Redetermination and absolute configuration of 6-hydroxy-salvinolone.

THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND [SYSTEMATIC NAME: 5,6,10-trihydr-oxy-7-isopropyl-1,1,4a-trimethyl-2,3,4,4a-tetra-hydro-phenanthren-9(1H)-one], C(20)H(26)O(4), has been reported previously [Salae et al. (2009 ▶). Acta Cryst. E65, o2379-o2380], but the absolute configuration could not be determined as there was no significant anomalous dispersion using data collected with Mo radiation. The absolute configuration has now been determined by refinement of the Flack parameter with data collected using Cu radiation. The absolute configuration at position 4a of the diterpenoid is (R)-methyl; other features of the mol-ecule and its crystal packing are similar to those previously described.

Related literature

For background to diterpenes, see: Fraga et al. (2005 ▶); Hueso-Rodríguez et al. (1983 ▶) and Topcu & Ulubelen (1996 ▶). For the previous determination, see: Salae et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C20H26O4

M = 330.41

Orthorhombic,

a = 9.4908 (1) Å

b = 13.1684 (2) Å

c = 13.8105 (2) Å

V = 1726.02 (4) Å3

Z = 4

Cu Kα radiation

μ = 0.70 mm−1

T = 100 K

0.35 × 0.30 × 0.27 mm

Data collection

Bruker APEX Duo CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.790, T max = 0.835

6410 measured reflections

2622 independent reflections

2581 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.089

S = 1.09

2622 reflections

317 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 1609 Friedel pairs

Flack parameter: 0.06 (17)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053197/sj2711sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053197/sj2711Isup2.hkl

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

C20H26O4	F(000) = 712
Mr = 330.41	Dx = 1.271 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2622 reflections
a = 9.4908 (1) Å	θ = 5.7–62.5°
b = 13.1684 (2) Å	µ = 0.70 mm−1
c = 13.8105 (2) Å	T = 100 K
V = 1726.02 (4) Å3	Block, colorless
Z = 4	0.35 × 0.30 × 0.27 mm

Bruker APEX Duo CCD area-detector diffractometer	2622 independent reflections
Radiation source: sealed tube	2581 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 62.5°, θmin = 5.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.790, Tmax = 0.835	k = −15→15
6410 measured reflections	l = −15→11

