Redetermination and absolute configuration of 7α-hy-droxy-royleanone.

THE TITLE COMPOUND [SYSTEMATIC NAME: 7α,12-dihy-droxy-8,12-abietadiene,11,14-dione or (4bS,8aS,10R)-3,10-dihy-droxy-2-isopropyl-4b,8,8-trimethyl-1,4,4b,5,6,7,8,8a,9,10-deca-hydro-phenanthrene-1,4-dione], C(20)H(28)O(4), is an abietane diterpen-oid, which was isolated from the roots of Premna obtusifolia (Verbenaceae). Its crystal structure has been reported previously [Chen et al. (2000 ▶). Jiegou Huaxue, 19, 122-125], but the absolute configuration could not be determined using data collected with Mo radiation. This redetermination using Cu radiation shows the the absolute configurations of the stereogenic centres at positions 4b, 8a and 10 to be S, S and R, respectively. Two intra-molecular O-H⋯O hydrogen bonds [one generating an S(5) ring and one generating an S(6) ring] and a number of short C-H⋯O contacts occur. In the crystal, mol-ecules are linked into infinite chains propagating in [100] by O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions.

Related literature

For background to Verbenaceae, diterpenes and their biological activity, see: Batista et al. (1994 ▶); Bunluepuech & Tewtrakul (2009 ▶); Jonathan et al. (1989 ▶); Kabouche et al. (2007 ▶); Kupchan et al. (1968 ▶, 1969 ▶); Nagy et al. (1999 ▶); Ulubelen et al. (2001 ▶). For the previous structure determination, see: Chen et al. (2000 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶) and for ring conformations, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C20H28O4

M = 332.42

Orthorhombic,

a = 7.6729 (1) Å

b = 9.3972 (1) Å

c = 24.1946 (3) Å

V = 1744.52 (4) Å3

Z = 4

Cu Kα radiation

μ = 0.70 mm−1

T = 100 K

0.28 × 0.28 × 0.20 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.829, T max = 0.871

6475 measured reflections

2578 independent reflections

2564 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.074

S = 1.04

2578 reflections

230 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.13 e Å−3

Absolute structure: Flack (1983 ▶), 970 Friedel pairs

Flack parameter: 0.13 (16)

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/S1600536810020544/hb5468sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020544/hb5468Isup2.hkl

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

C20H28O4	F(000) = 720
Mr = 332.42	Dx = 1.266 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2578 reflections
a = 7.6729 (1) Å	θ = 5.1–62.5°
b = 9.3972 (1) Å	µ = 0.70 mm−1
c = 24.1946 (3) Å	T = 100 K
V = 1744.52 (4) Å3	Block, yellow
Z = 4	0.28 × 0.28 × 0.20 mm

Bruker APEXII DUO CCD diffractometer	2578 independent reflections
Radiation source: sealed tube	2564 reflections with I > 2σ(I)
graphite	Rint = 0.015
φ and ω scans	θmax = 62.5°, θmin = 5.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→8
Tmin = 0.829, Tmax = 0.871	k = −10→10
6475 measured reflections	l = −27→27

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0454P)2 + 0.3997P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2578 reflections	Δρmax = 0.22 e Å−3
230 parameters	Δρmin = −0.12 e Å−3
0 restraints	Absolute structure: Flack (1983), 970 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.13 (16)

