Trichodermaerin: a diterpene lactone from Trichoderma asperellum.

The title compound, C20H28O3, known as 'trichodermaerin' [systematic name: (4E)-4,9,15,16,16-penta-methyl-6-oxa-tetra-cyclo-[10.3.1.0(1,10).0(5,9)]hexa-dec-4-ene-7,13-dione], is a diterpene lactone which was isolated from Trichoderma asperellum. The structure has a tetra-cycic 6-5-7-5 ring system, with the cyclo-hexa-none ring adopting a twisted half-chair conformation and the cyclo-pentane ring adopting a half-chair conformation, whereas the cyclo-heptene and tetra-hydro-furan-anone rings are in chair and envelope (with the methyl-substituted C atom as the flap) conformations, respectively. The three-dimensional architecture is stabilized by C-H⋯O inter-actions.

Related literature

For standard bond-length data, see: Allen et al. (1987 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For background to Trichoderma and diterpene lactones, see, for example: De los Santos-Villalobos et al. (2011 ▶); Evidente et al. (2006 ▶); Hajieghrari et al. (2008 ▶); Kumar et al. (2012 ▶); Vinale (2009 ▶); Xie et al. (2013 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C20H28O3

M = 316.42

Monoclinic,

a = 9.1703 (4) Å

b = 10.2234 (5) Å

c = 9.2681 (4) Å

β = 108.539 (1)°

V = 823.81 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.47 × 0.28 × 0.17 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.962, T max = 0.986

17364 measured reflections

2517 independent reflections

2492 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.069

S = 1.06

2517 reflections

213 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.16 e Å−3

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, PLATON (Spek, 2009 ▶), Mercury (Macrae et al., 2006 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814004632/hb7180sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814004632/hb7180Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814004632/hb7180Isup3.cml

CCDC reference: 989255

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

C20H28O3	F(000) = 344
Mr = 316.42	Dx = 1.276 Mg m−3
Monoclinic, P21	Melting point = 484.05–484.95 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.1703 (4) Å	Cell parameters from 2517 reflections
b = 10.2234 (5) Å	θ = 2.3–30.0°
c = 9.2681 (4) Å	µ = 0.08 mm−1
β = 108.539 (1)°	T = 100 K
V = 823.81 (6) Å3	Block, colorless
Z = 2	0.47 × 0.28 × 0.17 mm

Bruker APEX DUO CCD area-detector diffractometer	2517 independent reflections
Radiation source: sealed tube	2492 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.962, Tmax = 0.986	k = −14→14
17364 measured reflections	l = −13→12

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0476P)2 + 0.0833P] where P = (Fo2 + 2Fc2)/3
2517 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 0.29 e Å−3
1 restraint	Δρmin = −0.16 e Å−3