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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089	w = 1/[σ2(Fo2) + (0.062P)2 + 0.1924P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
2622 reflections	Δρmax = 0.22 e Å−3
317 parameters	Δρmin = −0.22 e Å−3
0 restraints	Absolute structure: Flack (1983), 1609 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (17)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.26498 (14)	0.14479 (8)	0.64508 (8)	0.0226 (3)
H1O1	0.266 (3)	0.2024 (19)	0.6146 (17)	0.045 (6)*
O2	0.25865 (15)	0.33763 (7)	0.66855 (7)	0.0248 (3)
O3	0.24268 (12)	0.46642 (8)	1.11130 (7)	0.0158 (2)
H1O3	0.247 (3)	0.530 (2)	1.1204 (17)	0.048 (6)*
O4	0.25736 (13)	0.27211 (7)	1.09810 (8)	0.0182 (3)
H1O4	0.257 (3)	0.3146 (19)	1.1402 (19)	0.049 (7)*
C1	0.14780 (17)	0.11004 (11)	0.98596 (11)	0.0173 (3)
H1A	0.188 (2)	0.1027 (15)	1.0541 (15)	0.028 (5)*
H1B	0.068 (2)	0.1522 (15)	0.9886 (15)	0.026 (5)*
C2	0.09572 (16)	0.00499 (11)	0.95493 (11)	0.0183 (3)
H2A	0.065 (2)	−0.0370 (17)	1.0113 (16)	0.034 (5)*
H2B	0.013 (2)	0.0121 (13)	0.9127 (14)	0.023 (4)*
C3	0.20793 (16)	−0.05336 (11)	0.89923 (11)	0.0161 (3)
H3A	0.1764 (18)	−0.1257 (14)	0.8862 (12)	0.016 (4)*
H3B	0.291 (2)	−0.0611 (15)	0.9379 (15)	0.026 (5)*
C4	0.24229 (18)	−0.00042 (10)	0.80241 (10)	0.0157 (3)
C5	0.24927 (16)	0.11556 (10)	0.81588 (11)	0.0134 (3)
C6	0.25717 (17)	0.17835 (11)	0.73906 (10)	0.0166 (3)
C7	0.25656 (17)	0.28940 (11)	0.74620 (10)	0.0165 (3)
C8	0.25203 (16)	0.33638 (10)	0.84151 (10)	0.0137 (3)
C9	0.25196 (14)	0.27429 (10)	0.92394 (10)	0.0125 (3)
C10	0.26072 (15)	0.15823 (10)	0.91813 (10)	0.0134 (3)
C11	0.25250 (15)	0.32477 (11)	1.01271 (10)	0.0128 (3)
C12	0.24735 (15)	0.43145 (11)	1.01817 (9)	0.0127 (3)
C13	0.24955 (15)	0.49239 (10)	0.93545 (10)	0.0134 (3)
C14	0.25173 (16)	0.44233 (10)	0.84755 (10)	0.0144 (3)
H14A	0.257 (2)	0.4837 (13)	0.7891 (12)	0.017 (4)*
C15	0.24936 (17)	0.60773 (10)	0.94334 (10)	0.0157 (3)
H15A	0.3062	0.6260	1.0000	0.019*
C16	0.3152 (2)	0.65897 (12)	0.85566 (14)	0.0298 (4)
H16A	0.412 (2)	0.6255 (18)	0.8398 (18)	0.050 (7)*
H16B	0.3240 (19)	0.7331 (16)	0.8679 (15)	0.029 (5)*
H16C	0.255 (2)	0.6499 (16)	0.8008 (16)	0.036 (5)*
C17	0.09970 (16)	0.64673 (11)	0.96111 (13)	0.0218 (4)
H17A	0.059 (2)	0.6171 (15)	1.0234 (16)	0.030 (5)*
H17B	0.039 (2)	0.6260 (16)	0.9072 (16)	0.034 (5)*
H17C	0.0999 (18)	0.7216 (14)	0.9708 (13)	0.021 (4)*