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	0.39089 (14)	0.84016 (12)	0.26305 (4)	0.0253 (3)
H1O1	0.310 (3)	0.830 (3)	0.2374 (11)	0.077 (9)*
O2	1.09134 (13)	0.67838 (11)	0.21951 (4)	0.0216 (2)
O3	1.04729 (13)	0.73182 (11)	0.11546 (4)	0.0209 (2)
H1O3	1.132 (3)	0.720 (2)	0.1363 (8)	0.040 (6)*
O4	0.44447 (13)	0.73046 (14)	0.15053 (4)	0.0300 (3)
C1	0.98219 (19)	0.80709 (16)	0.32516 (6)	0.0198 (3)
H1A	1.0903	0.7775	0.3079	0.024*
H1B	0.9519	0.9001	0.3106	0.024*
C2	1.00975 (19)	0.81849 (16)	0.38772 (6)	0.0228 (3)
H2A	1.0508	0.7278	0.4018	0.027*
H2B	1.0988	0.8892	0.3952	0.027*
C3	0.8428 (2)	0.85964 (17)	0.41773 (6)	0.0233 (3)
H3A	0.8124	0.9564	0.4076	0.028*
H3B	0.8648	0.8584	0.4572	0.028*
C4	0.68635 (19)	0.76239 (16)	0.40536 (6)	0.0204 (3)
C5	0.66970 (18)	0.74674 (15)	0.34161 (5)	0.0173 (3)
H5A	0.6466	0.8435	0.3284	0.021*
C6	0.51347 (18)	0.66017 (16)	0.32182 (6)	0.0199 (3)
H6A	0.5401	0.5594	0.3239	0.024*
H6B	0.4137	0.6790	0.3453	0.024*
C7	0.47085 (18)	0.70050 (16)	0.26259 (6)	0.0200 (3)
H7A	0.3897	0.6310	0.2468	0.024*
C8	0.63225 (18)	0.70964 (15)	0.22719 (6)	0.0181 (3)
C9	0.79457 (18)	0.70681 (15)	0.24799 (5)	0.0158 (3)
C10	0.83719 (18)	0.70011 (15)	0.31011 (6)	0.0169 (3)
C11	0.93920 (17)	0.70252 (15)	0.20709 (6)	0.0171 (3)
C12	0.90331 (18)	0.72713 (15)	0.14720 (6)	0.0168 (3)
C13	0.74123 (19)	0.74250 (15)	0.12654 (6)	0.0182 (3)
C14	0.59663 (18)	0.72713 (15)	0.16633 (6)	0.0188 (3)
C15	0.70086 (18)	0.77406 (17)	0.06671 (6)	0.0211 (3)
H15A	0.5738	0.7793	0.0632	0.025*
C16	0.7741 (2)	0.91900 (17)	0.04969 (7)	0.0285 (4)
H16A	0.7297	0.9912	0.0740	0.043*
H16B	0.7397	0.9398	0.0124	0.043*
H16C	0.8990	0.9169	0.0520	0.043*
C17	0.7642 (2)	0.65721 (17)	0.02752 (6)	0.0260 (4)
H17A	0.7154	0.5675	0.0386	0.039*
H17B	0.8890	0.6519	0.0289	0.039*
H17C	0.7278	0.6789	−0.0095	0.039*
C18	0.5232 (2)	0.83806 (18)	0.42719 (6)	0.0266 (3)
H18A	0.5417	0.8660	0.4649	0.040*
H18B	0.4253	0.7746	0.4252	0.040*
H18C	0.5004	0.9209	0.4051	0.040*
C19	0.7033 (2)	0.62112 (17)	0.43667 (6)	0.0248 (3)
H19A	0.6847	0.6372	0.4754	0.037*
H19B	0.8178	0.5827	0.4310	0.037*
H19C	0.6179	0.5551	0.4231	0.037*
C20	0.8991 (2)	0.54667 (15)	0.32229 (6)	0.0202 (3)
H20A	0.9797	0.5171	0.2942	0.030*
H20B	0.8005	0.4838	0.3225	0.030*
H20C	0.9554	0.5439	0.3577	0.030*