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	0.56994 (9)	0.42031 (8)	0.42963 (9)	0.01666 (16)
O2	0.36991 (11)	0.48960 (10)	0.49811 (11)	0.0247 (2)
O3	0.76108 (11)	1.06399 (9)	0.03459 (10)	0.02325 (19)
C1	0.67439 (12)	0.47448 (10)	0.36106 (11)	0.01291 (18)
C2	0.46151 (13)	0.51131 (11)	0.43292 (12)	0.01624 (19)
C3	0.47893 (11)	0.63000 (11)	0.34415 (12)	0.01470 (19)
H3A	0.4634	0.7112	0.3955	0.018*
H3B	0.4043	0.6281	0.2400	0.018*
C4	0.64611 (11)	0.62098 (10)	0.33997 (11)	0.01189 (17)
C5	0.64570 (11)	0.66703 (10)	0.18078 (11)	0.01136 (17)
H5A	0.5761	0.6033	0.1095	0.014*
C6	0.79247 (11)	0.66867 (11)	0.13020 (11)	0.01212 (17)
C7	0.92305 (11)	0.75723 (11)	0.23495 (11)	0.01437 (19)
H7A	0.9311	0.7310	0.3412	0.017*
C8	0.88414 (13)	0.90599 (12)	0.22599 (13)	0.0189 (2)
H8A	0.8515	0.9288	0.3149	0.023*
H8B	0.9798	0.9552	0.2359	0.023*
C9	0.76116 (13)	0.95343 (12)	0.08374 (12)	0.0166 (2)
C10	0.63987 (12)	0.85336 (11)	0.01091 (11)	0.01396 (19)
H10A	0.5598	0.8898	−0.0805	0.017*
C11	0.56749 (12)	0.80094 (11)	0.12984 (12)	0.01427 (19)
H11A	0.5880	0.8615	0.2174	0.017*
H11B	0.4549	0.7904	0.0837	0.017*
C12	0.72306 (12)	0.73384 (11)	−0.03161 (11)	0.01303 (18)
C13	0.84953 (12)	0.52859 (11)	0.12202 (12)	0.0158 (2)
H13A	0.9357	0.5320	0.0793	0.019*
H13B	0.7653	0.4781	0.0501	0.019*
C14	0.90411 (12)	0.45392 (12)	0.27425 (13)	0.0176 (2)
H14A	0.9707	0.3809	0.2633	0.021*
H14B	0.9686	0.5138	0.3528	0.021*
C15	0.77981 (11)	0.39824 (11)	0.33248 (11)	0.01390 (19)
C16	0.75106 (12)	0.69002 (12)	0.48303 (12)	0.0160 (2)
H16A	0.7178	0.6679	0.5706	0.024*
H16B	0.7446	0.7849	0.4672	0.024*
H16C	0.8575	0.6612	0.5023	0.024*
C17	1.08590 (12)	0.73508 (14)	0.22352 (14)	0.0221 (2)
H17A	1.1588	0.7943	0.2938	0.033*
H17B	1.0848	0.7526	0.1192	0.033*
H17C	1.1173	0.6443	0.2503	0.033*
C18	0.84033 (13)	0.77677 (12)	−0.10901 (12)	0.0170 (2)
H18A	0.7866	0.8195	−0.2060	0.026*
H18B	0.8958	0.7000	−0.1277	0.026*
H18C	0.9136	0.8382	−0.0428	0.026*
C19	0.60412 (13)	0.64867 (12)	−0.14867 (12)	0.0176 (2)
H19A	0.5600	0.6985	−0.2429	0.026*
H19B	0.5221	0.6234	−0.1074	0.026*
H19C	0.6546	0.5699	−0.1702	0.026*
C20	0.78631 (13)	0.25306 (11)	0.36025 (13)	0.0175 (2)
H20A	0.7042	0.2277	0.4012	0.026*
H20B	0.8863	0.2300	0.4334	0.026*
H20C	0.7727	0.2069	0.2642	0.026*

