Crystal structure of 4α-hy­droxy-5α,8β(H)-eudesm-7(11)-en-8,12-olide monohydrate

Abstract

The title compound, C₁₅H₂₂O₃·H₂O, is a natural producr isolated from Chloranthus japonicus, which is a eudesmane sesquiterpenoid. The two trans-fused six-membered rings have chair confomations. In the crystal, O—H⋯O hydrogen bonds link the components into corrugated layers parallel to the bc plane. There are C—H⋯O inter­actions present within and between the layers.

Related literature  

For the products isolated from the genus Chloranthus, see: Xiao et al. (2010 ▸); Sun et al. (2012 ▸). For the crystal structure of the related compound 6β-hy­droxy­eremophil-7(11)-en-8β,12-olide, see: Su et al. (2011 ▸).

Experimental  

Crystal data  

• C₁₅H₂₂O₃·H₂O

• M _r = 268.34

• Monoclinic,

• a = 10.2495 (2) Å

• b = 7.1061 (1) Å

• c = 10.5275 (2) Å

• β = 100.026 (1)°

• V = 755.05 (2) ų

• Z = 2

• Cu Kα radiation

• μ = 0.68 mm⁻¹

• T = 298 K

• 0.40 × 0.40 × 0.30 mm

Data collection  

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002 ▸) T _min = 0.772, T _max = 0.821

• 3081 measured reflections

• 1339 independent reflections

• 1303 reflections with I > 2σ(I)

• R _int = 0.018

Refinement  

• R[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 0.130

• S = 1.14

• 1339 reflections

• 174 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 2002 ▸); cell refinement: SAINT (Bruker, 2002 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL; software used to prepare material for publication: ORTEP (Johnson & Burnett, 1996 ▸).

Supplementary Material

CCDC reference: 1405865

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C5H5O4i	0.98	2.63	3.407(3)	136
C8H8O3ii	0.98	2.64	3.308(4)	126
O1H1O4i	0.82	1.91	2.718(3)	169
O4H4WAO3ii	0.83	2.05	2.850(3)	162
O4H4WBO1iii	0.86	1.94	2.764(3)	159

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

S1. Comment

Chloranthus japonicus (Chloranthaceae,"yin-xian-cao"in chinese) is mainly distributed in the east of Asia and traditionally used as Chinese herbal medicine in the treatment of fractures, carbuncles, trauma, and rheumatism. In our current phytochemical investigation, the title compound - an eudesmane sesquiterpenoid, was isolated from the whole plant of C. japonicus for the first time.The compound was identified by NMR spectroscopic data, which were also elucidated by comparing with the literature data (Xiao et al., 2010). Herein, we report its crystal structure.

The main molecule of the title compound consists of a fused three-ring system (Fig.1). The two methyl groups attached to C4 and C10 and the H atom at C8 are all in the axial position and assigned β-configuration, whereas, the hy­droxy group at C4 site has α-orientation.

In the crystal, inter­molecular O—H···O hydrogen bonds (Table 1, Fig. 2) link all moeties into corrugated layers parallel to bc plane, and weak C—H···O inter­actions (Table 1) consolidate further the crystal packing.

S2. Experimental

The title compound was isolated from the whole plant of C. japonicus following the known procedure (Xiao et al., 2010).

S3. Refinement

The hydrogen atoms were placed in calculated positions and refined as riding with U_iso(H) =1.2 U_eq (C) or 1.5 U_eq(C, O). The positions of methyl and hy­droxy hydrogens were rotationally optimized.

Figures

Fig. 1.

Molecular structure of the title compound showing the atomic numbering and 40% probability displacement ellipsoids.

Fig. 2.

A portion of the crystal packing showing O—H···O hydrogen bonds as dashed lines.

Crystal data

C15H22O3·H2O	F(000) = 292
Mr = 268.34	Dx = 1.180 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 2390 reflections
a = 10.2495 (2) Å	θ = 4.3–66.9°
b = 7.1061 (1) Å	µ = 0.68 mm−1
c = 10.5275 (2) Å	T = 298 K
β = 100.026 (1)°	Block, colourless
V = 755.05 (2) Å3	0.40 × 0.40 × 0.30 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1339 independent reflections
Radiation source: fine-focus sealed tube	1303 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
phi and ω scans	θmax = 64.0°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
Tmin = 0.772, Tmax = 0.821	k = −6→8
3081 measured reflections	l = −11→12