	U11	U22	U33	U12	U13	U23
O1	0.0192 (5)	0.0318 (6)	0.0248 (5)	0.0057 (5)	−0.0006 (5)	0.0037 (5)
O2	0.0130 (5)	0.0305 (6)	0.0214 (5)	0.0023 (4)	−0.0010 (4)	−0.0002 (5)
O3	0.0147 (5)	0.0290 (6)	0.0191 (5)	0.0004 (5)	0.0017 (4)	−0.0021 (5)
O4	0.0148 (5)	0.0531 (7)	0.0221 (5)	−0.0006 (5)	−0.0031 (4)	0.0068 (5)
C1	0.0162 (7)	0.0237 (7)	0.0194 (7)	−0.0028 (6)	0.0004 (6)	−0.0023 (6)
C2	0.0203 (7)	0.0257 (7)	0.0224 (7)	−0.0049 (7)	−0.0038 (6)	−0.0034 (6)
C3	0.0261 (8)	0.0248 (8)	0.0190 (7)	0.0001 (7)	−0.0014 (7)	−0.0037 (6)
C4	0.0194 (7)	0.0250 (8)	0.0168 (7)	0.0035 (6)	0.0000 (6)	0.0000 (6)
C5	0.0167 (7)	0.0185 (7)	0.0165 (6)	0.0012 (6)	−0.0003 (6)	0.0031 (6)
C6	0.0159 (7)	0.0256 (7)	0.0183 (7)	−0.0006 (6)	0.0021 (6)	0.0016 (6)
C7	0.0142 (6)	0.0268 (7)	0.0189 (7)	−0.0002 (7)	−0.0001 (6)	0.0019 (6)
C8	0.0168 (7)	0.0183 (7)	0.0192 (7)	−0.0001 (6)	−0.0008 (6)	0.0000 (6)
C9	0.0160 (7)	0.0140 (6)	0.0173 (7)	0.0003 (6)	0.0000 (6)	0.0010 (6)
C10	0.0138 (6)	0.0193 (7)	0.0177 (6)	0.0001 (6)	−0.0003 (6)	0.0003 (6)
C11	0.0160 (7)	0.0149 (7)	0.0205 (7)	−0.0008 (6)	−0.0005 (6)	−0.0026 (5)
C12	0.0163 (7)	0.0163 (6)	0.0178 (7)	−0.0003 (6)	0.0028 (6)	−0.0030 (6)
C13	0.0176 (7)	0.0184 (7)	0.0186 (7)	−0.0004 (6)	0.0007 (6)	−0.0023 (6)
C14	0.0159 (7)	0.0207 (7)	0.0198 (7)	0.0012 (6)	−0.0017 (6)	−0.0002 (6)
C15	0.0169 (7)	0.0291 (8)	0.0174 (7)	−0.0006 (7)	−0.0012 (6)	0.0005 (6)
C16	0.0341 (9)	0.0277 (8)	0.0237 (7)	0.0022 (8)	−0.0033 (7)	0.0057 (7)
C17	0.0295 (8)	0.0317 (8)	0.0169 (7)	−0.0059 (8)	0.0004 (7)	−0.0019 (6)
C18	0.0247 (8)	0.0348 (8)	0.0204 (7)	0.0048 (7)	0.0022 (6)	0.0003 (7)
C19	0.0257 (8)	0.0315 (8)	0.0171 (7)	−0.0025 (7)	−0.0007 (7)	0.0039 (6)
C20	0.0195 (7)	0.0211 (7)	0.0199 (7)	0.0019 (6)	−0.0028 (6)	−0.0007 (6)