	U11	U22	U33	U12	U13	U23
O1	0.0190 (3)	0.0147 (4)	0.0198 (4)	0.0004 (3)	0.0111 (3)	0.0019 (3)
O2	0.0280 (4)	0.0209 (4)	0.0337 (5)	−0.0020 (4)	0.0217 (4)	0.0015 (4)
O3	0.0322 (5)	0.0150 (4)	0.0242 (4)	−0.0030 (3)	0.0112 (3)	0.0008 (3)
C1	0.0145 (4)	0.0132 (4)	0.0119 (4)	0.0001 (3)	0.0052 (3)	0.0008 (3)
C2	0.0177 (4)	0.0148 (5)	0.0181 (4)	−0.0008 (4)	0.0084 (4)	−0.0013 (4)
C3	0.0138 (4)	0.0154 (5)	0.0172 (4)	0.0013 (4)	0.0082 (3)	0.0015 (4)
C4	0.0125 (4)	0.0122 (4)	0.0123 (4)	0.0010 (3)	0.0058 (3)	0.0003 (3)
C5	0.0112 (4)	0.0117 (4)	0.0120 (4)	0.0013 (3)	0.0049 (3)	0.0006 (3)
C6	0.0116 (4)	0.0140 (4)	0.0119 (4)	0.0012 (3)	0.0053 (3)	0.0002 (3)
C7	0.0114 (4)	0.0176 (5)	0.0136 (4)	−0.0012 (4)	0.0033 (3)	−0.0001 (4)
C8	0.0185 (5)	0.0187 (5)	0.0180 (5)	−0.0035 (4)	0.0035 (4)	−0.0027 (4)
C9	0.0203 (5)	0.0154 (5)	0.0164 (4)	−0.0006 (4)	0.0088 (4)	−0.0014 (4)
C10	0.0146 (4)	0.0135 (5)	0.0141 (4)	0.0009 (3)	0.0050 (3)	0.0018 (4)
C11	0.0145 (4)	0.0137 (5)	0.0160 (4)	0.0036 (3)	0.0068 (3)	0.0028 (4)
C12	0.0143 (4)	0.0135 (4)	0.0115 (4)	−0.0010 (3)	0.0045 (3)	0.0000 (3)
C13	0.0182 (4)	0.0152 (5)	0.0168 (4)	0.0040 (4)	0.0096 (4)	0.0010 (4)
C14	0.0156 (4)	0.0182 (5)	0.0211 (5)	0.0057 (4)	0.0088 (4)	0.0051 (4)
C15	0.0149 (4)	0.0138 (4)	0.0128 (4)	0.0023 (4)	0.0041 (3)	0.0012 (4)
C16	0.0183 (4)	0.0171 (5)	0.0128 (4)	−0.0020 (4)	0.0053 (3)	−0.0029 (4)
C17	0.0122 (4)	0.0313 (6)	0.0234 (5)	−0.0006 (4)	0.0066 (4)	0.0023 (5)
C18	0.0192 (4)	0.0198 (5)	0.0144 (4)	−0.0029 (4)	0.0085 (3)	0.0001 (4)
C19	0.0197 (4)	0.0190 (5)	0.0131 (4)	−0.0043 (4)	0.0038 (3)	−0.0013 (4)
C20	0.0191 (5)	0.0131 (5)	0.0184 (5)	0.0033 (4)	0.0033 (4)	0.0005 (4)