C18	0.38294 (17)	−0.04049 (11)	0.76212 (12)	0.0187 (3)
H18A	0.461 (2)	−0.0244 (14)	0.8056 (14)	0.023 (4)*
H18B	0.4045 (19)	−0.0088 (14)	0.6976 (13)	0.021 (4)*
H18C	0.3732 (19)	−0.1131 (16)	0.7533 (14)	0.024 (5)*
C19	0.12291 (17)	−0.02847 (12)	0.73087 (12)	0.0210 (4)
H19A	0.138 (2)	0.0003 (14)	0.6670 (14)	0.026 (5)*
H19B	0.028 (2)	−0.0059 (14)	0.7535 (15)	0.029 (5)*
H19C	0.1167 (18)	−0.1038 (14)	0.7267 (13)	0.017 (4)*
C20	0.41254 (15)	0.13291 (11)	0.95429 (11)	0.0159 (3)
H20A	0.481 (2)	0.1651 (14)	0.9128 (15)	0.026 (5)*
H20B	0.4291 (18)	0.0620 (15)	0.9528 (13)	0.021 (4)*
H20C	0.425 (2)	0.1618 (14)	1.0211 (15)	0.028 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0463 (7)	0.0115 (5)	0.0101 (5)	0.0010 (5)	0.0012 (5)	−0.0010 (4)
O2	0.0506 (7)	0.0120 (5)	0.0117 (5)	0.0003 (5)	0.0000 (5)	0.0024 (4)
O3	0.0281 (6)	0.0087 (5)	0.0106 (5)	−0.0025 (5)	0.0021 (4)	−0.0030 (4)
O4	0.0331 (6)	0.0110 (5)	0.0104 (5)	−0.0001 (5)	−0.0017 (5)	0.0004 (4)
C1	0.0216 (8)	0.0100 (7)	0.0203 (8)	0.0003 (6)	0.0057 (6)	0.0015 (6)
C2	0.0203 (8)	0.0157 (7)	0.0187 (7)	−0.0018 (6)	0.0050 (6)	0.0034 (6)
C3	0.0206 (7)	0.0095 (7)	0.0181 (8)	−0.0006 (5)	−0.0007 (6)	−0.0005 (6)
C4	0.0212 (7)	0.0117 (7)	0.0143 (7)	0.0001 (6)	0.0000 (6)	−0.0013 (5)
C5	0.0139 (7)	0.0109 (7)	0.0154 (7)	0.0012 (6)	−0.0008 (6)	−0.0002 (5)
C6	0.0239 (8)	0.0129 (7)	0.0129 (7)	0.0011 (6)	0.0004 (6)	−0.0022 (5)
C7	0.0248 (8)	0.0121 (7)	0.0125 (7)	−0.0001 (7)	−0.0012 (6)	0.0014 (5)
C8	0.0156 (7)	0.0135 (7)	0.0122 (7)	−0.0001 (6)	−0.0005 (6)	0.0002 (5)
C9	0.0111 (7)	0.0120 (7)	0.0142 (7)	0.0002 (5)	−0.0012 (6)	0.0005 (5)
C10	0.0165 (7)	0.0119 (7)	0.0120 (7)	0.0009 (6)	0.0016 (6)	0.0005 (6)
C11	0.0145 (7)	0.0114 (7)	0.0124 (7)	−0.0001 (6)	0.0004 (6)	0.0013 (5)
C12	0.0143 (7)	0.0130 (7)	0.0109 (7)	−0.0011 (6)	−0.0001 (6)	−0.0021 (5)
C13	0.0136 (6)	0.0110 (7)	0.0156 (7)	−0.0003 (6)	0.0011 (6)	0.0015 (5)
C14	0.0193 (7)	0.0112 (6)	0.0127 (7)	0.0005 (6)	0.0004 (6)	0.0014 (6)
C15	0.0245 (8)	0.0087 (7)	0.0139 (7)	−0.0007 (6)	−0.0013 (6)	−0.0016 (5)
C16	0.0545 (12)	0.0102 (8)	0.0247 (9)	0.0006 (8)	0.0132 (9)	−0.0004 (7)
C17	0.0255 (8)	0.0122 (7)	0.0277 (9)	0.0021 (7)	−0.0027 (7)	−0.0010 (7)
C18	0.0243 (8)	0.0116 (7)	0.0200 (8)	0.0024 (6)	0.0030 (7)	0.0005 (6)
C19	0.0273 (9)	0.0148 (8)	0.0208 (8)	−0.0025 (7)	−0.0050 (7)	−0.0025 (6)
C20	0.0194 (7)	0.0106 (7)	0.0177 (7)	0.0018 (6)	−0.0036 (6)	−0.0010 (6)