O1—C7	1.4488 (18)	C8—C9	1.344 (2)
O1—H1O1	0.88 (3)	C8—C14	1.5066 (19)
O2—C11	1.2266 (17)	C9—C11	1.4874 (19)
O3—C12	1.3461 (17)	C9—C10	1.5394 (18)
O3—H1O3	0.83 (2)	C10—C20	1.546 (2)
O4—C14	1.2288 (18)	C11—C12	1.4931 (19)
C1—C2	1.5322 (19)	C12—C13	1.348 (2)
C1—C10	1.543 (2)	C13—C14	1.476 (2)
C1—H1A	0.9700	C13—C15	1.5098 (19)
C1—H1B	0.9700	C15—C17	1.530 (2)
C2—C3	1.522 (2)	C15—C16	1.530 (2)
C2—H2A	0.9700	C15—H15A	0.9800
C2—H2B	0.9700	C16—H16A	0.9600
C3—C4	1.538 (2)	C16—H16B	0.9600
C3—H3A	0.9700	C16—H16C	0.9600
C3—H3B	0.9700	C17—H17A	0.9600
C4—C18	1.534 (2)	C17—H17B	0.9600
C4—C19	1.534 (2)	C17—H17C	0.9600
C4—C5	1.5547 (18)	C18—H18A	0.9600
C5—C6	1.526 (2)	C18—H18B	0.9600
C5—C10	1.5570 (19)	C18—H18C	0.9600
C5—H5A	0.9800	C19—H19A	0.9600
C6—C7	1.5178 (19)	C19—H19B	0.9600
C6—H6A	0.9700	C19—H19C	0.9600
C6—H6B	0.9700	C20—H20A	0.9600
C7—C8	1.5082 (19)	C20—H20B	0.9600
C7—H7A	0.9800	C20—H20C	0.9600
C7—O1—H1O1	101.4 (19)	C1—C10—C20	109.94 (11)
C12—O3—H1O3	107.0 (14)	C9—C10—C5	106.92 (11)
C2—C1—C10	112.22 (12)	C1—C10—C5	107.24 (11)
C2—C1—H1A	109.2	C20—C10—C5	115.00 (12)
C10—C1—H1A	109.2	O2—C11—C9	123.52 (13)
C2—C1—H1B	109.2	O2—C11—C12	116.22 (13)
C10—C1—H1B	109.2	C9—C11—C12	120.26 (12)
H1A—C1—H1B	107.9	O3—C12—C13	122.83 (12)
C3—C2—C1	111.88 (12)	O3—C12—C11	114.03 (12)
C3—C2—H2A	109.2	C13—C12—C11	123.13 (12)
C1—C2—H2A	109.2	C12—C13—C14	116.18 (12)
C3—C2—H2B	109.2	C12—C13—C15	124.46 (13)
C1—C2—H2B	109.2	C14—C13—C15	119.36 (13)
H2A—C2—H2B	107.9	O4—C14—C13	120.59 (13)
C2—C3—C4	114.40 (12)	O4—C14—C8	118.62 (13)
C2—C3—H3A	108.7	C13—C14—C8	120.78 (12)
C4—C3—H3A	108.7	C13—C15—C17	112.84 (12)
C2—C3—H3B	108.7	C13—C15—C16	110.95 (12)
C4—C3—H3B	108.7	C17—C15—C16	110.82 (12)
H3A—C3—H3B	107.6	C13—C15—H15A	107.3
C18—C4—C19	107.48 (12)	C17—C15—H15A	107.3
C18—C4—C3	107.13 (12)	C16—C15—H15A	107.3
C19—C4—C3	110.61 (12)	C15—C16—H16A	109.5
C18—C4—C5	108.58 (11)	C15—C16—H16B	109.5
C19—C4—C5	114.52 (12)	H16A—C16—H16B	109.5
C3—C4—C5	108.26 (11)	C15—C16—H16C	109.5
C6—C5—C4	115.24 (11)	H16A—C16—H16C	109.5
C6—C5—C10	110.17 (11)	H16B—C16—H16C	109.5
C4—C5—C10	116.38 (11)	C15—C17—H17A	109.5
C6—C5—H5A	104.5	C15—C17—H17B	109.5
C4—C5—H5A	104.5	H17A—C17—H17B	109.5
C10—C5—H5A	104.5	C15—C17—H17C	109.5
C7—C6—C5	109.42 (12)	H17A—C17—H17C	109.5
C7—C6—H6A	109.8	H17B—C17—H17C	109.5
C5—C6—H6A	109.8	C4—C18—H18A	109.5
C7—C6—H6B	109.8	C4—C18—H18B	109.5
C5—C6—H6B	109.8	H18A—C18—H18B	109.5
H6A—C6—H6B	108.2	C4—C18—H18C	109.5
O1—C7—C8	107.49 (11)	H18A—C18—H18C	109.5
O1—C7—C6	108.07 (12)	H18B—C18—H18C	109.5
C8—C7—C6	111.93 (12)	C4—C19—H19A	109.5
O1—C7—H7A	109.8	C4—C19—H19B	109.5
C8—C7—H7A	109.8	H19A—C19—H19B	109.5
C6—C7—H7A	109.8	C4—C19—H19C	109.5
C9—C8—C14	122.44 (12)	H19A—C19—H19C	109.5
C9—C8—C7	123.18 (12)	H19B—C19—H19C	109.5
C14—C8—C7	114.35 (12)	C10—C20—H20A	109.5
C8—C9—C11	116.29 (12)	C10—C20—H20B	109.5