O1—C2	1.3691 (14)	C10—H10A	1.0000
O1—C1	1.4195 (12)	C11—H11A	0.9900
O2—C2	1.2012 (14)	C11—H11B	0.9900
O3—C9	1.2186 (15)	C12—C18	1.5343 (14)
C1—C15	1.3323 (14)	C12—C19	1.5403 (15)
C1—C4	1.5220 (15)	C13—C14	1.5410 (15)
C2—C3	1.5027 (16)	C13—H13A	0.9900
C3—C4	1.5486 (14)	C13—H13B	0.9900
C3—H3A	0.9900	C14—C15	1.5185 (15)
C3—H3B	0.9900	C14—H14A	0.9900
C4—C16	1.5398 (14)	C14—H14B	0.9900
C4—C5	1.5476 (14)	C15—C20	1.5043 (16)
C5—C11	1.5480 (14)	C16—H16A	0.9800
C5—C6	1.5597 (13)	C16—H16B	0.9800
C5—H5A	1.0000	C16—H16C	0.9800
C6—C13	1.5349 (15)	C17—H17A	0.9800
C6—C7	1.5674 (14)	C17—H17B	0.9800
C6—C12	1.5783 (14)	C17—H17C	0.9800
C7—C17	1.5470 (15)	C18—H18A	0.9800
C7—C8	1.5582 (17)	C18—H18B	0.9800
C7—H7A	1.0000	C18—H18C	0.9800
C8—C9	1.5165 (16)	C19—H19A	0.9800
C8—H8A	0.9900	C19—H19B	0.9800
C8—H8B	0.9900	C19—H19C	0.9800
C9—C10	1.5040 (15)	C20—H20A	0.9800
C10—C11	1.5517 (14)	C20—H20B	0.9800
C10—C12	1.5561 (15)	C20—H20C	0.9800
C2—O1—C1	110.06 (9)	C5—C11—H11B	110.7
C15—C1—O1	119.76 (10)	C10—C11—H11B	110.7
C15—C1—C4	130.91 (10)	H11A—C11—H11B	108.8
O1—C1—C4	109.25 (9)	C18—C12—C19	106.08 (8)
O2—C2—O1	120.97 (11)	C18—C12—C10	111.51 (9)
O2—C2—C3	129.62 (11)	C19—C12—C10	109.14 (8)
O1—C2—C3	109.40 (9)	C18—C12—C6	115.73 (8)
C2—C3—C4	104.12 (9)	C19—C12—C6	114.33 (9)
C2—C3—H3A	110.9	C10—C12—C6	99.96 (8)
C4—C3—H3A	110.9	C6—C13—C14	115.69 (9)
C2—C3—H3B	110.9	C6—C13—H13A	108.4
C4—C3—H3B	110.9	C14—C13—H13A	108.4
H3A—C3—H3B	109.0	C6—C13—H13B	108.4
C1—C4—C16	107.83 (9)	C14—C13—H13B	108.4
C1—C4—C5	111.74 (8)	H13A—C13—H13B	107.4
C16—C4—C5	119.53 (9)	C15—C14—C13	116.69 (9)
C1—C4—C3	100.66 (8)	C15—C14—H14A	108.1
C16—C4—C3	107.69 (8)	C13—C14—H14A	108.1
C5—C4—C3	107.66 (8)	C15—C14—H14B	108.1
C4—C5—C11	114.85 (8)	C13—C14—H14B	108.1
C4—C5—C6	123.30 (8)	H14A—C14—H14B	107.3
C11—C5—C6	105.02 (8)	C1—C15—C20	122.34 (10)
C4—C5—H5A	103.8	C1—C15—C14	121.70 (10)
C11—C5—H5A	103.8	C20—C15—C14	115.93 (9)
C6—C5—H5A	103.8	C4—C16—H16A	109.5
C13—C6—C5	110.19 (8)	C4—C16—H16B	109.5
C13—C6—C7	111.36 (8)	H16A—C16—H16B	109.5
C5—C6—C7	112.48 (8)	C4—C16—H16C	109.5
C13—C6—C12	112.81 (8)	H16A—C16—H16C	109.5
C5—C6—C12	99.45 (8)	H16B—C16—H16C	109.5
C7—C6—C12	110.03 (8)	C7—C17—H17A	109.5
C17—C7—C8	110.42 (9)	C7—C17—H17B	109.5
C17—C7—C6	115.91 (9)	H17A—C17—H17B	109.5
C8—C7—C6	114.45 (8)	C7—C17—H17C	109.5
C17—C7—H7A	104.9	H17A—C17—H17C	109.5
C8—C7—H7A	104.9	H17B—C17—H17C	109.5
C6—C7—H7A	104.9	C12—C18—H18A	109.5
C9—C8—C7	116.93 (9)	C12—C18—H18B	109.5
C9—C8—H8A	108.1	H18A—C18—H18B	109.5
C7—C8—H8A	108.1	C12—C18—H18C	109.5
C9—C8—H8B	108.1	H18A—C18—H18C	109.5
C7—C8—H8B	108.1	H18B—C18—H18C	109.5
H8A—C8—H8B	107.3	C12—C19—H19A	109.5
