4	1.378 (4)	C12—H12B	0.9800
C3—H3	0.9500	C12—H12C	0.9800
C4—C4A	1.390 (4)	C13—H13A	0.9800
C4—H4	0.9500	C13—H13B	0.9800
C4A—C10A	1.402 (4)	C13—H13C	0.9800
C4A—C4B	1.542 (3)	C14—H14A	0.9800
C4B—C5	1.540 (4)	C14—H14B	0.9800
C4B—C14	1.547 (4)	C14—H14C	0.9800
C4B—C8A	1.550 (4)	C15—H15A	0.9800
C5—C6	1.523 (4)	C15—H15B	0.9800
C5—H5A	0.9900	C15—H15C	0.9800
C5—H5B	0.9900	C16—H16A	0.9800
C6—C7	1.518 (4)	C16—H16B	0.9800
C6—H6A	0.9900	C16—H16C	0.9800
C6—H6B	0.9900	C17—C18	1.474 (4)
C7—C8	1.528 (4)	C18—C19	1.387 (4)
C7—H7A	0.9900	C18—C23	1.392 (4)
C7—H7B	0.9900	C19—C20	1.380 (4)
C8—C15	1.528 (4)	C19—H19	0.9500
C8—C16	1.531 (4)	C20—C21	1.390 (5)
C8—C8A	1.557 (4)	C20—H20	0.9500
C8A—C9	1.518 (4)	C21—C22	1.369 (5)
C8A—H8A	1.0000	C21—H21	0.9500
C9—C10	1.518 (4)	C22—C23	1.378 (4)
C9—H9A	0.9900	C22—H22	0.9500
C9—H9B	0.9900	C23—H23	0.9500
C17—O1—C2	116.01 (19)	C10A—C10—H10B	108.5
C2—C1—C10A	117.7 (2)	H10A—C10—H10B	107.5
C2—C1—C11	121.2 (3)	C4A—C10A—C1	120.6 (3)
C10A—C1—C11	121.2 (3)	C4A—C10A—C10	120.4 (2)
C3—C2—C1	122.8 (2)	C1—C10A—C10	119.0 (2)
C3—C2—O1	117.6 (2)	C12—C11—C13	110.5 (3)
C1—C2—O1	119.6 (2)	C12—C11—C1	114.6 (3)
C2—C3—C4	118.7 (3)	C13—C11—C1	112.1 (3)
C2—C3—H3	120.7	C12—C11—H11	106.3
C4—C3—H3	120.7	C13—C11—H11	106.3
C3—C4—C4A	121.8 (2)	C1—C11—H11	106.3
C3—C4—H4	119.1	C11—C12—H12A	109.5
C4A—C4—H4	119.1	C11—C12—H12B	109.5
C4—C4A—C10A	118.5 (2)	H12A—C12—H12B	109.5
C4—C4A—C4B	118.9 (2)	C11—C12—H12C	109.5
C10A—C4A—C4B	122.6 (2)	H12A—C12—H12C	109.5
C5—C4B—C4A	110.8 (2)	H12B—C12—H12C	109.5
C5—C4B—C14	108.4 (2)	C11—C13—H13A	109.5
C4A—C4B—C14	105.85 (19)	C11—C13—H13B	109.5
C5—C4B—C8A	108.6 (2)	H13A—C13—H13B	109.5
C4A—C4B—C8A	108.4 (2)	C11—C13—H13C	109.5
C14—C4B—C8A	114.9 (2)	H13A—C13—H13C	109.5
C6—C5—C4B	113.1 (2)	H13B—C13—H13C	109.5
C6—C5—H5A	109.0	C4B—C14—H14A	109.5
C4B—C5—H5A	109.0	C4B—C14—H14B	109.5
C6—C5—H5B	109.0	H14A—C14—H14B	109.5
C4B—C5—H5B	109.0	C4B—C14—H14C	109.5
H5A—C5—H5B	107.8	H14A—C14—H14C	109.5
C7—C6—C5	111.0 (2)	H14B—C14—H14C	109.5
C7—C6—H6A	109.4	C8—C15—H15A	109.5
C5—C6—H6A	109.4	C8—C15—H15B	109.5
C7—C6—H6B	109.4	H15A—C15—H15B	109.5
C5—C6—H6B	109.4	C8—C15—H15C	109.5
H6A—C6—H6B	108.0	H15A—C15—H15C	109.5
C6—C7—C8	113.5 (2)	H15B—C15—H15C	109.5
C6—C7—H7A	108.9	C8—C16—H16A	109.5
C8—C7—H7A	108.9	C8—C16—H16B	109.5
C6—C7—H7B	108.9	H16A—C16—H16B	109.5
C8—C7—H7B	108.9	C8—C16—H16C	109.5
H7A—C7—H7B	107.7	H16A—C16—H16C	109.5
C15—C8—C7	110.4 (2)	H16B—C16—H16C	109.5
C15—C8—C16	107.4 (3)	O2—C17—O1	122.5 (2)
C7—C8—C16	107.5 (2)	O2—C17—C18	125.0 (2)
C15—C8—C8A	114.1 (2)	O1—C17—C18	112.4 (2)
C7—C8—C8A	108.4 (2)	C19—C18—C23	119.5 (3)
C16—C8—C8A	108.7 (2)	C19—C18—C17	123.3 (2)
C9—C8A—C4B	109.0 (2)	C23—C18—C17	117.2 (2)
C9—C8A—C8	114.9 (2)	C20—C19—C18	120.3 (3)
C4B—C8A—C8	116.9 (2)	C20—C19—H19	119.9
C9—C8A—H8A	104.9	C18—C19—H19	119.9
C4B—C8A—H8A	104.9	C19—C20—C21	119.5 (3)
C8—C8A—H8A	104.9	C19—C20—H20	120.2
C10—C9—C8A	111.3 (3)	C21—C20—H20	120.2
C10—C9—H9A	109.4	C22—C21—C20	120.4 (3)
C8A—C9—H9A	109.4	C22—C21—H21	119.8
C10—C9—H9B	109.4	C20—C21—H21	119.8
C8A—C9—H9B	109.4	C21—C22—C23	120.3 (3)
H9A—C9—H9B	108.0	C21—C22—H22	119.8
C9—C10—C10A	115.0 (2)	C23—C22—H22	119.8
C9—C10—H10A	108.5	C22—C23—C18	120.0 (3)
C10A—C10—H10A	108.5	C22—C23—H23	120.0
C9—C10—H10B	108.5	C18—C23—H23	120.0