O1—C6	1.3732 (17)	C9—C11	1.394 (2)
O1—H1O1	0.87 (3)	C9—C10	1.5327 (18)
O2—C7	1.2465 (18)	C10—C20	1.561 (2)
O3—C12	1.3669 (16)	C11—C12	1.408 (2)
O3—H1O3	0.85 (3)	C12—C13	1.3962 (19)
O4—C11	1.3688 (16)	C13—C14	1.381 (2)
O4—H1O4	0.81 (3)	C13—C15	1.5228 (17)
C1—C2	1.530 (2)	C14—H14A	0.975 (18)
C1—C10	1.558 (2)	C15—C16	1.520 (2)
C1—H1A	1.02 (2)	C15—C17	1.530 (2)
C1—H1B	0.94 (2)	C15—H15A	0.9800
C2—C3	1.522 (2)	C16—H16A	1.04 (2)
C2—H2A	1.00 (2)	C16—H16B	0.99 (2)
C2—H2B	0.99 (2)	C16—H16C	0.96 (2)
C3—C4	1.543 (2)	C17—H17A	1.02 (2)
C3—H3A	1.014 (19)	C17—H17B	0.98 (2)
C3—H3B	0.96 (2)	C17—H17C	0.996 (18)
C4—C18	1.540 (2)	C18—H18A	0.98 (2)
C4—C5	1.5399 (18)	C18—H18B	1.005 (19)
C4—C19	1.548 (2)	C18—H18C	0.97 (2)
C5—C6	1.347 (2)	C19—H19A	0.970 (19)
C5—C10	1.5236 (19)	C19—H19B	1.00 (2)
C6—C7	1.4656 (19)	C19—H19C	0.995 (18)
C7—C8	1.455 (2)	C20—H20A	0.97 (2)
C8—C14	1.3978 (19)	C20—H20B	0.947 (19)
C8—C9	1.4016 (19)	C20—H20C	1.00 (2)
C6—O1—H1O1	100.3 (15)	O4—C11—C9	121.07 (12)
C12—O3—H1O3	118.0 (16)	O4—C11—C12	117.42 (12)
C11—O4—H1O4	105.7 (17)	C9—C11—C12	121.51 (12)
C2—C1—C10	114.96 (12)	O3—C12—C13	125.22 (12)
C2—C1—H1A	107.1 (11)	O3—C12—C11	112.81 (12)
C10—C1—H1A	109.4 (11)	C13—C12—C11	121.96 (12)
C2—C1—H1B	106.5 (12)	C14—C13—C12	116.42 (13)
C10—C1—H1B	109.7 (12)	C14—C13—C15	122.60 (13)
H1A—C1—H1B	108.9 (17)	C12—C13—C15	120.98 (12)
C3—C2—C1	111.83 (12)	C13—C14—C8	121.92 (13)
C3—C2—H2A	108.6 (12)	C13—C14—H14A	117.5 (10)
C1—C2—H2A	112.2 (12)	C8—C14—H14A	120.6 (10)
C3—C2—H2B	108.0 (10)	C16—C15—C13	112.65 (12)
C1—C2—H2B	109.8 (11)	C16—C15—C17	111.12 (14)
H2A—C2—H2B	106.2 (16)	C13—C15—C17	110.32 (13)
C2—C3—C4	110.96 (12)	C16—C15—H15A	107.5
C2—C3—H3A	111.0 (10)	C13—C15—H15A	107.5
C4—C3—H3A	109.4 (10)	C17—C15—H15A	107.5
C2—C3—H3B	110.3 (12)	C15—C16—H16A	110.0 (13)
C4—C3—H3B	110.9 (12)	C15—C16—H16B	109.6 (12)
H3A—C3—H3B	104.0 (15)	H16A—C16—H16B	112.1 (16)
C18—C4—C5	110.26 (13)	C15—C16—H16C	109.2 (13)
C18—C4—C3	109.98 (12)	H16A—C16—H16C	108.0 (18)
C5—C4—C3	110.64 (12)	H16B—C16—H16C	107.9 (17)
C18—C4—C19	108.79 (12)	C15—C17—H17A	110.9 (11)
C5—C4—C19	110.20 (12)	C15—C17—H17B	109.4 (12)
C3—C4—C19	106.89 (12)	H17A—C17—H17B	108.1 (16)
C6—C5—C10	119.96 (12)	C15—C17—H17C	110.6 (10)
C6—C5—C4	121.06 (13)	H17A—C17—H17C	105.5 (15)
C10—C5—C4	118.74 (12)	H17B—C17—H17C	112.2 (16)
C5—C6—O1	123.36 (13)	C4—C18—H18A	111.3 (11)
C5—C6—C7	124.01 (13)	C4—C18—H18B	110.8 (10)
O1—C6—C7	112.63 (12)	H18A—C18—H18B	107.4 (15)
O2—C7—C8	124.20 (12)	C4—C18—H18C	107.5 (11)
O2—C7—C6	116.78 (12)	H18A—C18—H18C	111.3 (16)
C8—C7—C6	119.02 (12)	H18B—C18—H18C	108.5 (16)
C14—C8—C9	122.27 (12)	C4—C19—H19A	112.3 (11)
C14—C8—C7	118.58 (12)	C4—C19—H19B	113.0 (12)
C9—C8—C7	119.13 (12)	H19A—C19—H19B	107.5 (16)
C11—C9—C8	115.85 (12)	C4—C19—H19C	108.5 (10)
C11—C9—C10	121.41 (12)	H19A—C19—H19C	110.1 (15)