O3—C9—C10	123.42 (10)	C12—C19—H19B	109.5
O3—C9—C8	122.25 (11)	H19A—C19—H19B	109.5
C10—C9—C8	114.33 (10)	C12—C19—H19C	109.5
C9—C10—C11	109.78 (9)	H19A—C19—H19C	109.5
C9—C10—C12	107.20 (8)	H19B—C19—H19C	109.5
C11—C10—C12	105.28 (8)	C15—C20—H20A	109.5
C9—C10—H10A	111.4	C15—C20—H20B	109.5
C11—C10—H10A	111.4	H20A—C20—H20B	109.5
C12—C10—H10A	111.4	C15—C20—H20C	109.5
C5—C11—C10	105.11 (8)	H20A—C20—H20C	109.5
C5—C11—H11A	110.7	H20B—C20—H20C	109.5
C10—C11—H11A	110.7
C2—O1—C1—C15	−173.20 (10)	C7—C8—C9—O3	−150.53 (11)
C2—O1—C1—C4	9.64 (11)	C7—C8—C9—C10	30.16 (14)
C1—O1—C2—O2	−173.44 (10)	O3—C9—C10—C11	−124.95 (11)
C1—O1—C2—C3	7.53 (12)	C8—C9—C10—C11	54.36 (12)
O2—C2—C3—C4	160.06 (12)	O3—C9—C10—C12	121.19 (12)
O1—C2—C3—C4	−21.02 (11)	C8—C9—C10—C12	−59.51 (11)
C15—C1—C4—C16	−85.57 (13)	C4—C5—C11—C10	156.08 (8)
O1—C1—C4—C16	91.17 (9)	C6—C5—C11—C10	17.42 (10)
C15—C1—C4—C5	47.72 (15)	C9—C10—C11—C5	−100.89 (10)
O1—C1—C4—C5	−135.54 (8)	C12—C10—C11—C5	14.19 (10)
C15—C1—C4—C3	161.77 (11)	C9—C10—C12—C18	−45.64 (11)
O1—C1—C4—C3	−21.50 (10)	C11—C10—C12—C18	−162.50 (8)
C2—C3—C4—C1	24.59 (10)	C9—C10—C12—C19	−162.51 (9)
C2—C3—C4—C16	−88.18 (10)	C11—C10—C12—C19	80.63 (10)
C2—C3—C4—C5	141.69 (9)	C9—C10—C12—C6	77.25 (9)
C1—C4—C5—C11	161.08 (8)	C11—C10—C12—C6	−39.61 (9)
C16—C4—C5—C11	−71.71 (12)	C13—C6—C12—C18	−74.27 (11)
C3—C4—C5—C11	51.45 (11)	C5—C6—C12—C18	169.02 (9)
C1—C4—C5—C6	−68.68 (12)	C7—C6—C12—C18	50.76 (12)
C16—C4—C5—C6	58.53 (13)	C13—C6—C12—C19	49.47 (11)
C3—C4—C5—C6	−178.31 (9)	C5—C6—C12—C19	−67.25 (10)
C4—C5—C6—C13	65.63 (12)	C7—C6—C12—C19	174.50 (8)
C11—C5—C6—C13	−160.19 (8)	C13—C6—C12—C10	165.87 (8)
C4—C5—C6—C7	−59.28 (13)	C5—C6—C12—C10	49.15 (9)
C11—C5—C6—C7	74.90 (10)	C7—C6—C12—C10	−69.10 (9)
C4—C5—C6—C12	−175.68 (9)	C5—C6—C13—C14	−64.06 (11)
C11—C5—C6—C12	−41.51 (9)	C7—C6—C13—C14	61.49 (11)
C13—C6—C7—C17	39.01 (12)	C12—C6—C13—C14	−174.21 (9)
C5—C6—C7—C17	163.27 (9)	C6—C13—C14—C15	77.90 (13)
C12—C6—C7—C17	−86.84 (11)	O1—C1—C15—C20	4.36 (15)
C13—C6—C7—C8	169.33 (9)	C4—C1—C15—C20	−179.19 (10)
C5—C6—C7—C8	−66.41 (11)	O1—C1—C15—C14	−173.71 (9)
C12—C6—C7—C8	43.47 (11)	C4—C1—C15—C14	2.75 (17)
C17—C7—C8—C9	110.78 (10)	C13—C14—C15—C1	−59.24 (14)
C6—C7—C8—C9	−22.18 (13)	C13—C14—C15—C20	122.58 (11)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O3i	0.99	2.60	3.5649 (14)	165
C16—H16B···O2ii	0.98	2.41	3.2810 (16)	148
C20—H20C···O3iii	0.98	2.56	3.5292 (15)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O3i	0.99	2.60	3.5649 (14)	165
C16—H16B⋯O2ii	0.98	2.41	3.2810 (16)	148
C20—H20C⋯O3iii	0.98	2.56	3.5292 (15)	173

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