C8—C9—C10	124.29 (12)	H20A—C20—H20B	109.5
C11—C9—C10	119.34 (12)	C10—C20—H20C	109.5
C9—C10—C1	110.91 (11)	H20A—C20—H20C	109.5
C9—C10—C20	106.82 (12)	H20B—C20—H20C	109.5
C10—C1—C2—C3	−56.85 (16)	C2—C1—C10—C5	55.46 (15)
C1—C2—C3—C4	54.11 (17)	C6—C5—C10—C9	52.09 (15)
C2—C3—C4—C18	−166.79 (12)	C4—C5—C10—C9	−174.34 (12)
C2—C3—C4—C19	76.36 (15)	C6—C5—C10—C1	171.09 (11)
C2—C3—C4—C5	−49.87 (16)	C4—C5—C10—C1	−55.33 (16)
C18—C4—C5—C6	−60.53 (17)	C6—C5—C10—C20	−66.31 (15)
C19—C4—C5—C6	59.57 (16)	C4—C5—C10—C20	67.26 (16)
C3—C4—C5—C6	−176.51 (12)	C8—C9—C11—O2	−168.73 (14)
C18—C4—C5—C10	168.22 (12)	C10—C9—C11—O2	8.2 (2)
C19—C4—C5—C10	−71.68 (16)	C8—C9—C11—C12	10.76 (19)
C3—C4—C5—C10	52.23 (16)	C10—C9—C11—C12	−172.31 (12)
C4—C5—C6—C7	157.64 (12)	O2—C11—C12—O3	−5.63 (19)
C10—C5—C6—C7	−68.21 (14)	C9—C11—C12—O3	174.85 (12)
C5—C6—C7—O1	−73.43 (14)	O2—C11—C12—C13	174.01 (13)
C5—C6—C7—C8	44.75 (16)	C9—C11—C12—C13	−5.5 (2)
O1—C7—C8—C9	107.73 (15)	O3—C12—C13—C14	176.88 (13)
C6—C7—C8—C9	−10.8 (2)	C11—C12—C13—C14	−2.7 (2)
O1—C7—C8—C14	−70.35 (15)	O3—C12—C13—C15	−3.3 (2)
C6—C7—C8—C14	171.12 (12)	C11—C12—C13—C15	177.11 (13)
C14—C8—C9—C11	−7.9 (2)	C12—C13—C14—O4	−175.35 (15)
C7—C8—C9—C11	174.19 (13)	C15—C13—C14—O4	4.8 (2)
C14—C8—C9—C10	175.36 (13)	C12—C13—C14—C8	5.73 (19)
C7—C8—C9—C10	−2.6 (2)	C15—C13—C14—C8	−174.11 (13)
C8—C9—C10—C1	−134.70 (14)	C9—C8—C14—O4	−179.11 (15)
C11—C9—C10—C1	48.64 (17)	C7—C8—C14—O4	−1.0 (2)
C8—C9—C10—C20	105.50 (16)	C9—C8—C14—C13	−0.2 (2)
C11—C9—C10—C20	−71.16 (15)	C7—C8—C14—C13	177.93 (13)
C8—C9—C10—C5	−18.10 (19)	C12—C13—C15—C17	61.75 (19)
C11—C9—C10—C5	165.24 (11)	C14—C13—C15—C17	−118.43 (14)
C2—C1—C10—C9	171.86 (12)	C12—C13—C15—C16	−63.29 (18)
C2—C1—C10—C20	−70.22 (15)	C14—C13—C15—C16	116.53 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2i	0.88 (2)	2.24 (3)	2.9502 (15)	137 (2)
O1—H1O1···O4	0.88 (2)	2.52 (3)	2.9399 (14)	109.8 (19)
O3—H1O3···O2	0.83 (2)	2.075 (19)	2.5892 (14)	119.8 (19)
O3—H1O3···O4ii	0.83 (2)	2.42 (2)	3.1635 (14)	148.8 (18)
C1—H1A···O2	0.97	2.33	2.9493 (18)	121
C5—H5A···O1	0.98	2.52	2.9933 (17)	110
C7—H7A···O2i	0.98	2.42	3.0998 (17)	126
C15—H15A···O4	0.98	2.38	2.8549 (17)	109
C16—H16C···O3	0.96	2.58	3.1654 (19)	119
C17—H17B···O3	0.96	2.53	3.1204 (18)	119
C20—H20A···O2	0.96	2.51	3.1451 (18)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2i	0.88 (2)	2.24 (3)	2.9502 (15)	137 (2)
O1—H1O1⋯O4	0.88 (2)	2.52 (3)	2.9399 (14)	109.8 (19)
O3—H1O3⋯O2	0.83 (2)	2.075 (19)	2.5892 (14)	119.8 (19)
O3—H1O3⋯O4ii	0.83 (2)	2.42 (2)	3.1635 (14)	148.8 (18)
C1—H1A⋯O2	0.97	2.33	2.9493 (18)	121
C5—H5A⋯O1	0.98	2.52	2.9933 (17)	110
C7—H7A⋯O2i	0.98	2.42	3.0998 (17)	126
C15—H15A⋯O4	0.98	2.38	2.8549 (17)	109
C16—H16C⋯O3	0.96	2.58	3.1654 (19)	119
C17—H17B⋯O3	0.96	2.53	3.1204 (18)	119
C20—H20A⋯O2	0.96	2.51	3.1451 (18)	124

Symmetry codes: (i) ; (ii) .