C8—C9—C10	122.62 (12)	H19B—C19—H19C	105.1 (14)
C5—C10—C9	114.36 (11)	C10—C20—H20A	109.9 (11)
C5—C10—C1	110.97 (12)	C10—C20—H20B	110.9 (11)
C9—C10—C1	109.71 (12)	H20A—C20—H20B	107.8 (15)
C5—C10—C20	106.47 (12)	C10—C20—H20C	108.6 (11)
C9—C10—C20	104.26 (12)	H20A—C20—H20C	107.5 (16)
C1—C10—C20	110.82 (11)	H20B—C20—H20C	112.0 (16)
C10—C1—C2—C3	28.97 (17)	C6—C5—C10—C20	−103.23 (16)
C1—C2—C3—C4	−64.94 (16)	C4—C5—C10—C20	71.28 (16)
C2—C3—C4—C18	163.23 (12)	C11—C9—C10—C5	176.24 (12)
C2—C3—C4—C5	41.17 (16)	C8—C9—C10—C5	−7.9 (2)
C2—C3—C4—C19	−78.83 (15)	C11—C9—C10—C1	50.82 (18)
C18—C4—C5—C6	67.99 (19)	C8—C9—C10—C1	−133.35 (13)
C3—C4—C5—C6	−170.13 (14)	C11—C9—C10—C20	−67.90 (16)
C19—C4—C5—C6	−52.1 (2)	C8—C9—C10—C20	107.93 (15)
C18—C4—C5—C10	−106.46 (15)	C2—C1—C10—C5	25.05 (17)
C3—C4—C5—C10	15.42 (19)	C2—C1—C10—C9	152.39 (13)
C19—C4—C5—C10	133.43 (14)	C2—C1—C10—C20	−93.02 (15)
C10—C5—C6—O1	171.82 (14)	C8—C9—C11—O4	−177.74 (13)
C4—C5—C6—O1	−2.6 (2)	C10—C9—C11—O4	−1.6 (2)
C10—C5—C6—C7	−9.0 (2)	C8—C9—C11—C12	2.6 (2)
C4—C5—C6—C7	176.61 (15)	C10—C9—C11—C12	178.69 (13)
C5—C6—C7—O2	−177.13 (14)	O4—C11—C12—O3	−2.3 (2)
O1—C6—C7—O2	2.1 (2)	C9—C11—C12—O3	177.35 (13)
C5—C6—C7—C8	2.2 (3)	O4—C11—C12—C13	176.60 (12)
O1—C6—C7—C8	−178.55 (12)	C9—C11—C12—C13	−3.7 (2)
O2—C7—C8—C14	−0.8 (2)	O3—C12—C13—C14	−178.86 (14)
C6—C7—C8—C14	179.89 (14)	C11—C12—C13—C14	2.3 (2)
O2—C7—C8—C9	−179.14 (16)	O3—C12—C13—C15	1.1 (2)
C6—C7—C8—C9	1.6 (2)	C11—C12—C13—C15	−177.71 (13)
C14—C8—C9—C11	−0.4 (2)	C12—C13—C14—C8	−0.1 (2)
C7—C8—C9—C11	177.83 (14)	C15—C13—C14—C8	179.93 (14)
C14—C8—C9—C10	−176.45 (13)	C9—C8—C14—C13	−0.8 (2)
C7—C8—C9—C10	1.8 (2)	C7—C8—C14—C13	−179.08 (14)
C6—C5—C10—C9	11.3 (2)	C14—C13—C15—C16	−25.5 (2)
C4—C5—C10—C9	−174.14 (12)	C12—C13—C15—C16	154.57 (15)
C6—C5—C10—C1	136.09 (15)	C14—C13—C15—C17	99.31 (17)
C4—C5—C10—C1	−49.39 (18)	C12—C13—C15—C17	−80.62 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2	0.87 (2)	1.93 (2)	2.5607 (14)	128 (2)
O3—H1O3···O2i	0.85 (3)	1.87 (3)	2.6988 (14)	167 (2)
O4—H1O4···O3	0.81 (3)	2.04 (3)	2.5690 (14)	123 (2)
C14—H14A···O3ii	0.975 (17)	2.542 (17)	3.4774 (17)	160.8 (14)
C15—H15A···O2i	0.98	2.45	3.1933 (17)	132
C18—H18B···O1	1.005 (18)	2.524 (18)	3.1335 (19)	118.7 (13)
C19—H19A···O1	0.971 (19)	2.273 (19)	2.903 (2)	121.7 (14)
C20—H20C···O4	1.01 (2)	2.403 (19)	3.0779 (18)	123.9 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2	0.87 (2)	1.93 (2)	2.5607 (14)	128 (2)
O3—H1O3⋯O2i	0.85 (3)	1.87 (3)	2.6988 (14)	167 (2)
O4—H1O4⋯O3	0.81 (3)	2.04 (3)	2.5690 (14)	123 (2)
C14—H14A⋯O3ii	0.975 (17)	2.542 (17)	3.4774 (17)	160.8 (14)
C15—H15A⋯O2i	0.98	2.45	3.1933 (17)	132
C18—H18B⋯O1	1.005 (18)	2.524 (18)	3.1335 (19)	118.7 (13)
C19—H19A⋯O1	0.971 (19)	2.273 (19)	2.903 (2)	121.7 (14)
C20—H20C⋯O4	1.01 (2)	2.403 (19)	3.0779 (18)	123.9 (14)

Symmetry codes: (i) ; (ii) .