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.18	w = 1/[σ2(Fo2) + (0.092P)2 + 0.043P] where P = (Fo2 + 2Fc2)/3
1339 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.22 e Å−3
1 restraint	Δρmin = −0.34 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.0506 (3)	−0.0853 (6)	0.6719 (3)	0.0694 (9)
H1A	−0.0282	−0.0510	0.6111	0.083*
H1B	0.0885	−0.1959	0.6384	0.083*
C2	0.0108 (3)	−0.1346 (10)	0.7998 (3)	0.0938 (16)
H2A	−0.0511	−0.2391	0.7881	0.113*
H2B	−0.0331	−0.0277	0.8313	0.113*
C3	0.1333 (3)	−0.1883 (7)	0.8991 (3)	0.0795 (12)
H3A	0.1061	−0.2173	0.9807	0.095*
H3B	0.1732	−0.3005	0.8700	0.095*
C4	0.2366 (3)	−0.0303 (5)	0.9198 (2)	0.0545 (7)
C5	0.2709 (2)	0.0271 (3)	0.7882 (2)	0.0400 (5)
H5	0.3093	−0.0863	0.7567	0.048*
C6	0.3814 (2)	0.1752 (4)	0.7989 (2)	0.0482 (6)
H6A	0.3501	0.2943	0.8272	0.058*
H6B	0.4571	0.1352	0.8616	0.058*
C7	0.4201 (2)	0.1974 (3)	0.6697 (2)	0.0438 (5)
C8	0.3125 (3)	0.2269 (4)	0.5558 (2)	0.0493 (6)
H8	0.2754	0.3536	0.5590	0.059*
C9	0.2037 (2)	0.0820 (4)	0.5517 (2)	0.0468 (6)
H9A	0.2377	−0.0411	0.5347	0.056*
H9B	0.1317	0.1120	0.4820	0.056*
C10	0.1512 (2)	0.0772 (4)	0.6805 (2)	0.0480 (6)
C11	0.5357 (2)	0.1772 (4)	0.6310 (2)	0.0469 (6)
C12	0.5101 (3)	0.1860 (4)	0.4896 (3)	0.0507 (6)
C13	0.6713 (3)	0.1422 (6)	0.7066 (3)	0.0659 (8)
H13A	0.6695	0.1563	0.7970	0.099*
H13B	0.7324	0.2312	0.6812	0.099*
H13C	0.6990	0.0169	0.6901	0.099*
C14	0.0832 (4)	0.2651 (6)	0.7002 (4)	0.0763 (10)
H14A	0.0210	0.2956	0.6237	0.114*
H14B	0.1487	0.3627	0.7171	0.114*
H14C	0.0373	0.2545	0.7720	0.114*
C15	0.1959 (3)	0.1322 (8)	0.9998 (3)	0.0838 (13)
H15A	0.1939	0.0893	1.0859	0.126*
H15B	0.1096	0.1764	0.9613	0.126*
H15C	0.2588	0.2329	1.0025	0.126*
O1	0.35464 (17)	−0.1021 (3)	0.99853 (14)	0.0547 (5)
H1	0.3829	−0.1911	0.9619	0.082*
O2	0.37912 (19)	0.2109 (3)	0.44542 (16)	0.0572 (5)
O3	0.5884 (2)	0.1702 (4)	0.41479 (17)	0.0635 (6)
O4	0.4640 (3)	0.6381 (4)	0.85924 (19)	0.0861 (8)
H4WA	0.4612	0.6284	0.7803	0.103*
H4WB	0.5174	0.5467	0.8853	0.103*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0398 (13)	0.106 (3)	0.0599 (16)	−0.0191 (17)	0.0010 (11)	0.0081 (18)
C2	0.0463 (14)	0.165 (5)	0.0689 (19)	−0.033 (2)	0.0068 (13)	0.020 (3)
C3	0.0572 (17)	0.123 (3)	0.0595 (16)	−0.025 (2)	0.0128 (13)	0.025 (2)
C4	0.0433 (13)	0.0820 (19)	0.0394 (12)	0.0026 (13)	0.0106 (9)	0.0026 (14)
C5	0.0330 (11)	0.0499 (13)	0.0371 (11)	0.0018 (9)	0.0065 (8)	−0.0020 (9)
C6	0.0447 (12)	0.0580 (14)	0.0414 (11)	−0.0076 (12)	0.0057 (9)	−0.0093 (12)
C7	0.0467 (12)	0.0426 (12)	0.0412 (11)	−0.0065 (10)	0.0054 (9)	−0.0028 (10)
C8	0.0525 (13)	0.0519 (13)	0.0432 (12)	0.0018 (11)	0.0072 (10)	0.0079 (11)
C9	0.0416 (12)	0.0578 (14)	0.0384 (11)	0.0031 (11)	−0.0006 (9)	0.0050 (11)
C10	0.0352 (11)	0.0638 (15)	0.0433 (12)	0.0049 (12)	0.0022 (9)	0.0014 (12)
C11	0.0474 (12)	0.0495 (13)	0.0441 (12)	−0.0106 (11)	0.0090 (9)	−0.0033 (11)
C12	0.0594 (14)	0.0468 (13)	0.0481 (12)	−0.0101 (12)	0.0152 (10)	0.0021 (12)
C13	0.0443 (13)	0.094 (2)	0.0591 (15)	−0.0076 (16)	0.0085 (11)	−0.0161 (17)
C14	0.0619 (18)	0.095 (3)	0.0706 (19)	0.0369 (19)	0.0087 (14)	0.0012 (18)
C15	0.0711 (19)	0.135 (4)	0.0500 (15)	0.036 (2)	0.0229 (13)	−0.010 (2)
O1	0.0528 (10)	0.0745 (13)	0.0355 (8)	0.0038 (9)	0.0039 (7)	0.0017 (8)
O2	0.0614 (11)	0.0679 (12)	0.0431 (9)	−0.0022 (10)	0.0112 (7)	0.0131 (9)
O3	0.0697 (12)	0.0720 (13)	0.0536 (10)	−0.0126 (11)	0.0248 (9)	0.0002 (11)
O4	0.1200 (19)	0.0856 (18)	0.0479 (10)	0.0426 (17)	0.0013 (11)	−0.0041 (11)

Geometric parameters (Å, º)

C1—C2	1.515 (4)	C8—C9	1.512 (4)
C1—C10	1.541 (4)	C8—H8	0.9800
C1—H1A	0.9700	C9—C10	1.545 (3)
C1—H1B	0.9700	C9—H9A	0.9700
C2—C3	1.536 (5)	C9—H9B	0.9700
C2—H2A	0.9700	C10—C14	1.537 (4)
C2—H2B	0.9700	C11—C12	1.468 (4)
C3—C4	1.532 (5)	C11—C13	1.497 (4)
C3—H3A	0.9700	C12—O3	1.223 (3)
C3—H3B	0.9700	C12—O2	1.354 (4)
C4—O1	1.436 (3)	C13—H13A	0.9600
C4—C15	1.530 (5)	C13—H13B	0.9600
C4—C5	1.542 (3)	C13—H13C	0.9600
C5—C6	1.536 (3)	C14—H14A	0.9600
C5—C10	1.559 (3)	C14—H14B	0.9600
C5—H5	0.9800	C14—H14C	0.9600
C6—C7	1.490 (3)	C15—H15A	0.9600
C6—H6A	0.9700	C15—H15B	0.9600
C6—H6B	0.9700	C15—H15C	0.9600
C7—C11	1.325 (3)	O1—H1	0.8200
C7—C8	1.496 (3)	O4—H4WA	0.8291
C8—O2	1.451 (3)	O4—H4WB	0.8628
C2—C1—C10	113.7 (3)	O2—C8—H8	109.8
C2—C1—H1A	108.8	C7—C8—H8	109.8
C10—C1—H1A	108.8	C9—C8—H8	109.8
C2—C1—H1B	108.8	C8—C9—C10	110.9 (2)
C10—C1—H1B	108.8	C8—C9—H9A	109.5
H1A—C1—H1B	107.7	C10—C9—H9A	109.5
C1—C2—C3	110.4 (2)	C8—C9—H9B	109.5
C1—C2—H2A	109.6	C10—C9—H9B	109.5
C3—C2—H2A	109.6	H9A—C9—H9B	108.0
C1—C2—H2B	109.6	C14—C10—C1	110.2 (2)
C3—C2—H2B	109.6	C14—C10—C9	109.5 (2)
H2A—C2—H2B	108.1	C1—C10—C9	107.3 (2)
C4—C3—C2	112.2 (4)	C14—C10—C5	114.7 (2)
C4—C3—H3A	109.2	C1—C10—C5	107.8 (2)
C2—C3—H3A	109.2	C9—C10—C5	107.04 (18)
C4—C3—H3B	109.2	C7—C11—C12	107.2 (2)
C2—C3—H3B	109.2	C7—C11—C13	130.6 (2)
H3A—C3—H3B	107.9	C12—C11—C13	122.1 (2)
O1—C4—C15	103.5 (2)	O3—C12—O2	120.9 (3)
O1—C4—C3	108.3 (3)	O3—C12—C11	128.9 (3)
C15—C4—C3	112.5 (3)	O2—C12—C11	110.2 (2)
O1—C4—C5	108.18 (19)	C11—C13—H13A	109.4
C15—C4—C5	114.9 (3)	C11—C13—H13B	109.4
C3—C4—C5	109.1 (2)	H13A—C13—H13B	109.5
C6—C5—C4	113.3 (2)	C11—C13—H13C	109.5
C6—C5—C10	112.0 (2)	H13A—C13—H13C	109.5
C4—C5—C10	116.10 (19)	H13B—C13—H13C	109.5
C6—C5—H5	104.7	C10—C14—H14A	109.5
C4—C5—H5	104.7	C10—C14—H14B	109.5
C10—C5—H5	104.7	H14A—C14—H14B	109.5
C7—C6—C5	108.42 (18)	C10—C14—H14C	109.5
C7—C6—H6A	110.0	H14A—C14—H14C	109.5
C5—C6—H6A	110.0	H14B—C14—H14C	109.5
C7—C6—H6B	110.0	C4—C15—H15A	109.5
C5—C6—H6B	110.0	C4—C15—H15B	109.5
H6A—C6—H6B	108.4	H15A—C15—H15B	109.5
C11—C7—C6	131.6 (2)	C4—C15—H15C	109.5
C11—C7—C8	110.0 (2)	H15A—C15—H15C	109.5
C6—C7—C8	118.0 (2)	H15B—C15—H15C	109.5
O2—C8—C7	104.3 (2)	C4—O1—H1	109.5
O2—C8—C9	111.8 (2)	C12—O2—C8	108.18 (19)
C7—C8—C9	111.4 (2)	H4WA—O4—H4WB	99.5
C10—C1—C2—C3	−58.1 (6)	C2—C1—C10—C5	53.2 (4)
C1—C2—C3—C4	57.9 (5)	C8—C9—C10—C14	65.4 (3)
C2—C3—C4—O1	−171.6 (3)	C8—C9—C10—C1	−175.0 (2)
C2—C3—C4—C15	74.7 (3)	C8—C9—C10—C5	−59.5 (3)
C2—C3—C4—C5	−54.1 (4)	C6—C5—C10—C14	−60.4 (3)
O1—C4—C5—C6	−58.2 (3)	C4—C5—C10—C14	71.8 (3)
C15—C4—C5—C6	56.8 (3)	C6—C5—C10—C1	176.4 (2)
C3—C4—C5—C6	−175.8 (2)	C4—C5—C10—C1	−51.3 (3)
O1—C4—C5—C10	170.1 (2)	C6—C5—C10—C9	61.3 (3)
C15—C4—C5—C10	−74.9 (3)	C4—C5—C10—C9	−166.4 (2)
C3—C4—C5—C10	52.6 (3)	C6—C7—C11—C12	170.7 (3)
C4—C5—C6—C7	171.3 (2)	C8—C7—C11—C12	−1.8 (3)
C10—C5—C6—C7	−55.0 (3)	C6—C7—C11—C13	−6.6 (5)
C5—C6—C7—C11	−122.4 (3)	C8—C7—C11—C13	−179.0 (3)
C5—C6—C7—C8	49.6 (3)	C7—C11—C12—O3	−178.5 (3)
C11—C7—C8—O2	3.0 (3)	C13—C11—C12—O3	−1.0 (5)
C6—C7—C8—O2	−170.6 (2)	C7—C11—C12—O2	−0.1 (3)
C11—C7—C8—C9	123.7 (2)	C13—C11—C12—O2	177.4 (3)
C6—C7—C8—C9	−49.9 (3)	O3—C12—O2—C8	−179.4 (3)
O2—C8—C9—C10	169.80 (19)	C11—C12—O2—C8	2.1 (3)
C7—C8—C9—C10	53.6 (3)	C7—C8—O2—C12	−3.0 (3)
C2—C1—C10—C14	−72.7 (4)	C9—C8—O2—C12	−123.5 (2)
C2—C1—C10—C9	168.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4i	0.98	2.63	3.407 (3)	136
C8—H8···O3ii	0.98	2.64	3.308 (4)	126
O1—H1···O4i	0.82	1.91	2.718 (3)	169
O4—H4WA···O3ii	0.83	2.05	2.850 (3)	162
O4—H4WB···O1iii	0.86	1.94	2.764 (3)	159

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y+1/2, −z+1; (iii) −x+1, y+1/2, −z+2.